CN111778506B - Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof - Google Patents

Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof Download PDF

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CN111778506B
CN111778506B CN202010390535.XA CN202010390535A CN111778506B CN 111778506 B CN111778506 B CN 111778506B CN 202010390535 A CN202010390535 A CN 202010390535A CN 111778506 B CN111778506 B CN 111778506B
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diamond
boron doped
doped diamond
gradient
dimensional
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CN111778506A (en
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魏秋平
马莉
周科朝
康翱龙
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Central South University
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    • C—CHEMISTRY; METALLURGY
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/04—Casting by dipping
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3732—Diamonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic substrates

Abstract

The invention discloses a gradient boron doped diamond reinforced metal matrix composite material, a preparation method and application thereof, wherein the composite material comprises a gradient boron doped diamond reinforcing body and a metal matrix; the gradient boron doped diamond reinforcement comprises a diamond reinforcement body and a gradient boron doped diamond modification layer arranged on the surface of the diamond reinforcement body. The configuration of the diamond reinforcement comprises one or more of a zero-dimensional particle configuration, a one-dimensional linear configuration, a two-dimensional sheet configuration, and a three-dimensional continuous network skeleton configuration. The coupling of gradient boron doped diamond reinforcing bodies with different dimensions can greatly improve the volume of diamond in the composite material and improve the heat conductivity. In addition, in the gradient boron doped diamond reinforcing body added in the invention, the gradient boron doped diamond modifying layer has a small proportion, the heat conductivity of diamond is not affected, and the wettability with metal can be greatly improved.

Description

Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof
Technical Field
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material and a preparation method and application thereof, belonging to the technical field of preparation of thermal management composite materials.
Background
With the development of information technology and the advent of the 5G age, the pace of interconnection of everything is continuously accelerated, and electronic products are gradually developing towards the directions of intelligence, multifunction, light weight, thinning and the like. In the process of increasingly strong electronic product performance, the volumes of integrated circuit chips and electronic components are continuously reduced, and the continuous improvement of high-density integrated assembly technology leads to rapid increase of power consumption and heating value, so that the heat dissipation requirements of people on thermal management materials are higher and higher. In addition, the rapid development of aerospace and transportation industries is increasingly stringent in terms of the requirement for lightweight materials. Therefore, high thermal conductivity, low thermal expansion coefficient, and light weight are three major core elements that must be considered in developing modern electronic packaging materials.
Diamond is one of the materials with the highest thermal conductivity in nature (2200W/mK at room temperature), and also has a low thermal expansion coefficient (0.86 ppm/K) and a low density (3.52 g/cm 3), is an excellent reinforcement in a thermal management composite material, and can obtain more excellent thermal conductivity while theoretically ensuring the ideal thermal expansion coefficient and low density by compounding the diamond with high-thermal-conductivity metal. However, the thermal conductivity of the diamond metal-based composite material prepared at present is lower, and some of the diamond metal-based composite material is even lower than that of the metal matrix, and the thermal conductivity of the diamond metal-based composite material is lower than that of the metal matrix, so that the metal material and the diamond are in weak combination, and many structural defects and gaps exist on an interface, so that electrons and phonons are scattered at the interface, higher interface thermal resistance is formed, and the improvement of the thermal conductivity of the composite material is limited. Currently, researchers mainly improve interface wettability by strengthening interfaces and reduce interface thermal resistance.
In order to improve the direct interface wettability of diamond and a metal matrix, a concentrated interface modification method is researched, wherein the most common method for improving the interface wettability is diamond surface modification and metal matrix alloying, the diamond surface modification is to add a transition layer to the diamond surface to form carbide, and the interface bonding capability of the modified diamond particles is improved when the modified diamond particles are compounded with the metal matrix; the metal matrix alloying is to add some materials (such as boron, chromium, zirconium and the like) which are easy to form carbide into the metal matrix, and the metal matrix also forms a layer of carbide when being compounded with diamond particles, so that the bonding capability of the metal matrix and the diamond particles is enhanced. Ultimately, both form a carbide transition layer to enhance the interfacial bonding capability of diamond and metallic materials as they are combined. However, the thermal conductivity of the carbide transition layer formed tends to be low, which also severely affects the thermal conductivity of the composite.
Disclosure of Invention
The invention aims to overcome the defects of the prior diamond metal matrix composite interface modification technology, and provides a gradient boron doped diamond reinforced metal matrix composite material, a preparation method and application thereof, wherein a layer of boron doped diamond layer is deposited on the surface of a high-purity diamond layer by a chemical vapor deposition technology, the boron doped diamond layer is gradually increased in boron doping concentration and is compounded with a metal matrix, the thin boron doped diamond layer has little influence on the heat conductivity of diamond, the high heat conductivity of a reinforcement is ensured, and meanwhile, the wettability of the diamond reinforcement and the metal matrix is improved by the gradient boron doping, so that the heat conduction efficiency of the composite material is greatly improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a gradient boron doped diamond reinforced metal matrix composite material, which comprises a gradient boron doped diamond reinforcing body and a metal matrix; the gradient boron doped diamond reinforcing body comprises an undoped diamond reinforcing body and a gradient boron doped diamond modifying layer arranged on the surface of the diamond reinforcing body.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein the configuration of a diamond reinforcing body comprises one or more of a zero-dimensional particle configuration, a one-dimensional linear configuration, a two-dimensional sheet configuration and a three-dimensional continuous network skeleton configuration.
The coupling of the gradient boron doped diamond reinforcing bodies with different dimensions can greatly improve the volume of diamond in the composite material and improve the heat conductivity.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein a diamond reinforcement body with a zero-dimensional particle configuration is pure diamond or natural diamond prepared by a high-temperature high-pressure method; the diamond reinforcing body with one-dimensional linear configuration, two-dimensional sheet-shaped configuration and three-dimensional continuous network skeleton configuration is obtained by depositing a diamond layer on the surface of a substrate with corresponding configuration through chemical vapor deposition.
Preferably, the diamond layer is uniformly deposited on the surface of the substrate by a chemical vapor deposition method, and the thickness is 10-100 mu m, preferably 10-40 mu m
The gradient boron doped diamond reinforced metal matrix composite material is characterized in that a gradient boron doped diamond modified layer is deposited on the surface of a diamond reinforcing body through chemical vapor deposition.
The configuration of the gradient boron doped diamond reinforcement is consistent with the diamond reinforcement.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, which sequentially comprises a boron doped diamond bottom layer, a boron doped diamond middle layer and a boron doped diamond top layer, wherein the boron content of the boron doped diamond bottom layer is increased in a gradient manner from bottom to top; in the boron doped diamond bottom layer, B/C is 3333-8332ppm according to atomic ratio; in the boron doped diamond middle layer, B/C is 9999-15000ppm according to atomic ratio; in the boron doped diamond top layer, B/C is 16665-21665ppm according to atomic ratio.
