CN111778506A - Gradient boron-doped diamond enhanced metal matrix composite material and preparation method and application thereof - Google Patents

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

Info

Publication number
CN111778506A
CN111778506A CN202010390535.XA CN202010390535A CN111778506A CN 111778506 A CN111778506 A CN 111778506A CN 202010390535 A CN202010390535 A CN 202010390535A CN 111778506 A CN111778506 A CN 111778506A
Authority
CN
China
Prior art keywords
diamond
boron
doped diamond
dimensional
gradient
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010390535.XA
Other languages
Chinese (zh)
Other versions
CN111778506B (en
Inventor
魏秋平
马莉
周科朝
康翱龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202010390535.XA priority Critical patent/CN111778506B/en
Publication of CN111778506A publication Critical patent/CN111778506A/en
Application granted granted Critical
Publication of CN111778506B publication Critical patent/CN111778506B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C23C28/32—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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-based composite material and a preparation method and application thereof, wherein the composite material comprises a gradient boron-doped diamond reinforcement body and a metal matrix; the gradient boron-doped diamond reinforcement body 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 body comprises one or more of zero-dimensional particle configuration, one-dimensional linear configuration, two-dimensional sheet configuration and three-dimensional continuous network framework configuration. The coupling of the gradient boron-doped diamond reinforcement bodies with different dimensions can greatly improve the amount of diamond in the composite material and improve the thermal conductivity. In addition, in the gradient boron-doped diamond reinforcement body added in the invention, the proportion of the gradient boron-doped diamond modification layer is small, the heat conductivity of diamond is not influenced, and the wettability of the diamond with metal can be greatly improved.

Description

Gradient boron-doped diamond enhanced metal matrix composite material and preparation method and application thereof
Technical Field
The invention relates to a gradient boron-doped diamond reinforced metal-based 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 coming of the 5G era, the pace of interconnection of everything is accelerating, and electronic products are gradually developing in the directions of intellectualization, multifunction, lightness, thinness and the like. In the process of increasingly stronger 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 the rapid increase of power consumption and heat productivity, so that people have increasingly higher heat dissipation requirements on heat management materials. In addition, the rapid development of the aerospace and transportation industries has increasingly stringent requirements on the light weight of materials. Therefore, high thermal conductivity, low coefficient of thermal expansion 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), has a low thermal expansion coefficient (0.86ppm/K) and a low density (3.52g/cm3), is an excellent reinforcement in a thermal management composite material, is compounded with a high-thermal-conductivity metal, and can obtain more excellent thermal conductivity while ensuring ideal thermal expansion coefficient and low density theoretically. However, the thermal conductivity of the diamond metal matrix composite prepared at present is low, and some are even lower than that of the metal matrix, and the reason is that the metal material and the diamond are poor in wettability and are weakly combined, so that a plurality of structural defects and gaps exist on an interface, electrons and phonons are scattered at the interface, high interface thermal resistance is formed, and the improvement of the thermal conductivity of the composite is limited. At present, researchers mainly improve the wettability of an interface by strengthening the interface and reduce the thermal resistance of the interface.
In order to improve the direct interface wettability of diamond and a metal matrix, people research a concentrated interface modification method, wherein the most common method for improving the interface wettability is that the diamond surface is modified and alloyed with the metal matrix, the diamond surface is modified by adding a transition layer on 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; in the alloying of the metal matrix, some materials (such as boron, chromium, zirconium and the like) which are easy to form carbide are added into the metal matrix, and a layer of carbide is also formed when the metal matrix is compounded with the diamond particles, so that the bonding capability of the metal matrix and the diamond particles is enhanced. Finally, a carbide transition layer is formed when the diamond and the metal material are compounded to enhance the interface bonding capability of the diamond and the metal material. However, the thermal conductivity of the resulting carbide transition layer tends to be low, which also severely affects the thermal conductivity of the composite material.
Disclosure of Invention
The invention aims to overcome the defects of the existing interface modification technology of diamond metal matrix composites, and provides a gradient boron-doped diamond reinforced metal matrix composite and a preparation method and application thereof.
In order to achieve the purpose, the 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 reinforcement body and a metal matrix; the gradient boron-doped diamond reinforcement body comprises an undoped diamond reinforcement body and a gradient boron-doped diamond modification layer arranged on the surface of the diamond reinforcement body.
The invention relates to a gradient boron-doped diamond-reinforced metal-based composite material, wherein the configuration of a diamond reinforcement 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 framework configuration.
The amount of diamond in the composite material can be greatly improved through the coupling of the gradient boron-doped diamond reinforcement bodies with different dimensions, and the thermal conductivity is improved.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, 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 reinforcement body with the one-dimensional linear configuration, the two-dimensional sheet configuration and the three-dimensional continuous network framework configuration is obtained by depositing a diamond layer on the surface of the substrate with the 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 to a thickness of 10-100 μm, preferably 10-40 μm
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein a gradient boron-doped diamond modified layer is deposited on the surface of a diamond reinforced body through chemical vapor deposition.
The configuration of the gradient boron-doped diamond reinforcement body is consistent with that of the diamond reinforcement body.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein a gradient boron-doped diamond modified layer 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, the B/C is 3333-8332ppm in terms of atomic ratio; in the boron-doped diamond middle layer, the B/C is 9999-15000ppm in terms of atomic ratio; in the boron-doped diamond top layer, the B/C is 16665-21665ppm by atomic ratio.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein the thickness of a gradient boron-doped diamond modified layer is 0.01-20 μm, preferably: 0.5-3 μm.
The invention relates to a gradient boron-doped diamond reinforced metal-based composite material, wherein the volume fraction of a gradient boron-doped diamond modified layer in a diamond reinforcement body is less than or equal to 3%.
The invention relates to a gradient boron-doped diamond enhanced metal matrix composite, wherein micropores and/or pointed 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 reinforcing body is at least one of cylindrical and columnar spiral shapes, and the outer diameter of a linear diamond is 0.05-20 mm.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein the shape of the two-dimensional sheet configuration is at least one of a plane shape, a wave shape and a curved surface shape; the through holes arranged on the sheet-shaped structure are uniformly distributed or randomly distributed; the shape of the through hole arranged on the sheet-shaped heat conduction material is selected from at least one of circle, ellipse and polygon; the size range of the through hole is 0.5-50 mm; the thickness of the sheet-shaped heat conduction material is 0.02-50 mm.