The gradient boron doped diamond reinforced metal matrix composite material provided by the invention has the advantages that the thickness of the gradient boron doped diamond modified layer is 0.01-20 mu m, and the gradient boron doped diamond modified layer is preferably: 0.5 μm-3 μm.
The gradient boron doped diamond reinforced metal matrix composite material provided by the invention has the advantage that the volume fraction of the gradient boron doped diamond modified layer in the diamond reinforcement is less than or equal to 3%.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein micropores and/or sharp cones are distributed on the surface of a gradient boron doped diamond modified layer.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite, wherein the shape of a one-dimensional linear configuration reinforcement is at least one of a cylindrical shape and a columnar spiral shape, and the outer diameter of linear diamond is 0.05mm-20mm.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite, wherein the shape of a two-dimensional sheet-like configuration is at least one of plane shape, wave shape and curved shape; the through holes arranged on the sheet-shaped configuration are uniformly distributed or randomly distributed; the shape of the through hole of the flaky heat conducting material is at least one selected from a circle, an ellipse and a polygon; the size range of the through hole is 0.5-50mm; the thickness of the flaky heat conducting material is 0.02-50mm.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein a diamond reinforcement with a three-dimensional continuous network skeleton configuration comprises a three-dimensional continuous network metal skeleton and a diamond layer arranged on the surface of the three-dimensional continuous network metal skeleton.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein in a diamond reinforcement body with a three-dimensional continuous network skeleton configuration, the volume fraction of a three-dimensional continuous network metal skeleton is 20-40vol%. In the invention, the volume fraction of the metal framework is smaller, and only the supporting function is realized.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein the metal in a three-dimensional continuous network metal framework is selected from one or more of nickel, copper, titanium, chromium, iron, silicon, aluminum, niobium, tantalum, tungsten, molybdenum and zirconium; the aperture of the three-dimensional continuous network metal framework is 0.01-10mm, the aperture ratio is 40-99%, and the holes are uniformly distributed or randomly distributed.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite, wherein the three-dimensional continuous network diamond reinforcement further comprises a transition layer, and the transition layer is positioned between a three-dimensional continuous network metal framework and a boron doped diamond layer; the transition layer material is selected from one or more of nickel, niobium, tantalum, titanium, cobalt, tungsten, molybdenum and chromium, and the thickness of the transition layer is 0.5-30 mu m.
The inventor finds that the performance of the diamond reinforcing phase can be further improved by introducing the transition layer under the following two conditions, and firstly, when the difference between the metal phase and the diamond in the metal framework is overlarge, the thermal stress of the high-purity diamond layer/metal framework interface can be effectively reduced by introducing the transition layer with proper thermal expansion coefficient. The service performance and the service life of the material are enhanced. And secondly, when the metal phase in the metal framework is unsuitable for diamond nucleation, the introduced transition layer can effectively improve the chemical vapor deposition efficiency, the continuity of the film layer and the combination of the film layer and the metal framework.
In the invention, as long as the thickness of the transition layer can be satisfied and the requirement of good bonding property is met, the preparation method of the transition layer is not limited, for example, one of electroplating, chemical plating, vapor plating, magnetron sputtering, chemical vapor deposition and physical vapor deposition in the prior art can be adopted.
According to the invention, in-situ boron doping is carried out on the surface of the diamond, the boron doping concentration is gradually increased, the wettability of the diamond is improved, the high heat conductivity of the diamond is maintained, and the heat conducting property of the composite material is improved.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, which is prepared by the following steps: placing the diamond reinforcing body in a chemical vapor deposition furnace for three-stage deposition, wherein the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the first-stage deposition; the boron-containing gas accounts for 0.005-0.0075 percent of the total gas mass flow in the furnace; the temperature of the first stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa, the time is 0.5-1.0h; during the second stage deposition, the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace; the second stage deposition temperature of boron-containing gas accounting for 0.015-0.0225% of the total gas mass flow percentage in the furnace is 600-1000 ℃ and the air pressure is 10% 3 -10 4 Pa, the time is 0.5-1.0h, and the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the third-stage deposition; the boron-containing gas accounts for 0.025 to 0.0325 percent of the total mass flow of the gas in the furnace; the temperature of the third stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa; the time is 1.0-2.0h.
Preferably, the method further comprisesCarrying out heat treatment on the gradient boron doped diamond modified layer in an air atmosphere, wherein the heat treatment temperature is 700-1000 ℃ and the treatment time is 30-100min; the pressure in the furnace is 10Pa-10 5 Pa. And (3) through heat treatment, micropores and/or pointed cones are distributed on the surface of the gradient boron doped diamond modified layer, and an activated surface is obtained.
The invention relates to a gradient boron doped diamond reinforced metal matrix composite material, wherein the metal matrix comprises one or more of Al, mg, cu, ag, zn.
The gradient boron doped diamond reinforced metal matrix composite material also contains a small amount of carbide alloy elements which can be formed on the surface of the gradient boron doped diamond reinforced body or in a metal matrix, and the alloy elements are one or more selected from B, si, ti, cr, zr, nb, ta, W, mo.
The carbide alloy elements can be added in a mode of dispersing in molten metal in the preparation process of the metal matrix, and are added on the surface of the gradient boron doped diamond reinforcing body in a mode of electroplating, chemical plating, vapor plating, magnetron sputtering, chemical vapor deposition and physical vapor deposition.
In the invention, when the gradient boron doped diamond reinforcing body with a zero-dimensional particle configuration, a one-dimensional linear configuration and a two-dimensional sheet configuration is adopted, the gradient boron doped diamond reinforcing body with the zero-dimensional particle configuration, the one-dimensional linear configuration and the two-dimensional sheet configuration is only required to be dispersed in molten metal for preparing the gradient boron doped diamond reinforcing body with the zero-dimensional particle configuration, the one-dimensional linear configuration and the two-dimensional sheet configuration, and the gradient boron doped diamond reinforcing body is cooled to obtain the gradient boron doped diamond reinforcing metal-based composite material, or the metal matrix is compounded with the reinforcing body with the one-dimensional or two-dimensional configuration by a vacuum extrusion casting method.
Preferably, the gradient boron doped diamond reinforced metal matrix composite material is characterized in that the configuration of the diamond reinforcement body is a three-dimensional continuous network skeleton configuration and a zero-dimensional particle configuration; wherein the volume fraction of the diamond reinforcing body with the three-dimensional continuous network skeleton structure in the gradient boron doped diamond reinforcing metal matrix composite material is 10-40%, preferably 10-20vol%; the volume fraction of the diamond reinforcing body in the zero-dimensional particle configuration in the gradient boron doped diamond reinforced metal matrix composite is 10-40%, preferably 10-25vol%, and the particle size of the diamond reinforcing body in the zero-dimensional particle configuration is 10-80 μm.
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite, which comprises the following steps:
step one, planting seed crystals on a three-dimensional continuous network metal framework
Placing a three-dimensional continuous network metal framework or a three-dimensional continuous network metal framework provided with a transition layer into a suspension containing nanocrystalline diamond particles, heating to boiling, performing ultrasonic treatment, and drying; obtaining a three-dimensional continuous network metal framework with nano-crystal diamond particles adsorbed on the surface;
step two, depositing a diamond layer
Placing the three-dimensional continuous network metal framework with the nano-crystal diamond particles adsorbed on the surface obtained in the step one into a chemical vapor deposition furnace for diamond layer deposition, wherein the deposition parameters are as follows: the carbon-containing gas accounts for 0.5 to 10.0 percent of the total gas mass flow in the furnace; the deposition temperature is 600-1000 ℃ and the deposition air pressure is 10 3 -10 4 Pa; the deposition time is 12-24 hours;
step three, depositing a gradient boron doped diamond modification layer
Placing the three-dimensional continuous network metal skeleton with the diamond layer deposited in the second step into a chemical vapor deposition furnace, and performing three-stage deposition to obtain a gradient boron doped diamond modified layer, wherein the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the first stage deposition; the boron-containing gas accounts for 0.005-0.0075 percent of the total gas mass flow in the furnace; the temperature of the first stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa, the time is 0.5-1.0h; during the second stage deposition, the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace; the boron-containing gas accounts for 0.015-0.0225% of the total gas mass flow in the furnace, the temperature of the second stage deposition is 600-1000 ℃, and the air pressure is 10% 3 -10 4 Pa, the time is 0.5-1.0h, and the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the third-stage deposition; boron-containing gas occupying furnaceThe mass flow percentage of the total gas in the reactor is 0.025% -0.0325%; the temperature of the third stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa; the time is 1.0-2.0h; etching the boron doped diamond layer at 700-900 ℃ in hydrogen atmosphere after the deposition is completed; obtaining a gradient boron doped diamond reinforcement of a three-dimensional continuous network skeleton configuration;
step four, adding the diamond reinforcing body with zero-dimensional particle configuration
Placing the gradient boron doped diamond reinforcement with the three-dimensional continuous network skeleton configuration obtained in the step three into a suspension of the gradient boron doped diamond reinforcement with the zero-dimensional particle configuration; heating to boiling, ultrasonic treatment, drying to make the gradient boron doped diamond reinforcing body with zero-dimensional grain structure inlaid in the pore space of diamond reinforcing body with three-dimensional continuous network skeleton structure,
Step five, heat treatment
Performing heat treatment on the diamond reinforcement with the three-dimensional continuous network skeleton configuration obtained in the step four in an air atmosphere to obtain an activated gradient boron doped diamond reinforcement;
step six, compounding gradient boron doped diamond reinforcing body and metal matrix
And (3) adopting a pressure infiltration process to infiltrate the metal into the activated gradient boron doped diamond reinforcing body, and cooling to obtain the gradient boron doped diamond reinforced metal matrix composite.
In the actual operation process, the three-dimensional continuous network metal skeleton is subjected to cleaning treatment in advance, acetone and absolute ethyl alcohol are sequentially adopted for ultrasonic cleaning for 10min to remove oil stains and impurities on the surface for standby, and if a transition layer is required to be arranged, then one method of electroplating, chemical plating, vapor deposition, magnetron sputtering, chemical vapor deposition and physical vapor deposition is adopted to prepare an intermediate transition layer on the surface of the substrate, wherein the intermediate transition layer comprises a composite transition layer of one or more of nickel, niobium, tantalum, titanium, cobalt, tungsten, molybdenum and chromium.
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite material, which comprises the following steps of; the mass fraction of the nanocrystalline diamond particles in the suspension containing the nanocrystalline particles is 0.01% -0.05%, and the sizes of the nanocrystalline diamond particles are 10nm-100nm.
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite material, which comprises the following steps of; the ultrasonic vibration treatment time is 5-30min. After the ultrasonic treatment is completed, the material is taken out, washed clean by deionized water and/or absolute ethyl alcohol, and dried.
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite material, which comprises the following steps that in the second step, carbon-containing gas is CH 4 。
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite material.
In the invention, hydrogen is used as both diluent gas and etching gas in the chemical deposition process, and after the deposition is completed, boron-containing gas and carbon-containing gas are closed first and hydrogen is continuously introduced for a period of time to etch graphite phase on the surface of boron doped diamond.
In the actual operation process, when the deposition is required to be carried out on two sides of a planar substrate or on multiple sides of a substrate with a three-dimensional structure, the deposition of the boron doped diamond layer on one side is finished, and then the deposition of other layers is carried out after cooling, washing and drying are carried out.
In the invention, one of solid, gas and liquid boron sources can be selected as the boron source, and gasification treatment is carried out first when the solid and liquid boron sources are selected.
Preferably, the boron-containing gas is B 2 H 6 The carbon-containing gas is CH 4 。
Preferably, in the preparation method of the gradient boron doped diamond enhanced metal matrix composite material, in the third step, when the first section is deposited, the gas flow rate ratio is hydrogen: carbon-containing gas: boron-containing gas = 98sccm:2sccm:0.1-0.25sccm; during the second stage deposition, the gas flow rate ratio is hydrogen: carbon-containing gas: boron-containing gas = 98sccm:2sccm:0.3-0.45sccm; during the third stage deposition, the gas flow rate ratio is hydrogen: carbon-containing gas: boron-containing gas = 98sccm:2sccm:0.5-0.65sccm.
In the fourth step, in the suspension of the gradient diamond reinforcing body containing the zero-dimensional particle configuration, the mass fraction of the gradient diamond reinforcing body containing the zero-dimensional particle configuration is 0.01% -0.1%, and the size of the gradient diamond reinforcing body containing the zero-dimensional particle configuration is 10 mu m-80 mu m;
the invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite, which comprises the following steps of; the pressure in the furnace is 10Pa-10 5 Pa。
According to the invention, the boron doped diamond layer is uniformly deposited on the surface of the diamond layer by a chemical vapor deposition method to form the boron doped diamond reinforcement, and after the deposition, the surface of the diamond is subjected to heat treatment, so that the surface of the diamond is activated, and at the moment, the interface bonding capability of the foam diamond is more excellent when the foam diamond is compounded with a metal matrix.
The invention relates to a preparation method of a gradient boron doped diamond reinforced metal matrix composite, which comprises the following steps: placing metal above the activated gradient boron doped diamond reinforcing body, heating to melt the metal, preserving heat for 20-40 min after the metal is melted, simultaneously applying pressure of 3-10MPa in the heat preservation process, and then cooling.
The ultra-thin boron doped diamond layer has little influence on the intrinsic heat conductivity of the diamond reinforcing body, ensures the high heat conductivity of the diamond reinforcing body, and ensures the high wettability of the reinforcing body and the matrix and the heat conductivity of the composite material only by adding few extra carbides when carbide modification is carried out on the surface of a metal matrix or the reinforcing body.
The invention relates to an application of a gradient boron doped diamond reinforced metal matrix composite, which is used for an electronic packaging material.