The invention relates to a gradient boron-doped diamond-reinforced metal matrix composite, wherein a diamond reinforcement body with a three-dimensional continuous network framework structure comprises a three-dimensional continuous network metal framework and a diamond layer arranged on the surface of the three-dimensional continuous network metal framework.
The invention relates to a gradient boron-doped diamond-reinforced metal-based composite material, wherein in a diamond reinforcement body with a three-dimensional continuous network framework structure, the volume fraction of a three-dimensional continuous network metal framework is 20-40 vol%. The volume fraction of the metal framework in the invention is small and only plays a supporting role.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein 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 or randomly distributed.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein a three-dimensional continuous network diamond reinforcement body also 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 is made of one or more of nickel, niobium, tantalum, titanium, cobalt, tungsten, molybdenum and chromium, and has a thickness of 0.5-30 μm.
The inventor finds that the performance of the diamond reinforcing phase can be further improved by introducing the transition layer under two conditions, namely, when the difference between the metal phase in the metal framework and the diamond is too large, the thermal stress of the interface of the high-purity diamond layer and the metal framework 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 not suitable for diamond nucleation, the introduced transition layer is introduced, so that the chemical vapor deposition efficiency, the continuity of the thin film layer and the bonding property of the thin film layer and the metal framework can be effectively improved.
In the invention, as long as the requirements of the thickness and the good bonding property of the transition layer can be met, the preparation method of the transition layer is not limited, and for example, one of electroplating, chemical plating, evaporation, 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 thermal conductivity of the diamond is kept, and the thermal conductivity of the composite material is improved.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, which comprises a preparation method of a gradient boron-doped diamond modified layer, wherein the preparation method comprises the following steps: placing the diamond reinforcement body in a chemical vapor deposition furnace for three-stage deposition, wherein during the first-stage deposition, the mass flow of carbon-containing gas accounts for 0.5-10% of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005-0.0075%; the deposition temperature of the first section is 600-1000 ℃, and the air pressure is 103-104Pa, the time is 0.5-1.0 h; during the second-stage deposition, the mass flow percentage of the carbon-containing gas in the furnace is 0.5-10%; the second-stage deposition temperature of the boron-containing gas accounting for 0.015-0.0225 percent of the mass flow of the total gas in the furnace is 600 ℃ and 1000 ℃, and the gas pressure is 103-104Pa for 0.5-1.0h, and during the third stage of deposition, the carbon-containing gas accounts for 0.5-10% of the mass flow of the whole gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.025-0.0325%; the deposition temperature of the third section is 600-3-104Pa; the time is 1.0-2.0 h.
Preferably, the gradient boron-doped diamond modified layer is subjected to heat treatment in the air atmosphere, wherein the heat treatment temperature is 700-1000 ℃, and the treatment time is 30-100 min; the pressure in the furnace is 10Pa-105Pa. And (3) carrying out heat treatment to ensure that micropores and/or sharp cones are distributed on the surface of the gradient boron-doped diamond modified layer and obtain an activated surface.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein a metal matrix comprises one or more of Al, Mg, Cu, Ag and Zn.
The invention relates to a gradient boron-doped diamond reinforced metal matrix composite, wherein the surface or the metal matrix of the gradient boron-doped diamond reinforced body also contains a small amount of alloying elements capable of forming carbide, and the alloying elements are selected from one or more of B, Si, Ti, Cr, Zr, Nb, Ta, W and Mo.
The carbide alloy elements can be formed and added in a mode of dispersing in molten metal in the preparation process of the metal matrix, and the carbide alloy elements are added on the surface of the gradient boron-doped diamond reinforcement body in the modes of electroplating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition and physical vapor deposition.
In the invention, when the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration, the one-dimensional linear configuration and the two-dimensional sheet configuration is adopted, the preparation of the gradient boron-doped diamond reinforced metal-based composite material only needs to disperse the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration, the one-dimensional linear configuration and the two-dimensional sheet configuration in molten metal, and then the gradient boron-doped diamond reinforced metal-based composite material is obtained by cooling, or a metal matrix is compounded with the one-dimensional or two-dimensional configuration reinforcement body by a vacuum extrusion casting method.
Preferably, the gradient boron-doped diamond reinforced metal matrix composite material has the structure of a three-dimensional continuous network framework and a zero-dimensional particle; wherein the volume fraction of the diamond reinforcement body with the three-dimensional continuous network framework configuration in the gradient boron-doped diamond-reinforced metal matrix composite material is 10-40%, preferably 10-20 vol%; the volume fraction of the diamond reinforcement body with the zero-dimensional particle configuration in the gradient boron-doped diamond-reinforced metal matrix composite material is 10-40%, preferably 10-25 vol%, and the particle size of the diamond reinforcement body with 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 crystal by three-dimensional continuous network metal framework
Placing the three-dimensional continuous network metal framework or the three-dimensional continuous network metal framework provided with the transition layer into a suspension containing nanocrystalline diamond particles, heating to boil, performing ultrasonic treatment, and drying; obtaining a three-dimensional continuous network metal framework with nanocrystalline diamond particles adsorbed on the surface;
step two, depositing a diamond layer
Placing the three-dimensional continuous network metal framework with the nanocrystalline diamond particles adsorbed on the surface, which is obtained in the step one, in a chemical vapor deposition furnace for diamond layer deposition, wherein the deposition parameters are as follows: the mass flow percentage of the carbon-containing gas in the whole furnace is 0.5-10.0%; the deposition temperature is 600-1000 ℃, and the deposition pressure is 10 DEG3-104Pa; the deposition time is 12-24 h;
step three, depositing a gradient boron-doped diamond modified layer
Placing the three-dimensional continuous network metal framework deposited with the diamond layer in the second step into a chemical vapor deposition furnace, and performing three-section deposition to obtain gradient boron dopingThe first stage of the heterodiamond modified layer is deposited, and the mass flow percentage of the carbon-containing gas in the furnace is 0.5-10%; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005-0.0075%; the deposition temperature of the first section is 600-1000 ℃, and the air pressure is 103-104Pa, the time is 0.5-1.0 h; during the second-stage deposition, the mass flow percentage of the carbon-containing gas in the furnace is 0.5-10%; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.015-0.0225%, the deposition temperature of the second stage is 600-3-104Pa for 0.5-1.0h, and during the third stage of deposition, the carbon-containing gas accounts for 0.5-10% of the mass flow of the whole gas in the furnace; the percentage of the boron-containing gas to the mass flow of the whole gas in the furnace is 0.025-0.0325%; the temperature of the third stage deposition is 600-1000 ℃, and the air pressure is 103-104Pa; the time is 1.0 to 2.0 hours; etching the boron-doped diamond layer at the temperature of 700-900 ℃ in a hydrogen atmosphere after the deposition is finished; obtaining a gradient boron-doped diamond reinforcement body with a three-dimensional continuous network framework configuration;
step four, adding the diamond reinforcement body with the zero-dimensional particle configuration
Placing the gradient boron-doped diamond reinforcement body with the three-dimensional continuous network skeleton configuration obtained in the third step into suspension of the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration; heating to boiling, ultrasonic processing and drying to enable the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration to be embedded in the pores of the diamond reinforcement body with the three-dimensional continuous network bone framework type,
step five, heat treatment
Carrying out heat treatment on the diamond reinforcement body with the three-dimensional continuous network framework configuration obtained in the fourth step in the air atmosphere to obtain an activated gradient boron-doped diamond reinforcement body;
step six, compounding the gradient boron-doped diamond reinforcement body with the metal matrix
And infiltrating metal into the activated gradient boron-doped diamond reinforcement body by adopting a pressure infiltration process, and cooling to obtain the gradient boron-doped diamond reinforced metal-based composite material.