Advantageous effects
The composite material provided by the invention contains reinforcements with different dimensions, so that the volume of diamond can be increased together, the heat conductivity is improved, and especially when the configuration of the diamond reinforcements is a three-dimensional continuous network skeleton configuration and a zero-dimensional particle configuration, the effect is more excellent, on one hand, the thermal expansion coefficient of the composite material can be effectively reduced due to the fact that the zero-dimensional diamond particles and the diamond with a three-dimensional network structure can be effectively reduced, on the other hand, the distribution of the diamond with the communicated three-dimensional network structure in a matrix can have more efficient heat conduction efficiency than that of a two-dimensional structure, and meanwhile, the volume of diamond in the composite material is increased due to the addition of the zero-dimensional particles, and the heat conductivity of the composite material is greatly improved.
In addition, the reinforced phase formed by carrying out gradient boron doped diamond deposition on the surface of the pure diamond layer is deposited with three sections of different boron contents during the deposition of the boron doped diamond, wherein the bottom layer of the boron doped diamond contacted with the high purity diamond layer is used as the reinforced layer, the high purity of the diamond is reserved through the doping of a small amount of boron, and the diamond has compact and uniform crystal grains and few defects and higher heat conductivity due to the high purity of the diamond, and the top layer of the boron doped diamond is compounded with a metal matrix, so that the diamond and the metal matrix have better wettability and interface bonding capability due to the proper boron doping amount, and the heat conducting property of the composite material is greatly enhanced.
Meanwhile, when the boron doped diamond layer is deposited on the high-purity diamond layer to form a diamond reinforcing body, the boron doped diamond layer is subjected to heat treatment, so that micropores or sharp cones are uniformly distributed on the surface of the boron doped diamond. The surface microstructure can greatly improve the interfacial bonding capability of the diamond reinforcing body and the metal matrix.
In a word, through the operation, the boron doped diamond enhanced metal matrix composite material has the characteristics of high heat conductivity and low thermal expansion coefficient, and can meet the requirements of heat management materials with more and more strict requirements on the heat conductivity and the thermal expansion coefficient.
Detailed Description
Example 1 boron doped diamond reinforced copper matrix composite (reinforcement configuration is three dimensional network configuration)
(1) Pretreatment of a substrate: in this example, a three-dimensional network configuration uses copper foam with a pore size of 0.25mm, a diameter of 12.3mm, and a thickness of 2.0mm as a substrate. Firstly, cleaning a copper foil substrate with a three-dimensional network structure according to the step (2), and then depositing a chromium film with the thickness of 50nm on the surface of a copper skeleton with the three-dimensional network structure by adopting a magnetron sputtering technology according to the step (2) to serve as an intermediate transition layer.
(2) And (3) placing the nanocrystalline and the metal skeleton substrate in the step (1) in a beaker, mixing, heating to boiling, then placing in high-power ultrasonic waves for oscillation, taking out the three-dimensional continuous network skeleton substrate after uniform dispersion, and drying to obtain the three-dimensional continuous network skeleton substrate with a large number of nanocrystalline embedded in meshes. Wherein, in the suspension containing nanocrystalline diamond particles, the mass fraction of the diamond particles is 0.03%, the ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is completed, the foam diamond is taken out, and the foam diamond is washed clean by deionized water and/or absolute ethyl alcohol and then dried.
(3) And then adopting chemical vapor deposition to deposit a diamond film on the copper substrate with the three-dimensional configuration adsorbed with nano diamond particles, and adopting a diamond deposition process: and (3) adopting hot filament CVD to deposit three-dimensional continuous network diamond on the surface of the foam matrix, wherein the hot filament is a straight tungsten filament with the thickness of 0.5mm, completely covering the straight filament above the substrate, then placing the pretreated substrate into a cavity of an HFCVD device, and adjusting the hot filament-base spacing (8 mm). After the installation, closing the cabin door for vacuumizing, then introducing hydrogen and methane according to the air source concentration ratio set by experiments, closing the air extraction valve after the reaction air sources are uniformly mixed, and adjusting the air pressure in the cavity to be set pressure by the micro-adjustment valve. Then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, meanwhile, the air pressure in the deposition chamber needs to be observed, after the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, the CH needs to be closed 4 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: gas ratio H 2 :CH 4 Deposition time was 14h =98 sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the diamond layer is 10-3 0μm。
(4) The diamond surface is doped with boron by adopting hot filament vapor deposition, and the hot filament isThe straight wire is completely covered over the substrate, and then the pretreated substrate is put into the cavity of the HFCVD equipment, and the distance between the hot wire and the base (8 mm) is adjusted. After the installation, closing the cabin door, vacuumizing, then introducing hydrogen, methane and borane (diborane used in the experiment is mixed gas of B2H26:H2=5:95) according to the concentration ratio of the air source set in the experiment, and after the reaction air sources are uniformly mixed, closing the air extraction valve, and regulating the air pressure in the cavity to be set pressure by the fine adjustment valve. And then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, the air pressure in the deposition chamber is required to be observed, if the air pressure is changed, the air pressure is required to be continuously regulated by the fine-tuning valve, and finally the boron-doped diamond film is deposited. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, CH needs to be closed 4 And B 2 H 6 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are as follows: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate is higher than H 2 :B 2 H 6 :CH 4 The deposition time was 1H, the second stage gas flow rate ratio H, =98 sccm:0.2sccm:2.0sccm 2 :B 2 H 6 :CH 4 98sccm 0.4sccm 2.0sccm, deposition pressure 3kPa, deposition temperature 850 ℃, deposition time 1H, third stage, deposition pressure 3kPa, deposition temperature 850 ℃, gas flow rate ratio H 2 :B 2 H 6 :CH 4 The deposition time was 2h =98 sccm:0.6sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 mu m.
(5) The obtained high-performance boron-doped diamond film material is put into a vacuum tube furnace for heat treatment, the two ends are not sealed, and the pressure is 10 5 Pa, setting the temperature to 800 ℃, and keeping for 60min.
(6) And (3) arranging the foam diamond reinforcements obtained in the step (5) in a mould in an oriented and uniform way, and placing copper-zirconium alloy which is 2 times of the skeleton volume of the high-conductivity continuous diamond reinforcement array above the skeleton, wherein the mass content of zirconium is 5wt%. Then placing the grinding tool into an infiltration device, setting the heating temperature to 1350 ℃, setting the heating rate to 12 ℃ per minute, finally preserving the heat at 1350 ℃ for 30 minutes, preserving the heat at the pressure of 5MPa, naturally cooling to room temperature, taking out the sample, removing surface metal by polishing, and cleaning to obtain the composite material.
(7) The prepared composite material has heat conductivity which is found to reach 687W/mK by testing the heat conductivity through a laser flash method.