In the actual operation process, the three-dimensional continuous network metal framework needs cleaning treatment in advance, acetone and absolute ethyl alcohol are sequentially adopted for ultrasonic cleaning for 10min to remove surface oil stains and impurities for standby application, if a transition layer needs to be arranged, then one of electroplating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition and physical vapor deposition is adopted to prepare an intermediate transition layer on the surface of the substrate, and the intermediate transition layer comprises one or more composite transition layers 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, 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 size of the nanocrystalline diamond particles is 10-100 nm.
The invention relates to a preparation method of a gradient boron-doped diamond reinforced metal matrix composite, which comprises the following steps of; the ultrasonic vibration treatment time is 5-30 min. And after the ultrasonic treatment is finished, taking out the material, washing the material by using deionized water and/or absolute ethyl alcohol, and drying the material.
The invention relates to a preparation method of a gradient boron-doped diamond enhanced metal matrix composite material, wherein in the second step, carbon-containing gas is CH4。
The invention relates to a preparation method of a gradient boron-doped diamond reinforced metal matrix composite, which comprises the third step that furnace gas comprises boron-containing gas, carbon-containing gas and hydrogen.
In the invention, hydrogen can be used as a diluting gas in the chemical deposition process and also as an etching gas, in the actual operation process, after the deposition is finished, the boron-containing gas and the carbon-containing gas are firstly closed, and hydrogen is continuously introduced for a period of time to etch the graphite phase on the surface of the boron-doped diamond.
In the actual operation process, when deposition needs to be carried out on two sides of a planar substrate or on multiple surfaces of a three-dimensional substrate, the boron-doped diamond layer in one surface is deposited, and then the boron-doped diamond layer is taken out, cooled, washed and dried, and then deposition of other layers is carried out.
In the invention, the boron source can be selected from one of solid, gas and liquid boron sources, and the gasification treatment is firstly carried out when the solid or liquid boron source is selected.
Preferably, the boron-containing gas is B2H6The carbon-containing gas is CH4。
Preferably, in the third step, during the first-stage deposition, the gas flow rate ratio of the introduced gas is hydrogen: carbon-containing gas: 98sccm of boron-containing gas, 2sccm, 0.1-0.25 sccm; and during the second-stage deposition, introducing hydrogen in the gas flow rate ratio: carbon-containing gas: 98sccm of boron-containing gas, 2sccm, 0.3-0.45 sccm; and during deposition in the third stage, introducing hydrogen in the gas flow rate ratio: carbon-containing gas: the boron-containing gas is 98sccm, 2sccm and 0.5-0.65 sccm.
Preferably, in the fourth step, in the suspension containing the gradient diamond reinforcement body with the zero-dimensional particle configuration, the mass fraction of the gradient diamond reinforcement body with the zero-dimensional particle configuration is 0.01-0.1%, and the size of the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration is 10-80 μm;
the invention relates to a preparation method of a gradient boron-doped diamond enhanced metal matrix composite, and in the fifth step, the heat treatment temperature is 700-1000 ℃, and the treatment time is 30-100 min; the pressure in the furnace is 10Pa-105Pa。
In 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 a boron-doped diamond reinforcement, and after the deposition, the heat treatment is carried out to carry out the heat treatment on the surface of the diamond, so that the surface of the diamond can be activated, and the bonding capability of the foam diamond and the metal matrix at the time of compounding is more excellent.
The invention relates to a preparation method of a gradient boron-doped diamond reinforced metal matrix composite, which comprises the following steps of: placing metal above the activated gradient boron-doped diamond reinforcement, 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 ultrathin boron-doped diamond layer has little influence on the intrinsic thermal conductivity of the diamond reinforcement body, ensures the high thermal conductivity of the diamond reinforcement body, and simultaneously ensures the high wettability of the reinforcement body and the matrix by only needing few extra carbides when the carbide modification is carried out on the surface of the metal matrix or the reinforcement body, thereby ensuring the thermal conductivity of the composite material.
The invention relates to application of a gradient boron-doped diamond reinforced metal-based composite material, which is used for an electronic packaging material.
Advantageous effects
The composite material of the invention contains the reinforcements with different dimensions, which can improve the amount of diamond and the thermal conductivity together, and especially when the configuration of the diamond reinforcement is three-dimensional continuous network skeleton configuration and 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 zero-dimensional diamond particles and the diamond with three-dimensional network structure, on the other hand, the distribution of the diamond with three-dimensional network structure in the matrix has more efficient thermal conductivity than that of the diamond with two-dimensional structure, and meanwhile, the amount of the diamond in the composite material is improved by adding the zero-dimensional particles, so that the thermal conductivity of the composite material is greatly improved.
In addition, the surface of the pure diamond layer is subjected to gradient boron-doped diamond deposition to form a reinforcing phase, three sections of depositions with different boron contents are carried out during the deposition of the boron-doped diamond, wherein the boron-doped diamond bottom layer which is in contact with the high-purity diamond layer is used as a reinforcing layer, the high purity of the diamond is kept through the doping of a small amount of boron, and because the diamond has high purity, diamond grains are compact and uniform, few defects and higher heat conductivity, while the boron-doped diamond top layer is compounded with a metal matrix, the diamond and the metal matrix can have better wettability and interface bonding capability due to proper boron doping amount, and the heat conduction performance of the composite material is greatly enhanced.
Meanwhile, when the boron-doped diamond layer is deposited to a high-purity diamond layer to form the diamond reinforcement body, the boron-doped diamond layer is subjected to heat treatment, so that micropores or pointed cones are uniformly distributed on the surface of the boron-doped diamond. The surface microstructure can greatly improve the interface bonding capability of the diamond reinforcement body and the metal matrix.
In conclusion, through the operation, the boron-doped diamond enhanced metal matrix composite material has the characteristics of high thermal conductivity and low thermal expansion coefficient, and can meet the requirements of thermal management materials with increasingly strict requirements on thermal conductivity and thermal expansion coefficient.
Detailed Description
Example 1 boron-doped Diamond-reinforced copper-based composite Material (the Reinforcement configuration is a three-dimensional network configuration)
(1) Pretreatment of the substrate: the three-dimensional network configuration in this example uses copper foam with a pore size of 0.25mm, a diameter of 12.3mm and a thickness of 2.0mm as the substrate. Firstly, cleaning a copper foil substrate with a three-dimensional network configuration according to the step (2), and then depositing a chromium film with the thickness of 50nm on the surface of a copper framework with the three-dimensional network configuration as an intermediate transition layer by adopting a magnetron sputtering technology according to the step (2).
(2) And (3) placing the nanocrystalline and the metal framework substrate in the step (1) into a beaker for mixing, heating to boil, then placing into high-power ultrasonic waves for oscillation, uniformly dispersing, taking out the three-dimensional continuous network framework substrate, and drying to obtain the three-dimensional continuous network framework substrate with a large number of nanocrystalline embedded in meshes. Wherein in the suspension containing the nanocrystalline diamond particles, the mass fraction of the diamond particles is 0.03%, the ultrasonic oscillation treatment time is 30min, after the ultrasonic treatment is finished, the foam diamond is taken out, washed clean by deionized water and/or absolute ethyl alcohol, and then dried.
(3) Then, depositing a diamond film on the copper substrate with the three-dimensional configuration adsorbed with the nano diamond particles by adopting chemical vapor deposition, wherein the diamond deposition process comprises the following steps: depositing three-dimensional continuous network diamond on the surface of the foam matrix by adopting hot filament CVD, wherein the used hot filament is a straight tungsten filament with the diameter of 0.5mm, completely covering the straight filament right above the substrate, and then pretreatingThe good substrate was placed inside the HFCVD apparatus chamber and the filament-substrate spacing (8mm) was adjusted. After the installation is finished, the cabin door is closed to vacuumize, then hydrogen and methane are introduced according to the concentration ratio of the air source set by the experiment, after the reaction air source is uniformly mixed, the air extraction valve is closed, and the fine adjustment valve is adjusted to adjust the air pressure in the cavity to the set pressure. Then turning on a power supply to adjust current, heating the hot wire to a set temperature, simultaneously observing the air pressure in the deposition chamber, after deposition is finished, adjusting the temperature of the deposition chamber to cool by adjusting the current, and turning off CH4Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: gas ratio H2:CH498sccm:2.0sccm, with a deposition time of 14 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the diamond layer is 10-30 μm.
(4) The boron-doped diamond layer is vapor-deposited on the surface of the diamond by adopting a hot wire, wherein the hot wire is
Figure BDA0002485553720000091
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (8mm) is adjusted. After the installation is finished, the cabin door is closed, the vacuum pumping is carried out, then hydrogen, methane and borane (diborane used in the experiment is mixed gas of B2H6: H2: 5: 95) are introduced according to the concentration ratio of the gas source set in the experiment, after the reaction gas source is uniformly mixed, the air suction valve is closed, and the fine adjustment valve is adjusted to adjust the air pressure in the cavity to the set pressure. And then turning on a power supply to adjust current, heating the hot wire to a set temperature, observing the air pressure in the deposition chamber, continuously adjusting by using a fine adjustment valve if the air pressure changes, and finally beginning to deposit the boron-doped diamond film. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled by regulating the current to reduce the temperature, and CH is required to be closed at the moment4And B2H6Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate ratio H2:B2H6:CH498sccm, 0.2sccm, 2.0sccm, deposition time 1H, and second-stage gas flow rate ratio H2:B2H6:CH498sccm, 0.4sccm, 2.0sccm, a deposition pressure of 3kPa, a deposition temperature of 850 ℃, a deposition time of 1H, and a third stage, wherein the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and a gas flow rate ratio H is2:B2H6:CH498sccm, 0.6sccm, 2.0sccm, and the deposition time was 2 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 μm.
(5) Placing the obtained high-performance boron-doped diamond film material into a vacuum tube furnace for heat treatment, wherein two ends are not closed, and the pressure is 105Pa, setting the temperature at 800 ℃ and keeping for 60 min.
(6) And (3) directionally and uniformly arranging the foamed diamond reinforcement bodies obtained in the step (5) in a mould, and placing a copper-zirconium alloy 2 times of the volume of the framework of the high-conductivity continuous diamond reinforcement body array above the framework, wherein the mass content of zirconium is 5 wt%. And then putting the 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, keeping the pressure at 5MPa during heat preservation, naturally cooling to room temperature, taking out a sample, removing surface metals through polishing, and cleaning to obtain the composite material.
(7) The prepared composite material is tested for thermal conductivity by a laser flash method, and the thermal conductivity reaches 687W/mK.
Example 2 boron-doped Diamond-reinforced copper-based composite Material (the configuration of the Reinforcement is a coupling of a three-dimensional network configuration and a zero-dimensional particle configuration)
(1) Pretreatment of the substrate: in this example, the three-dimensional network configuration used a copper foam having a pore size of 0.25mm, a diameter of 12.3mm and a thickness of 2.0mm as a substrate, and the zero-dimensional particle configuration used natural diamond particles having an average size of 50 μm. Firstly, cleaning a three-dimensional network substrate of a metal copper framework according to the step (2), and then depositing a chromium film with the thickness of 50nm on the surface of the foamed copper three-dimensional network framework as an intermediate transition layer by adopting a magnetron sputtering technology according to the step (2).
(2) And (2) placing the nano crystal grains and the three-dimensional metal framework substrate in the step (1) into a beaker for mixing, heating to boil, then placing into high-power ultrasonic waves for oscillation, uniformly dispersing, taking out the three-dimensional continuous network framework substrate, and drying to obtain the three-dimensional continuous network framework substrate with a large number of nano crystal grains embedded in meshes. Wherein in the suspension containing the nano-crystalline grains, the mass fraction of the diamond mixed particles is 0.03 percent, and the average size of the nano-crystalline grains is 25 nm. The ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is finished, the metal framework substrate is taken out, washed clean by deionized water and/or absolute ethyl alcohol and dried.