Example 2 boron doped Diamond enhanced copper matrix composite (reinforcement configuration is the coupling of three dimensional network configuration with zero dimensional particle configuration)
(1) Pretreatment of a substrate: in this example, a three-dimensional network configuration was formed using copper foam with a pore size of 0.25mm, a diameter of 12.3mm, and a thickness of 2.0mm as a substrate, and a zero-dimensional configuration was formed of natural diamond particles with an average size of 50. Mu.m. Firstly, cleaning a three-dimensional network substrate of a metal copper skeleton according to the step (2), and then depositing a chromium film with the thickness of 50nm on the surface of the three-dimensional network skeleton of the foam copper by adopting a magnetron sputtering technology according to the step (2) to serve as an intermediate transition layer.
(2) And (3) placing the nano-crystalline grains and the three-dimensional metal skeleton substrate in the step (1) in a beaker, mixing, heating to boiling, then placing in high-power ultrasonic waves for oscillation, taking out the three-dimensional continuous network skeleton substrate after uniform dispersion, and drying to obtain the three-dimensional continuous network skeleton substrate with a large number of nano-crystalline grains embedded in meshes. In the suspension containing the nano-crystalline grains, the mass fraction of the diamond mixed particles is 0.03%, and the average size of the nano-crystalline grains is 25nm. The ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is completed, the metal skeleton substrate is taken out, and is washed clean by deionized water and/or absolute ethyl alcohol and then dried.
(3) And then adopting chemical vapor deposition to deposit a diamond film on the copper substrate with the three-dimensional configuration adsorbed with nano diamond particles, and adopting a diamond deposition process: depositing three-dimensional continuous network diamond on the surface of the foam matrix by adopting hot filament CVD, wherein the hot filament is 0.5mmAnd (3) a straight tungsten wire, wherein the straight tungsten wire is completely covered over the substrate, and then the pretreated substrate is placed into a cavity of the HFCVD equipment, and the distance between a hot wire and a base (8 mm) is adjusted. After the installation, closing the cabin door for vacuumizing, then introducing hydrogen and methane according to the air source concentration ratio set by experiments, closing the air extraction valve after the reaction air sources are uniformly mixed, and adjusting the air pressure in the cavity to be set pressure by the micro-adjustment valve. Then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, meanwhile, the air pressure in the deposition chamber needs to be observed, after the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, the CH needs to be closed 4 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: gas ratio H 2 :CH 4 Deposition time was 14h =98 sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the diamond layer is 10-30 μm.
(4): the diamond surface is doped with boron by adopting hot filament vapor deposition, and the hot filament isThe straight wire is completely covered over the substrate, and then the pretreated substrate is put into the cavity of the HFCVD equipment, and the distance between the hot wire and the base (8 mm) is adjusted. After the installation, closing the cabin door, vacuumizing, and then introducing hydrogen, methane and borane according to the air source concentration ratio set by the experiment (diborane used by the experiment is B) 2 H 6 :H 2 Mixed gas of 5:95), when the reaction gas sources are uniformly mixed, the extraction valve is closed, and the air pressure in the cavity is adjusted to be set pressure by the adjusting fine tuning valve. And then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, the air pressure in the deposition chamber is required to be observed, if the air pressure is changed, the air pressure is required to be continuously regulated by the fine-tuning valve, and finally the boron-doped diamond film is deposited. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, CH needs to be closed 4 And B 2 H 6 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are as follows: in the first stage, the deposition pressure is 3kPaThe deposition temperature is 850 ℃, and the gas flow rate ratio H 2 :B 2 H 6 :CH 4 The deposition time was 1H, the second stage gas flow rate ratio H, =98 sccm:0.2sccm:2.0sccm 2 :B 2 H 6 :CH 4 98sccm 0.4sccm 2.0sccm, deposition pressure 3kPa, deposition temperature 850 ℃, deposition time 1H, third stage, deposition pressure 3kPa, deposition temperature 850 ℃, gas flow rate ratio H 2 :B 2 H 6 :CH 4 The deposition time was 2h =98 sccm:0.6sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 mu m.
(5) And (3) simultaneously placing the obtained high-performance boron-doped diamond film material and boron-doped zero-dimensional configuration diamond grains in a bottle, mixing, heating to boiling, then placing in high-power ultrasonic waves for oscillation, taking out the diamond reinforcement body after uniform dispersion, and drying to obtain the three-dimensional diamond reinforcement body with a large number of zero-dimensional diamond particle reinforcement bodies embedded in meshes. Wherein, in the suspension containing the zero-dimensional diamond particle reinforcement, the mass fraction of the diamond mixed particles is 0.05 percent, and the average size of the zero-dimensional diamond particles is 50 mu m. And the ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is finished, taking out the diamond with the three-dimensional network configuration containing the zero-dimensional diamond particles, washing the diamond with deionized water and/or absolute ethyl alcohol, and drying the diamond.
(6) The obtained high-performance boron-doped diamond film material is put into a vacuum tube furnace for heat treatment, the two ends are not sealed, and the pressure is 10 5 Pa, setting the temperature to 800 ℃, and keeping for 60min.
(7) And (3) arranging the foam diamond reinforcements obtained in the step (5) in a mould in an oriented and uniform way, and placing copper-zirconium alloy which is 2 times of the skeleton volume of the high-conductivity continuous diamond reinforcement array above the skeleton, wherein the mass content of zirconium is 0.3wt%. Then placing the grinding tool into an infiltration device, setting the heating temperature to 1350 ℃, setting the heating rate to 12 ℃ per minute, finally preserving the heat at 1350 ℃ for 30 minutes, preserving the heat at the pressure of 5MPa, naturally cooling to room temperature, taking out the sample, removing surface metal by polishing, and cleaning to obtain the composite material.
(8) The prepared composite material has thermal conductivity which is found to reach 795W/mK through a laser flash method test.
Example 3 boron doped diamond reinforced aluminum matrix composites (the metal matrix is an aluminum-titanium alloy and the reinforcement configuration is a coupling of a three-dimensional network configuration with a zero-dimensional particle configuration)
(1) Pretreatment of a substrate: in the embodiment, the foam copper with the aperture of 0.25mm, the diameter of 12.3mm and the thickness of 2.0mm is used as a substrate, firstly, the foam copper three-dimensional network substrate is cleaned according to the step (2), and then, a chromium film with the thickness of 50nm is deposited on the surface of the foam copper three-dimensional network skeleton according to the step (2) by adopting a magnetron sputtering technology to serve as an intermediate transition layer.
(2) And (3) placing the nanocrystalline diamond particles and the three-dimensional continuous network skeleton substrate in the step (1) into a beaker for mixing, heating to boiling, then placing into high-power ultrasonic waves for oscillation, taking out the three-dimensional continuous network skeleton substrate after uniform dispersion, and drying to obtain the three-dimensional continuous network skeleton substrate with a large number of nanocrystalline and micron-sized diamond particles embedded in meshes. Wherein, in the suspension containing mixed particles of nanocrystalline and/or micron-sized diamond, the mass fraction of the mixed particles of diamond is 0.01 percent, the ultrasonic vibration treatment time is 30 minutes, after the ultrasonic treatment is completed, the foam diamond is taken out, and the foam diamond is washed clean by deionized water and/or absolute ethyl alcohol and then dried.
(3) And then adopting chemical vapor deposition to deposit a diamond film on the copper substrate with the three-dimensional configuration adsorbed with nano diamond particles, and adopting a diamond deposition process: and (3) adopting hot filament CVD to deposit three-dimensional continuous network diamond on the surface of the foam matrix, wherein the hot filament is a straight tungsten filament with the thickness of 0.5mm, completely covering the straight filament above the substrate, then placing the pretreated substrate into a cavity of an HFCVD device, and adjusting the hot filament-base spacing (8 mm). After the installation, closing the cabin door for vacuumizing, then introducing hydrogen and methane according to the air source concentration ratio set by experiments, closing the air extraction valve after the reaction air sources are uniformly mixed, and adjusting the air pressure in the cavity to be set pressure by the micro-adjustment valve. Then, a power supply is turned on to regulate current, the hot wire is heated to a set temperature, meanwhile, the air pressure in the deposition chamber needs to be observed, after the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, at the moment, CH4 needs to be closed, and only H2 is used for etching graphite phases on the surface of the diamond. Deposition parameters used in this example: the gas ratio h2, ch4=98 sccm:2.0sccm, deposition time was 14H. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the diamond layer is 10-30 μm.
(4): the diamond surface is doped with boron by adopting hot filament vapor deposition, and the hot filament isThe straight wire is completely covered over the substrate, and then the pretreated substrate is put into the cavity of the HFCVD equipment, and the distance between the hot wire and the base (8 mm) is adjusted. After the installation, closing the cabin door, vacuumizing, and then introducing hydrogen, methane and borane according to the air source concentration ratio set by the experiment (diborane used by the experiment is B) 2 H 6 :H 2 Mixed gas of 5:95), when the reaction gas sources are uniformly mixed, the extraction valve is closed, and the air pressure in the cavity is adjusted to be set pressure by the adjusting fine tuning valve. And then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, the air pressure in the deposition chamber is required to be observed, if the air pressure is changed, the air pressure is required to be continuously regulated by the fine-tuning valve, and finally the boron-doped diamond film is deposited. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, CH needs to be closed 4 And B 2 H 6 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are as follows: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate is higher than H 2 :B 2 H 6 :CH 4 The deposition time was 1H, the second stage gas flow rate ratio H, =98 sccm:0.2sccm:2.0sccm 2 :B 2 H 6 :CH 4 98sccm 0.4sccm 2.0sccm, deposition pressure 3kPa, deposition temperature 850 ℃, deposition time 1H, third stage, deposition pressure 3kPa, deposition temperature 850 ℃, gas flow rate ratio H 2 :B 2 H 6 :CH 4 The deposition time was 2h =98 sccm:0.6sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; thickness of boron doped diamond filmThe degree was 2. Mu.m.
(5) And (3) simultaneously placing the obtained high-performance boron-doped diamond film material and boron-doped zero-dimensional configuration diamond grains in a bottle, mixing, heating to boiling, then placing in high-power ultrasonic waves for oscillation, taking out the diamond reinforcement body after uniform dispersion, and drying to obtain the three-dimensional diamond reinforcement body with a large number of zero-dimensional diamond particle reinforcement bodies embedded in meshes. Wherein, in the suspension containing the zero-dimensional diamond particle reinforcement, the mass fraction of the diamond mixed particles is 0.05 percent, and the average size of the zero-dimensional diamond particles is 50 mu m. And the ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is finished, taking out the diamond with the three-dimensional network configuration containing the zero-dimensional diamond particles, washing the diamond with deionized water and/or absolute ethyl alcohol, and drying the diamond.
(6) The obtained high-performance boron-doped diamond film material is put into a vacuum tube furnace for heat treatment, the two ends are not sealed, and the pressure is 10 5 Pa, setting the temperature to 800 ℃, and keeping for 60min.
(6) And (3) uniformly arranging the obtained foam diamond reinforcements in a mould in an oriented way, placing an aluminum-titanium alloy which is 2 times of the volume of a skeleton of a high-conductivity continuous diamond reinforcement array above the skeleton, wherein the mass content of metal titanium is 0.2wt%, then placing a grinding tool into an infiltration device, setting the heating temperature to 1350 ℃, the heating rate to 12 ℃ per minute, finally preserving the heat at 1350 ℃ for 30 minutes, preserving the heat at the pressure of 5MPa, naturally cooling to room temperature, taking out a sample, removing surface metal by polishing, and cleaning to obtain the composite material.
(7) The volume fraction of the foam diamond reinforcing body of the prepared composite material is 15vol%, and the thermal conductivity is measured by a laser flash method and found to reach 738W/mK.
Example 4 boron doped diamond reinforced aluminum matrix composites (reinforcement configuration is zero dimensional particle configuration)
(1) Diamond particles with the granularity of 80 mu m are prepared and put into the solution, the ultrasonic oscillation treatment time is 10min, after the ultrasonic treatment is completed, the diamond particles are taken out, washed clean by deionized water and/or absolute ethyl alcohol, and then dried.
(2) At the diamondThe surface of the stone adopts a hot wire vapor deposition boron doped diamond layer, and the hot wire is The straight wire is completely covered over the substrate, and then the pretreated substrate is put into the cavity of the HFCVD equipment, and the distance between the hot wire and the base (8 mm) is adjusted. After the installation, closing the cabin door, vacuumizing, and then introducing hydrogen, methane and borane according to the air source concentration ratio set by the experiment (diborane used by the experiment is B) 2 H 6 :H 2 Mixed gas of 5:95), when the reaction gas sources are uniformly mixed, the extraction valve is closed, and the air pressure in the cavity is adjusted to be set pressure by the adjusting fine tuning valve. And then the power supply is turned on to regulate the current, the hot wire is heated to the set temperature, the air pressure in the deposition chamber is required to be observed, if the air pressure is changed, the air pressure is required to be continuously regulated by the fine-tuning valve, and finally the boron-doped diamond film is deposited. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and at the moment, CH needs to be closed 4 And B 2 H 6 Using only H 2 To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are as follows: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate is higher than H 2 :B 2 H 6 :CH 4 The deposition time was 1H, the second stage gas flow rate ratio H, =98 sccm:0.2sccm:2.0sccm 2 :B 2 H 6 :CH 4 98sccm 0.4sccm 2.0sccm, deposition pressure 3kPa, deposition temperature 850 ℃, deposition time 1H, third stage, deposition pressure 3kPa, deposition temperature 850 ℃, gas flow rate ratio H 2 :B 2 H 6 :CH 4 The deposition time was 2h =98 sccm:0.6sccm:2.0 sccm. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 mu m.
(3) And (3) putting the obtained high-performance boron-doped diamond film material into a vacuum tube furnace for heat treatment, wherein the two ends of the high-performance boron-doped diamond film material are not sealed, the pressure is 105Pa, the temperature is set to be 800 ℃, and the high-performance boron-doped diamond film material is kept for 60 minutes.
(4) Placing an aluminum-titanium alloy, which is 2 times the volume of the diamond-enhanced particle skeleton, over the grinding tool in the stacking of the particle diamond-enhanced mold obtained in (3), wherein the mass content of titanium is 0.3wt%. Then placing the grinding tool into an infiltration device, setting the heating temperature to 780 ℃, setting the heating rate to 12 ℃ per minute, finally preserving the heat at 780 ℃ for 30 minutes, keeping the pressure at 5MPa during heat preservation, naturally cooling to room temperature, taking out a sample, removing surface metal through polishing, and cleaning to obtain the composite material.
(5) And (3) testing the thermal conductivity of the prepared composite material in the step (4) by a laser flash method, and finding that the thermal conductivity reaches 640W/mK.
Comparative example 1
Other conditions were the same as in example 1, except that the boron doped diamond layer was not deposited on the surface of the high purity diamond layer, and the same thickness of the W plating layer was used instead for modification, and the final measured thermal conductivity of the prepared composite material was 595W/mk, which was lower than that of the prepared boron doped diamond enhanced copper-based composite material (687W/mk)
Comparative example 2
Other conditions were the same as in example 1, except that no modified layer was deposited on the surface of the high purity diamond layer, and the Zr mass fraction in the copper-zirconium alloy was 1.0wt%, and the final measured thermal conductivity of the prepared composite was 602W/mk, which was lower than that of the prepared boron doped diamond enhanced copper-based composite (687W/mk).
Comparative example 3
Other conditions were the same as in example 1 except that gradient boron deposition was not performed during deposition of the diamond layer, and only one stage of deposition was used, and H was controlled during deposition 2 :B 2 H 6 :CH 4 =98 sccm:0.4sccm:2.0sccm, and the final measured thermal conductivity of the prepared composite material was 603W/mk. Lower than the thermal conductivity (687W/mk) of the composite material prepared in example 1.
Comparative example 4
Other conditions were the same as in example 3, except that no modified layer was deposited on the surface of the high purity diamond layer, and the mass fraction of Ti in the aluminum-titanium alloy was 1.0wt%, and the final measured thermal conductivity of the prepared composite material was 620W/mk, which was lower than the thermal conductivity (738W/mk) of the prepared boron doped diamond enhanced copper-based composite material.

Claims (9)

1. A gradient boron doped diamond reinforced metal matrix composite is characterized in that: the composite material comprises a gradient boron doped diamond reinforcement and a metal matrix; the gradient boron doped diamond reinforcing body comprises an undoped diamond reinforcing body and a gradient boron doped diamond modifying layer arranged on the surface of the diamond reinforcing body; the configuration of the diamond reinforcing body is a three-dimensional continuous network skeleton configuration and a zero-dimensional particle configuration;
Wherein the volume fraction of the diamond reinforcing body with the three-dimensional continuous network skeleton structure in the gradient boron doped diamond reinforced metal matrix composite material is 10-40%, the volume fraction of the diamond reinforcing body with the zero-dimensional particle structure in the gradient boron doped diamond reinforced metal matrix composite material is 10-40%, and the particle size of the diamond reinforcing body with the zero-dimensional particle structure is 10-80 mu m;
the diamond reinforcing body with the three-dimensional continuous network skeleton configuration comprises a three-dimensional continuous network metal skeleton and a diamond layer arranged on the surface of the three-dimensional continuous network metal skeleton;
the gradient boron doped diamond modification layer sequentially comprises a boron doped diamond bottom layer, a boron doped diamond middle layer and a boron doped diamond top layer with the boron content increasing in a gradient manner from bottom to top; in the boron doped diamond bottom layer, B/C is 3333-8332ppm according to atomic ratio; in the boron doped diamond middle layer, B/C is 9999-15000ppm according to atomic ratio; in the boron doped diamond top layer, B/C is 16665-21665ppm according to atomic ratio.
2. A gradient boron doped diamond enhanced metal matrix composite as in claim 1, wherein: the diamond reinforcing body with the zero-dimensional particle configuration is pure diamond or natural diamond prepared by a high-temperature high-pressure method; the diamond reinforcement with the three-dimensional continuous network skeleton configuration is obtained by chemical vapor deposition on the surface of a substrate with a corresponding configuration;
The gradient boron doped diamond modification layer is deposited on the surface of the diamond reinforcing body through chemical vapor deposition.
3. A gradient boron doped diamond enhanced metal matrix composite as in claim 1, wherein: the volume fraction of the gradient boron doped diamond modified layer in the gradient boron doped diamond reinforcing body is less than or equal to 3 percent.
4. A gradient boron doped diamond enhanced metal matrix composite as in claim 1, wherein: the metal matrix comprises one or more of Al, mg, cu, ag, zn;
the gradient boron doped diamond reinforcing body surface or metal matrix also contains a small amount of carbide alloy elements which can be formed, wherein the carbide alloy elements are selected from one or more of B, si, ti, cr, zr, nb, ta, W, mo.
5. A gradient boron doped diamond enhanced metal matrix composite as in claim 1, wherein:
the metal in the three-dimensional continuous network metal framework is selected from one or more of nickel, copper, titanium, chromium, iron, silicon, aluminum, niobium, tantalum, tungsten, molybdenum and zirconium; the aperture of the three-dimensional continuous network metal framework is 0.01-10mm, the aperture ratio is 40-99%, and the holes are uniformly distributed or randomly distributed; the three-dimensional continuous network metal framework structure is a planar structure or a three-dimensional structure;
The diamond reinforcing body with the three-dimensional continuous network skeleton configuration further comprises a transition layer, wherein the transition layer is positioned between the three-dimensional continuous network metal skeleton and the diamond layer; the transition layer material is selected from one or more of nickel, niobium, tantalum, titanium, cobalt, tungsten, molybdenum and chromium, and the thickness of the transition layer is 0.5-30 mu m.
6. A method of preparing a gradient boron doped diamond enhanced metal matrix composite according to claim 1, wherein: the method comprises the following steps:
step one, planting seed crystals on a three-dimensional continuous network metal framework
Placing the three-dimensional continuous network metal skeleton into suspension containing nanocrystalline diamond particles, heating to boiling, performing ultrasonic treatment and drying; obtaining a three-dimensional continuous network metal framework with nano-crystal diamond particles adsorbed on the surface;
step two, depositing a diamond layer
Placing the three-dimensional continuous network metal framework with the nano-crystal diamond particles adsorbed on the surface obtained in the step one into a chemical vapor deposition furnace for diamond layer deposition, wherein the deposition parameters are as follows: the carbon-containing gas accounts for 0.5 to 10.0 percent of the total gas mass flow in the furnace; the deposition temperature is 600-1000 ℃ and the deposition air pressure is 10 3 -10 4 Pa; the deposition time is 12-24 hours;
Step three, depositing a gradient boron doped diamond modification layer
Placing the three-dimensional continuous network metal skeleton with the diamond layer deposited in the second step into a chemical vapor deposition furnace, and performing three-stage deposition to obtain a gradient boron doped diamond modified layer, wherein the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the first stage deposition; the boron-containing gas accounts for 0.005-0.0075 percent of the total gas mass flow in the furnace; the temperature of the first stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa, the time is 0.5-1.0h; during the second stage deposition, the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace; the boron-containing gas accounts for 0.015-0.0225% of the total gas mass flow in the furnace, the temperature of the second stage deposition is 600-1000 ℃, and the air pressure is 10% 3 -10 4 Pa, the time is 0.5-1.0h, and the carbon-containing gas accounts for 0.5-10% of the total gas mass flow in the furnace during the third-stage deposition; the boron-containing gas accounts for 0.025 to 0.0325 percent of the total mass flow of the gas in the furnace; the temperature of the third stage deposition is 600-1000 ℃ and the air pressure is 10 3 -10 4 Pa; the time is 1.0-2.0h; etching the boron doped diamond layer at 700-900 ℃ in hydrogen atmosphere after the deposition is completed; obtaining a gradient boron doped diamond reinforcement of a three-dimensional continuous network skeleton configuration;
Step four, adding the diamond reinforcing body with zero-dimensional particle configuration
Placing the gradient boron doped diamond reinforcement with the three-dimensional continuous network skeleton configuration obtained in the step three into a suspension of the gradient boron doped diamond reinforcement with the zero-dimensional particle configuration; heating to boiling, ultrasonic treatment, drying to make the gradient boron doped diamond reinforcing body with zero-dimensional grain structure inlaid in the pore space of gradient boron doped diamond reinforcing body with three-dimensional continuous network skeleton structure,
step five, heat treatment
Performing heat treatment on the diamond reinforcement with the three-dimensional continuous network skeleton configuration obtained in the step four in an air atmosphere to obtain an activated gradient boron doped diamond reinforcement;
step six, compounding gradient boron doped diamond reinforcing body and metal matrix
And (3) adopting a pressure infiltration process to infiltrate the metal into the activated gradient boron doped diamond reinforcing body, and cooling to obtain the gradient boron doped diamond reinforced metal matrix composite.
7. The method for preparing the gradient boron doped diamond enhanced metal matrix composite according to claim 6, wherein the method comprises the following steps: step one; in the suspension containing the nanocrystalline diamond particles, the mass fraction of the nanocrystalline diamond particles is 0.01% -0.05%, and the size of the nanocrystalline diamond particles is 10nm-100nm; step one; the ultrasonic vibration treatment time is 5-30min;
In the fourth step, in the suspension containing the gradient boron doped diamond reinforcing body with the zero-dimensional particle configuration, the mass fraction of the gradient boron doped diamond reinforcing body with the zero-dimensional particle configuration is 0.01% -0.1%, and the size of the gradient boron doped diamond reinforcing body with the zero-dimensional particle configuration is 10 mu m-80 mu m;
in the fifth step, the heat treatment temperature is 700-1000 ℃ and the treatment time is 30-100min; the pressure in the furnace is 10Pa-10 5 Pa。
8. The method for preparing the gradient boron doped diamond enhanced metal matrix composite according to claim 6, wherein the method comprises the following steps: in the sixth step, the metal infiltration process is as follows: placing metal above the activated gradient boron doped diamond reinforcing body, heating to melt the metal, preserving heat for 20-40 min after the metal is melted, simultaneously applying pressure of 3-10MPa in the heat preservation process, and then cooling.
9. Use of a gradient boron doped diamond enhanced metal matrix composite according to any one of claims 1 to 5, wherein: the gradient boron doped diamond enhanced metal matrix composite is used in electronic packaging materials.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027504A1 (en) * 2008-09-08 2010-03-11 Materials And Electrochemical Research (Mer) Corporation Machinable metal/diamond metal matrix composite compound structure and method of making same
CN103370765A (en) * 2010-12-23 2013-10-23 六号元素有限公司 Controlling doping of synthetic diamond material
CN105239026A (en) * 2015-10-12 2016-01-13 中南大学 One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof
CN105695831A (en) * 2016-03-21 2016-06-22 中南大学 Superhigh-thermal-conductivity continuous diamond skeleton reinforced composite material and preparation method
CN105733192A (en) * 2016-03-21 2016-07-06 中南大学 Foam framework enhanced polymer composite material and preparation method thereof
CN105779804A (en) * 2016-03-21 2016-07-20 中南大学 Foam skeleton structure reinforced metal-matrix composite material and preparation method
CN105792605A (en) * 2016-03-21 2016-07-20 中南大学 Three-dimensional space network porous and high-efficiency heat sink and application
CN106435518A (en) * 2016-10-21 2017-02-22 中南大学 High-specific-surface-area boron-doped diamond electrode and preparation method and application thereof
CN106637111A (en) * 2016-10-21 2017-05-10 中南大学 Niobium-base boron doped diamond foam electrode and preparing method and application thereof
WO2017161993A1 (en) * 2016-03-21 2017-09-28 中南大学 Foam skeleton reinforced composite, preparation method therefor, and application thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027504A1 (en) * 2008-09-08 2010-03-11 Materials And Electrochemical Research (Mer) Corporation Machinable metal/diamond metal matrix composite compound structure and method of making same
CN103370765A (en) * 2010-12-23 2013-10-23 六号元素有限公司 Controlling doping of synthetic diamond material
CN105239026A (en) * 2015-10-12 2016-01-13 中南大学 One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof
CN105695831A (en) * 2016-03-21 2016-06-22 中南大学 Superhigh-thermal-conductivity continuous diamond skeleton reinforced composite material and preparation method
CN105733192A (en) * 2016-03-21 2016-07-06 中南大学 Foam framework enhanced polymer composite material and preparation method thereof
CN105779804A (en) * 2016-03-21 2016-07-20 中南大学 Foam skeleton structure reinforced metal-matrix composite material and preparation method
CN105792605A (en) * 2016-03-21 2016-07-20 中南大学 Three-dimensional space network porous and high-efficiency heat sink and application
WO2017161993A1 (en) * 2016-03-21 2017-09-28 中南大学 Foam skeleton reinforced composite, preparation method therefor, and application thereof
CN106435518A (en) * 2016-10-21 2017-02-22 中南大学 High-specific-surface-area boron-doped diamond electrode and preparation method and application thereof
CN106637111A (en) * 2016-10-21 2017-05-10 中南大学 Niobium-base boron doped diamond foam electrode and preparing method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
于琦等.金刚石简介.《纳米氧化锌与金刚石复合结构的研究与应用》.北京：北京邮电大学出版社,2016,第28-29页. *
邹建新等.梯度功能材料概述.《钒钛功能材料》.北京：冶金工艺出版社,2019,第108-109页. *

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