(3) Then, depositing a diamond film on the copper substrate with the three-dimensional configuration adsorbed with the nano diamond particles by adopting chemical vapor deposition, wherein the diamond deposition process comprises the following steps: depositing three-dimensional continuous network diamond on the surface of a foam matrix by adopting hot filament CVD, wherein the used hot filament is a straight tungsten filament with the diameter of 0.5mm, completely covering the straight filament right above a substrate, then putting the pretreated substrate into a cavity of HFCVD equipment, and adjusting the distance (8mm) between the hot filament and a substrate. After the installation is finished, the cabin door is closed to vacuumize, then hydrogen and methane are introduced according to the concentration ratio of the air source set by the experiment, after the reaction air source is uniformly mixed, the air extraction valve is closed, and the fine adjustment valve is adjusted to adjust the air pressure in the cavity to the set pressure. Then turning on a power supply to adjust current, heating the hot wire to a set temperature, simultaneously observing the air pressure in the deposition chamber, after deposition is finished, adjusting the temperature of the deposition chamber to cool by adjusting the current, and turning off CH4Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: gas ratio H2:CH498sccm:2.0sccm, with a deposition time of 14 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the diamond layer is 10-30 μm.
(4): the boron-doped diamond layer is vapor-deposited on the surface of the diamond by adopting a hot wire, wherein the hot wire is
Figure BDA0002485553720000111
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (8mm) is adjusted.After the installation is finished, the cabin door is closed, the vacuum pumping is carried out, and then hydrogen, methane and borane (diborane used for the experiment is B) are introduced according to the concentration ratio of the gas source set by the experiment2H6:H25: 95) when the reaction gas source is uniformly mixed, closing the air extraction valve, and adjusting the fine adjustment valve to adjust the air pressure in the cavity to the set pressure. And then turning on a power supply to adjust current, heating the hot wire to a set temperature, observing the air pressure in the deposition chamber, continuously adjusting by using a fine adjustment valve if the air pressure changes, and finally beginning to deposit the boron-doped diamond film. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled by regulating the current to reduce the temperature, and CH is required to be closed at the moment4And B2H6Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate ratio H2:B2H6:CH498sccm, 0.2sccm, 2.0sccm, deposition time 1H, and second-stage gas flow rate ratio H2:B2H6:CH498sccm, 0.4sccm, 2.0sccm, a deposition pressure of 3kPa, a deposition temperature of 850 ℃, a deposition time of 1H, and a third stage, wherein the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and a gas flow rate ratio H is2:B2H6:CH498sccm, 0.6sccm, 2.0sccm, and the deposition time was 2 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 μm.
(5) And simultaneously placing the obtained high-performance boron-doped diamond film material and boron-doped zero-dimensional diamond grains in a bottle for mixing, heating to boil, 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 grain reinforcement bodies embedded in meshes. Wherein in the suspension containing the zero-dimensional diamond particle reinforcement body, 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. The ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is finished, the three-dimensional network configuration diamond containing the zero-dimensional diamond particles is taken out, washed clean by deionized water and/or absolute ethyl alcohol, and dried.
(6) Placing the obtained high-performance boron-doped diamond film material into a vacuum tube furnace for heat treatment, wherein two ends are not closed, and the pressure is 105Pa, setting the temperature at 800 ℃ and keeping for 60 min.
(7) And (3) directionally and uniformly arranging the foamed diamond reinforcement bodies obtained in the step (5) in a mould, and placing copper-zirconium alloy 2 times of the volume of the framework of the high-conductivity continuous diamond reinforcement body array above the framework, wherein the mass content of zirconium is 0.3 wt%. And then putting the 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, wherein the pressure is 5MPa during heat preservation, then naturally cooling to room temperature, taking out a sample, removing surface metal through polishing, and cleaning to obtain the composite material.
(8) The prepared composite material is tested for thermal conductivity by a laser flash method, and the thermal conductivity is found to reach 795W/mK.
Example 3 boron-doped Diamond-reinforced aluminum matrix composite (Metal matrix is aluminum-titanium alloy, reinforcement configuration is coupling of three-dimensional network configuration and zero-dimensional particle configuration)
(1) Pretreatment of the substrate: in the method, 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 framework as an intermediate transition layer by adopting a magnetron sputtering technology according to the step (2).
(2) And (2) placing the nanocrystalline diamond particles and the three-dimensional continuous network framework substrate in the step (1) in a beaker for mixing, heating to boil, then placing in high-power ultrasonic waves for oscillation, taking out the three-dimensional continuous network framework substrate after uniform dispersion, and drying to obtain the three-dimensional continuous network framework substrate with a large number of nanocrystalline and microcrystalline diamond particles embedded in meshes. Wherein in the suspension containing the nanocrystalline and/or microcrystalline diamond mixed particles, the mass fraction of the diamond mixed particles is 0.01%, the ultrasonic oscillation treatment time is 30min, after the ultrasonic treatment is finished, the foam diamond is taken out, washed clean by deionized water and/or absolute ethyl alcohol, and then dried.
(3) Then, depositing a diamond film on the copper substrate with the three-dimensional configuration adsorbed with the nano diamond particles by adopting chemical vapor deposition, wherein the diamond deposition process comprises the following steps: depositing three-dimensional continuous network diamond on the surface of a foam matrix by adopting hot filament CVD, wherein the used hot filament is a straight tungsten filament with the diameter of 0.5mm, completely covering the straight filament right above a substrate, then putting the pretreated substrate into a cavity of HFCVD equipment, and adjusting the distance (8mm) between the hot filament and a substrate. After the installation is finished, the cabin door is closed to vacuumize, then hydrogen and methane are introduced according to the concentration ratio of the air source set by the experiment, after the reaction air source is uniformly mixed, the air extraction valve is closed, and the fine adjustment valve is adjusted to adjust the air pressure in the cavity to the set pressure. And then turning on a power supply to adjust current, heating the hot wire to a set temperature, simultaneously observing the air pressure in the deposition chamber, after the deposition is finished, adjusting the temperature of the deposition chamber to reduce the temperature by adjusting the current, turning off CH4 at the moment, and etching the graphite phase on the surface of the diamond by using H2 only. Deposition parameters used in this example: the gas ratio H2: CH4 was 98sccm:2.0sccm, and the 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 boron-doped diamond layer is vapor-deposited on the surface of the diamond by adopting a hot wire, wherein the hot wire is
Figure BDA0002485553720000131
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (8mm) is adjusted. After the installation is finished, the cabin door is closed, the vacuum pumping is carried out, and then hydrogen, methane and borane (diborane used for the experiment is B) are introduced according to the concentration ratio of the gas source set by the experiment2H6:H25: 95) when the reaction gas source is uniformly mixed, closing the air extraction valve, and adjusting the fine adjustment valve to adjust the air pressure in the cavity to the set pressure. And then turning on a power supply to adjust current, heating the hot wire to a set temperature, observing the air pressure in the deposition chamber, continuously adjusting by using a fine adjustment valve if the air pressure changes, and finally beginning to deposit the boron-doped diamond film. Is deposited completelyAfter the deposition is finished, the temperature of the deposition chamber is regulated and controlled to be reduced by regulating the current, and CH is required to be closed at the moment4And B2H6Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are: in the first stage, the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and the gas flow rate ratio H2:B2H6:CH498sccm, 0.2sccm, 2.0sccm, deposition time 1H, and second-stage gas flow rate ratio H2:B2H6:CH498sccm, 0.4sccm, 2.0sccm, a deposition pressure of 3kPa, a deposition temperature of 850 ℃, a deposition time of 1H, and a third stage, wherein the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and a gas flow rate ratio H is2:B2H6:CH498sccm, 0.6sccm, 2.0sccm, and the deposition time was 2 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 μm.
(5) And simultaneously placing the obtained high-performance boron-doped diamond film material and boron-doped zero-dimensional diamond grains in a bottle for mixing, heating to boil, 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 grain reinforcement bodies embedded in meshes. Wherein in the suspension containing the zero-dimensional diamond particle reinforcement body, 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. The ultrasonic vibration treatment time is 30min, after the ultrasonic treatment is finished, the three-dimensional network configuration diamond containing the zero-dimensional diamond particles is taken out, washed clean by deionized water and/or absolute ethyl alcohol, and dried.
(6) Placing the obtained high-performance boron-doped diamond film material into a vacuum tube furnace for heat treatment, wherein two ends are not closed, and the pressure is 105Pa, setting the temperature at 800 ℃ and keeping for 60 min.
(6) The obtained foam diamond reinforcements are directionally and uniformly arranged in a mould, aluminum-titanium alloy which is 2 times of the volume of the framework of the high-conductivity continuous diamond reinforcement array is placed above the framework, wherein the mass content of metallic titanium is 0.2 wt%, then a grinding tool is placed in an infiltration device, the heating temperature is set to 1350 ℃, the heating rate is 12 ℃ per minute, the temperature is finally kept at 1350 ℃ for 30 minutes, the pressure is 5MPa during the heat preservation, then the sample is naturally cooled to the room temperature, the surface metal is removed through polishing, and the composite material is obtained after cleaning.
(7) According to the prepared composite material, the volume fraction of the foam diamond reinforcement body is 15 vol%, and the thermal conductivity is tested by a laser flash method and is found to reach 738W/mK.
Example 4 boron-doped Diamond-reinforced aluminum matrix composite (the configuration of the reinforcement is zero-dimensional particle configuration)
(1) Placing diamond particles with the particle size of 80 microns into the solution, carrying out ultrasonic oscillation treatment for 10min, taking out the diamond particles after the ultrasonic treatment is finished, washing the diamond particles by using deionized water and/or absolute ethyl alcohol, and drying the diamond particles.
(2) The boron-doped diamond layer is vapor-deposited on the surface of the diamond by adopting a hot wire, wherein the hot wire is
Figure BDA0002485553720000141
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (8mm) is adjusted. After the installation is finished, the cabin door is closed, the vacuum pumping is carried out, and then hydrogen, methane and borane (diborane used for the experiment is B) are introduced according to the concentration ratio of the gas source set by the experiment2H6:H25: 95) when the reaction gas source is uniformly mixed, closing the air extraction valve, and adjusting the fine adjustment valve to adjust the air pressure in the cavity to the set pressure. And then turning on a power supply to adjust current, heating the hot wire to a set temperature, observing the air pressure in the deposition chamber, continuously adjusting by using a fine adjustment valve if the air pressure changes, and finally beginning to deposit the boron-doped diamond film. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled by regulating the current to reduce the temperature, and CH is required to be closed at the moment4And B2H6Using only H2To etch the graphite phase of the diamond surface. Deposition parameters used in this example: the specific deposition parameters are: in the first stage, the deposition pressure is 3kPa, and deposition is carried outThe temperature is 850 ℃, and the gas flow rate ratio H2:B2H6:CH498sccm, 0.2sccm, 2.0sccm, deposition time 1H, and second-stage gas flow rate ratio H2:B2H6:CH498sccm, 0.4sccm, 2.0sccm, a deposition pressure of 3kPa, a deposition temperature of 850 ℃, a deposition time of 1H, and a third stage, wherein the deposition pressure is 3kPa, the deposition temperature is 850 ℃, and a gas flow rate ratio H is2:B2H6:CH498sccm, 0.6sccm, 2.0sccm, and the deposition time was 2 h. The deposition pressure is 3kPa, and the deposition temperature is 850 ℃; the thickness of the boron-doped diamond film layer is 2 μm.
(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 are not closed, the pressure is 105Pa, the set temperature is 800 ℃, and the temperature is kept for 60 min.
(4) And (3) stacking the particle diamond reinforcement die obtained in the step (3), and placing an aluminum-titanium alloy which is 2 times of the volume of the particle skeleton of the diamond reinforcement above the grinding tool, wherein the mass content of titanium is 0.3 wt%. And then putting the grinding tool into an infiltration device, setting the heating temperature to 780 ℃, 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
The other conditions are the same as example 1, but no boron-doped diamond layer is deposited on the surface of the high-purity diamond layer, the W coating with the same thickness is used for modification, and the finally measured thermal conductivity of the prepared composite material is 595W/mk, which is lower than that of the prepared boron-doped diamond reinforced copper-based composite material (687W/mk)
Comparative example 2
The other conditions were the same as example 1, but no modification layer was deposited on the surface of the high-purity diamond layer, and the mass fraction of Zr in the copper-zirconium alloy was 1.0 wt%, and the prepared composite material finally measured a thermal conductivity of 602W/mk, which was lower than that of the prepared boron-doped diamond-reinforced copper-based composite material (687W/mk).
Comparative example 3
The other conditions are the same as the example 1, only when the diamond layer is deposited, the gradient boron deposition is not carried out, only one-section deposition is adopted, and H is controlled during the deposition2:B2H6:CH4The prepared composite material finally measured a thermal conductivity of 603W/mk, 98sccm:0.4sccm:2.0 sccm. Lower than the thermal conductivity (687W/mk) of the composite material prepared in example 1.
Comparative example 4
The other conditions are the same as those of the example 3, but no modified layer is deposited on the surface of the high-purity diamond layer, the mass fraction of Ti in the aluminum-titanium alloy is 1.0 wt%, and the prepared composite material finally has the measured thermal conductivity of 620W/mk which is lower than that of the prepared boron-doped diamond reinforced copper-based composite material (738W/mk).

Claims (10)

1. A gradient boron-doped diamond enhanced metal matrix composite material is characterized in that: the composite material comprises a gradient boron-doped diamond reinforcement body and a metal matrix; the gradient boron-doped diamond reinforcement body comprises an undoped diamond reinforcement body and a gradient boron-doped diamond modification layer arranged on the surface of the diamond reinforcement body.
2. The gradient boron doped diamond enhanced metal matrix composite of claim 1, wherein: the configuration of the diamond reinforcement body comprises one or more of zero-dimensional particle configuration, one-dimensional linear configuration, two-dimensional sheet configuration and three-dimensional continuous network framework configuration;
the diamond reinforcement body with the zero-dimensional particle configuration is pure diamond or natural diamond prepared by a high-temperature high-pressure method; the diamond reinforcement bodies with one-dimensional linear configuration, two-dimensional sheet configuration and three-dimensional continuous network framework configuration are obtained by chemical vapor deposition on the surface of the substrate with corresponding configuration;
the gradient boron-doped diamond modified layer is deposited on the surface of the diamond reinforcing body through chemical vapor deposition.
3. The gradient boron doped diamond enhanced metal matrix composite of claim 1, wherein: 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, wherein the boron content of the boron-doped diamond bottom layer is increased in a gradient manner; in the boron-doped diamond bottom layer, the B/C is 3333-8332ppm in terms of atomic ratio; in the boron-doped diamond middle layer, the B/C is 9999-15000ppm in terms of atomic ratio; in the boron-doped diamond top layer, the B/C is 16665-21665ppm by atomic ratio.
4. The gradient boron doped diamond enhanced metal matrix composite of claim 1, wherein: the volume fraction of the gradient boron-doped diamond modified layer in the gradient boron-doped diamond reinforcement body is less than or equal to 3 percent.
5. The gradient boron doped diamond enhanced metal matrix composite of claim 1, wherein: the metal matrix comprises one or more of Al, Mg, Cu, Ag and Zn;
the surface or the metal matrix of the gradient boron-doped diamond reinforcing body also contains a small amount of alloying elements capable of forming carbide, and the alloying elements are selected from one or more of B, Si, Ti, Cr, Zr, Nb, Ta, W and Mo.
6. The gradient boron doped diamond enhanced metal matrix composite of claim 2, wherein: the configuration of the diamond reinforcement body is a three-dimensional continuous network framework configuration and a zero-dimensional particle configuration;
wherein the volume fraction of the diamond reinforcement body with the three-dimensional continuous network framework configuration in the gradient boron-doped diamond-reinforced metal-based composite material is 10-40%, preferably 10-20 vol%; the volume fraction of the diamond reinforcement body with the zero-dimensional particle configuration in the gradient boron-doped diamond-reinforced metal matrix composite material is 10-40%, preferably 10-25 vol%, and the particle size of the diamond reinforcement body with the zero-dimensional particle configuration is 10-80 μm;
the diamond reinforcement body with the three-dimensional continuous network framework structure comprises a three-dimensional continuous network metal framework and a diamond layer arranged on the surface of the three-dimensional continuous network metal framework;
the metal in the three-dimensional continuous network metal skeleton 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 or randomly distributed; the three-dimensional continuous network metal framework structure is a plane structure or a three-dimensional structure;
the diamond reinforcement body with the three-dimensional continuous network framework structure also comprises a transition layer, wherein the transition layer is positioned between the three-dimensional continuous network metal framework and the diamond layer; the transition layer is made of one or more of nickel, niobium, tantalum, titanium, cobalt, tungsten, molybdenum and chromium, and has a thickness of 0.5-30 μm.
7. A method of making a gradient boron doped diamond enhanced metal matrix composite as claimed in claim 6, wherein: the method comprises the following steps:
step one, planting seed crystal by three-dimensional continuous network metal framework
Placing the three-dimensional continuous network metal framework or the three-dimensional continuous network metal framework provided with the transition layer into a suspension containing nanocrystalline diamond particles, heating to boil, performing ultrasonic treatment, and drying; obtaining a three-dimensional continuous network metal framework with nanocrystalline diamond particles adsorbed on the surface;
step two, depositing a diamond layer
Placing the three-dimensional continuous network metal framework with the nanocrystalline diamond particles adsorbed on the surface, which is obtained in the step one, in a chemical vapor deposition furnace for diamond layer deposition, wherein the deposition parameters are as follows: the mass flow percentage of the carbon-containing gas in the total gas in the furnace is 0.5-10.0%; the deposition temperature is 600-1000 ℃, and the deposition pressure is 10 DEG3-104Pa; the deposition time is 12-24 h;
step three, depositing a gradient boron-doped diamond modified layer
Placing the three-dimensional continuous network metal framework deposited with the diamond layer in the chemical vapor deposition furnace, and performing three-stage deposition to obtain a gradient boron-doped diamond modified layer, wherein during the first-stage deposition, the mass flow of carbon-containing gas accounts for 0.5-10% of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005-0.0075%; the deposition temperature of the first section is 600-1000 ℃, and the air pressure is 103-104Pa, the time is 0.5-1.0 h; during the second-stage deposition, the mass flow percentage of the carbon-containing gas in the furnace is 0.5-10%; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.015-0.0225%, the temperature of the second-stage deposition is 600-1000 ℃, and the gas pressure is 103-104Pa for 0.5-1.0h, and during the third stage of deposition, the carbon-containing gas accounts for 0.5-10% of the mass flow of the whole gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.025-0.0325%; the temperature of the third stage deposition is 600-1000 ℃, and the air pressure is 103-104Pa; the time is 1.0 to 2.0 hours; etching the boron-doped diamond layer at the temperature of 700-900 ℃ in a hydrogen atmosphere after the deposition is finished; obtaining a gradient boron-doped diamond reinforcement body with a three-dimensional continuous network framework configuration;
step four, adding the diamond reinforcement body with the zero-dimensional particle configuration
Placing the gradient boron-doped diamond reinforcement body with the three-dimensional continuous network skeleton configuration obtained in the third step into suspension of the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration; heating to boiling, performing ultrasonic treatment, drying to enable the gradient boron-doped diamond reinforcement body with the zero-dimensional particle configuration to be embedded in the pores of the gradient boron-doped diamond reinforcement body with the three-dimensional continuous network framework configuration,
step five, heat treatment
Carrying out heat treatment on the diamond reinforcement body with the three-dimensional continuous network framework configuration obtained in the fourth step in the air atmosphere to obtain an activated gradient boron-doped diamond reinforcement body;
step six, compounding the gradient boron-doped diamond reinforcement body with the metal matrix
And infiltrating metal into the activated gradient boron-doped diamond reinforcement body by adopting a pressure infiltration process, and cooling to obtain the gradient boron-doped diamond reinforced metal-based composite material.
8. The method of claim 7, wherein the step of preparing the gradient boron-doped diamond enhanced metal matrix composite material comprises the steps of: in the first step; 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 10-100 nm; in the first step; the ultrasonic vibration treatment time is 5-30 min;
in the fourth step, in the suspension containing the gradient boron-doped diamond reinforcement with the zero-dimensional particle configuration, the mass fraction of the gradient boron-doped diamond reinforcement with the zero-dimensional particle configuration is 0.01-0.1%, and the size of the gradient boron-doped diamond reinforcement with the zero-dimensional particle configuration is 10-80 μm;
step five, the heat treatment temperature is 700-; the pressure in the furnace is 10Pa-105Pa。
9. The method of claim 7, wherein the step of preparing the gradient boron-doped diamond enhanced metal matrix composite material comprises the steps of: in the sixth step, the metal infiltration process comprises the following steps: placing metal above the activated gradient boron-doped diamond reinforcement, 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.
10. Use of a gradient boron doped diamond enhanced metal matrix composite according to any one of claims 1 to 6, wherein: the gradient boron-doped diamond reinforced metal matrix composite material is used for an electronic packaging material.
CN202010390535.XA 2020-05-11 2020-05-11 Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof Active CN111778506B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010390535.XA CN111778506B (en) 2020-05-11 2020-05-11 Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010390535.XA CN111778506B (en) 2020-05-11 2020-05-11 Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111778506A true CN111778506A (en) 2020-10-16
CN111778506B CN111778506B (en) 2023-10-03

Family

ID=72753242

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010390535.XA Active CN111778506B (en) 2020-05-11 2020-05-11 Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111778506B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981365A (en) * 2021-04-20 2021-06-18 北京科技大学 Preparation method of mesh cage multilayer structure boron-doped diamond electrode
CN113770381A (en) * 2021-09-15 2021-12-10 中南大学 3D printing diamond/metal matrix composite material and preparation method and application thereof
CN113802180A (en) * 2021-09-15 2021-12-17 中南大学 Diamond/metal-based composite material and preparation method and application thereof
WO2023064972A1 (en) 2021-10-22 2023-04-27 Carboncompetence Gmbh Apparatus and method for producing doped diamond layers

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: "《纳米氧化锌与金刚石复合结构的研究与应用》", 30 August 2016, 北京：北京邮电大学出版社, pages: 28 - 29 *
邹建新等: "《钒钛功能材料》", 31 March 2019, 北京：冶金工艺出版社, pages: 108 - 109 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981365A (en) * 2021-04-20 2021-06-18 北京科技大学 Preparation method of mesh cage multilayer structure boron-doped diamond electrode
CN113770381A (en) * 2021-09-15 2021-12-10 中南大学 3D printing diamond/metal matrix composite material and preparation method and application thereof
CN113802180A (en) * 2021-09-15 2021-12-17 中南大学 Diamond/metal-based composite material and preparation method and application thereof
WO2023064972A1 (en) 2021-10-22 2023-04-27 Carboncompetence Gmbh Apparatus and method for producing doped diamond layers

Also Published As

Publication number Publication date
CN111778506B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN111471978B (en) High-volume diamond-reinforced metal-based composite material and preparation method and application thereof
CN111778506A (en) Gradient boron-doped diamond enhanced metal matrix composite material and preparation method and application thereof
CN105779804B (en) A kind of foam framework structure enhancing metal-base composites and preparation method
Zhang et al. Construction of 3D interconnected diamond networks in Al-matrix composite for high-efficiency thermal management
US10995192B2 (en) Composite material reinforced by foamed skeleton and preparation method and uses thereof
CN105112754B (en) Three-dimensional network diamond framework strengthens metal-base composites and preparation method
CN105603265B (en) Foamy graphite alkene skeleton reinforced aluminum matrix composites and preparation method thereof
CN105671354B (en) A kind of foam diamond framework reinforced aluminum matrix composites and preparation method thereof
CN105603248B (en) A kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method
CN105779805B (en) Foam diamond framework strengthens Cu-base composites and preparation method
CN105220049B (en) A kind of lamellar diamond reinforced metal-base composite material and preparation method
CN110241325B (en) Titanium metal graphite flake reinforced aluminum-based composite material and preparation method and application thereof
CN105543803B (en) A kind of the diamond/carbon boron composite coating and preparation method of cemented carbide substrate
CN110724845A (en) Diamond/aluminum composite material with high heat conductivity and high reliability and preparation process thereof
Zhan et al. Fabrication of graphite/Cu composite foils with ultrahigh thermal conductivity by adding an intermediate nickel layer and vacuum hot pressing treatment
CN108611638A (en) High wear resistance ratio, high fracture strength micron diamond thick film and preparation method thereof
CN110846617B (en) Copper-zirconium-aluminum ternary amorphous alloy film and preparation method thereof
CN111945027A (en) Method for strengthening GNPs/Ti composite material interface combination by directional growth of TiBw
CN113758326B (en) VC radiator with built-in copper/diamond composite-configuration liquid absorption core and preparation method thereof
CN111647873B (en) Three-dimensional continuous network hydrophilic boron-doped diamond heat radiator and preparation method and application thereof
CN112142440A (en) Diamond film radiating fin and preparation method thereof
US20230052246A1 (en) Composite vc heat sink containing copper/diamond composite wick structure and method for preparing same
Zhou et al. A review of diamond interfacial modification and its effect on the properties of diamond/Cu matrix composites
Dou et al. Lightweight diamond/Cu interface tuning for outstanding heat conduction
Liu et al. Preparation of diamond/Cu microchannel heat sink by chemical vapor deposition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant