CN112863722B - Cladding material/nanocrystalline/carbon nanotube composite structure material and preparation method thereof - Google Patents

Cladding material/nanocrystalline/carbon nanotube composite structure material and preparation method thereof Download PDF

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CN112863722B
CN112863722B CN201911185896.4A CN201911185896A CN112863722B CN 112863722 B CN112863722 B CN 112863722B CN 201911185896 A CN201911185896 A CN 201911185896A CN 112863722 B CN112863722 B CN 112863722B
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nanocrystalline
carbon nanotube
cladding material
temperature
carbon
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CN112863722A (en
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邰凯平
毛鹏燕
崔刊
乔吉祥
赵洋
康斯清
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Institute of Metal Research of CAS
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Abstract

The invention belongs to the fields of composite materials and radiation damage resistant materials, and particularly relates to a cladding material/nanocrystalline/carbon nanotube composite structure material and a preparation method thereof. The composite material comprises: the self-supporting CNTs are taken as a matrix, and nano crystals and a high-temperature stable cladding material are uniformly attached to the surface of the CNTs. The preparation method comprises the following steps: uniformly depositing nanocrystals on a CNTs substrate at a temperature of 20-800 ℃ by using a physical or chemical vapor deposition method; and then physical or chemical vapor deposition, pyrolysis of organic matters and other techniques are utilized to deposit amorphous carbon or metal oxide with high temperature stability. The composite material has a high-density nanowire structure, high conductivity, good irradiation resistance, high-temperature heat stability, chemical stability and flexible bending performance, can be prepared in a large area, and can be spread on the surface of an object with any curvature. The invention is used for electronic devices and sensor materials working at medium and high temperature, and the like, and can also be used as a protective layer material for the irradiation damage field.

Description

Cladding material/nanocrystalline/carbon nanotube composite structure material and preparation method thereof
Technical Field
The invention relates to the field of composite materials and radiation damage resistant materials, in particular to a structural design and a preparation method of a high-stability cladding material (such as amorphous Carbon or metal oxide) with a three-layer nanofiber network structure/nanocrystalline/Carbon Nanotubes (CNTs) composite material.
Background
Energy transformation is an important mark of the progress of human civilization, and in the 21 st century, human beings are gradually transforming from an energy system mainly using fossil energy to a clean, low-carbon, safe and efficient energy system. China is the largest developing country in the world, supports sustainable development of socioeconomic, and actively advances to transform a green clean low-carbon energy system into a new historical mission. The nuclear power is one of three main props of world energy because of safety, cleanness, reliability and high efficiency, and is the only basic energy source capable of replacing thermal power in large scale in the long term. The development of nuclear power has important significance for guaranteeing national energy safety, adjusting energy structure, improving atmospheric environment, improving the equipment manufacturing level in China and promoting technological progress.
In order to further improve the utilization rate of nuclear fuel and the running economy, safety and stability of the nuclear power station, on one hand, the second-generation and third-generation nuclear reactors in service and in construction at present are to be improved and upgraded, and on the other hand, the fourth-generation nuclear reactors and the controllable nuclear fusion reactors are also under intense research and development in countries around the world. This places more stringent demands on the core structural materials of the nuclear reactor, such as: the operating temperature of the fourth generation nuclear reactor core is up to 500-1000 ℃, the irradiation damage dose exceeds 150dpa (displacement per atom), while the operating temperature of the first wall of the commercial fusion reactor is expected to be above 1000 ℃, and the nuclear reactor core is also exposed to the irradiation of neutrons with energy up to 14MeV and the high-flux deuterium, tritium and helium plasma impact. The development of a novel efficient nuclear reactor is necessary to develop nuclear materials which can be stably used for a long time under extreme conditions such as high temperature and high pressure, stress, strong irradiation and the like, and the existing materials are difficult to meet the requirements. Radiation damage is the most special and difficult problem faced by nuclear materials, and the radiation damage resistance of the materials directly affects the reliability and safety of nuclear reactor operation. The development of new materials with excellent radiation damage resistance is one of the most urgent and troublesome problems facing the nuclear energy field at present.
Disclosure of Invention
In order to solve the problem of developing a high-performance radiation damage resistant material, the invention aims to provide a cladding material/nanocrystalline/Carbon Nanotubes (CNTs) composite material and a preparation method thereof, wherein the composite material has a high-density nanowire structure, and can maintain extremely high structural stability under a high-temperature condition; meanwhile, under high-energy ion irradiation, the composite material also has good radiation damage resistance and flexible bending performance, and can be spread on the surface of an object with any curvature. The composite material can be prepared in a large area, can be used for electronic devices and sensor materials working at medium and high temperature, and can also be used as a protective layer material for the irradiation damage field.
The technical scheme of the invention is as follows:
the self-supporting carbon nanotube substrate is of a single-wall carbon nanotube film tube bundle structure, nano crystals are uniformly deposited on the surface by utilizing a physical vapor deposition technology or a chemical vapor deposition technology, and then a cladding material layer is deposited by utilizing the physical vapor deposition technology, the chemical vapor deposition technology or a pyrolysis organic matter vapor technology, so that a three-layer composite three-dimensional network composite material with a nano-scale fiber structure, high conductivity and structural stability is formed; wherein, the volume fraction of the carbon nano tube film tube bundle matrix is 5-30%.
The cladding material/nano-crystal/carbon nano-tube composite structure material takes a bundle of carbon nano-tube film as a matrix, and is composed of bundle-shaped carbon nano-tubes which are randomly oriented and distributed and have diameters of 2-20 nm, and the length of the carbon nano-tubes in the carbon nano-tube film is 5-50 mu m.
The cladding material/nanocrystalline/carbon nanotube composite structure material is depositedThe deposited nano-crystal is Al, cu, ni, fe, nb, W high-purity metal or alloy or nonmetal nano-crystal material; for Cu or Ni high-purity metal nanocrystalline, the composite material has higher conductivity, and the conductivity in the range of 25 ℃ to 600 ℃ is 1 multiplied by 10 6 ～5×10 6 S·m -1 。
The cladding material/nanocrystalline/carbon nanotube composite structure material has the advantages that the thickness of the nanocrystalline deposited on the surface of the carbon nanotube is uniform, the nanocrystalline is randomly oriented and distributed, the grain size is 10-300 nm, the grain size in the direction perpendicular to the axis of the carbon nanotube is 30-500 nm, and the thickness and the grain size of the nanocrystalline can be continuously regulated and controlled.
The thickness of the deposited cladding material layer of the cladding material/nanocrystalline/carbon nanotube composite structure material is 1-50 nm, the thickness of the cladding material layer can be regulated and controlled uniformly and continuously, and the cladding material is amorphous Al 2 O 3 Amorphous carbon or other high strength, high melting point, chemically inert, high temperature stable materials.
The cladding material/nanocrystalline/carbon nanotube composite structure material has good interface combination among the carbon nanotube matrix, the nanocrystalline and the cladding material layer, and does not generate interface detachment or cracking under the conditions of repeated bending and vibration; the composite material has good structural thermal stability, and can still keep the initial morphology above the recrystallization temperature of the nanocrystals, and the nanocrystals do not have obvious agglomeration and grain growth; the composite material has higher flexibility, is spread on the surface of an object with any curvature, realizes large-scale preparation of reel-to-reel, and is cut into any size by laser processing.
The cladding material/nanocrystalline/carbon nanotube composite structure material has good performance of resisting high-energy particle irradiation damage, and the composite material does not generate observable structural instability after being irradiated by 50 keV-5 MeV high-energy particles with the dose of 1 dpa-10 dpa at the temperature of 25-500 ℃, wherein the high-energy particles are He ions, ni ions or Fe ions.
The preparation method of the cladding material/nanocrystalline/carbon nanotube composite structure material comprises the following specific steps:
(S1) self-supporting carbon nanotube substrate preparation:
preparing a metal bracket, wherein the bracket material is a high-heat-conductivity high-temperature-resistant material, and Mo, ti, cu or alloy materials thereof are adopted; carrying out ultrasonic cleaning treatment on a surface solution, wherein the cleaning solution comprises acetone, alcohol and deionized water, and then transferring the carbon nanotube film substrate onto a metal bracket to form a suspension state;
(S2) mounting a metal bracket:
fixing the metal bracket carrying the carbon nano tube after being cleaned in the step (S1) on a sample stage of a thin film deposition device, and adhering the metal bracket by using conductive silver adhesive to ensure that the bracket and the sample stage are in good thermal contact, wherein the distance between the metal bracket and a deposition target is 5-20 cm;
(S3) carrying out high-temperature treatment on the carbon nano tube substrate in a high-vacuum environment:
in a magnetron sputtering deposition system: background vacuum degree (1-3). Times.10 -5 Pa, introducing high-purity argon with the flow of 30-50 sccm, heating the carbon nano tube substrate at 500-800 ℃ for 1-2 h, and fully removing impurity atoms adsorbed on the surface;
(S4) depositing metal nanocrystals:
single-target or multi-target sputtering is carried out in a magnetron sputtering deposition system, pure metal or alloy nanocrystalline is deposited, and the growth conditions are as follows: the sputtering target material is commercial block high-purity target material, and the background vacuum degree is (1-3) multiplied by 10 -5 Pa, high-purity argon with working gas of 0.1-3 Pa, growth temperature of 20-800 ℃, deposition rate of 0.1-5 mu m/h, deposition power of 10-300W, and rotation speed of the metal bracket of 1-20 r/min to form the nanocrystalline/carbon nanotube composite material;
(S5) uniformly depositing a high-stability cladding material layer:
the cladding material has the characteristics of high strength, high melting point, chemical inertness and high temperature stability, and adopts amorphous Al 2 O 3 Or amorphous carbon material, and thus can dynamically stabilize the inner layer of the nanocrystalline material.
In the preparation method of the cladding material/nanocrystalline/carbon nanotube composite structure material, in the step (S4), after magnetron sputtering deposition, annealing is carried out at the temperature of 100-800 ℃ for 1-10 h; in the step (S5), after the high-stability cladding material layer is uniformly deposited, annealing is carried out at the temperature of 100-800 ℃ for 1-10 h.
The preparation method of the cladding material/nanocrystalline/carbon nanotube composite structure material comprises the following steps of (S5):
amorphous Al 2 O 3 Deposition is carried out by adopting an atomic layer deposition system, and the precursor is commercial Al (CH) 3 ) 3 The working gas is high-purity argon with the pressure of 0.1-1 MPa, the deposition temperature range is 50-300 ℃, and the deposition rate is 0.1-1 nm/min;
amorphous carbon is prepared by a method of cracking organic matters by high-energy ions, and the background vacuum degree is 1-3 multiplied by 10 in a high vacuum environment -5 Pa, the deposition temperature range is 20-800 ℃, and 200-400 keV helium ions are utilized for cracking for 1-15 h.
The design idea of the invention is as follows:
firstly, for the polycrystalline nanowire material, crystal grains grow up to form a bamboo joint structure at high temperature, then a crystal boundary groove effect is generated, crystal boundaries are necked until spheroidized fracture occurs through surface diffusion, and poor inherent form stability is shown, which is unfavorable for circuit connection in a medium-high temperature electronic device and prevents the polycrystalline nanowire material from being applied to the irradiation damage field as a protective layer material. Therefore, after the nanocrystalline material is uniformly deposited on the surfaces of CNTs, a layer of uniform high-stability cladding material is deposited on the surfaces of CNTs by utilizing the technologies of physical or chemical vapor deposition, cracking organic matters and the like, and the high-stability circuit connection is realized by means of the good high-temperature stability of the cladding material and the regulation and control of the interfacial energy and grain boundary energy among the cladding material, the nanocrystalline and the CNTs, so that the nanocrystalline material in a metastable state has good high-temperature structural stability and good high-energy particle irradiation damage resistance, and the application prospect in the fields of electronic devices, sensor materials and the like working at medium and high temperatures can be foreseen. And secondly, the high-stability cladding material/nanocrystalline/Carbon Nano Tubes (CNTs) composite material can realize roll-to-roll large-area preparation, can be used as a nuclear reactor shielding coating material, prolongs the service life of a nuclear reactor, and improves the economy, reliability, perpetual motion performance and safety of the nuclear reactor.
Based on the main guiding design ideas of the two points, the invention successfully realizes that ultrathin CNTs film materials are used as a matrix, various nanocrystalline film materials are deposited by using a physical or chemical vapor deposition technology, a layer of high-stability cladding material is wrapped on the surface of the nanocrystalline film materials, and the roll-to-roll large-scale preparation can be realized, so that the structural stability, the oxidation resistance and the irradiation damage resistance of the nanocrystalline film materials are greatly improved.
The invention has the advantages and beneficial effects as follows:
1. the invention can be used for various nanocrystalline film materials by utilizing physical or chemical vapor deposition technology, such as: cu, ni, fe, nb, W, etc., and alloys thereof, or nanocrystals of non-metallic materials. Further, physical or chemical vapor deposition, pyrolysis of organic matter and other techniques are utilized to deposit amorphous carbon or metal oxide with high temperature stability.
2. The composite material provided by the invention has excellent capability of retarding crack growth in microcosmic, has certain flexible deformation capability, has good interface combination among CNTs matrix, nanocrystalline and cladding material layers, and can not generate interface detachment or cracking phenomenon under the conditions of repeated bending and vibration.
3. The composite material provided by the invention has good structural thermal stability, can still keep the initial morphology above the recrystallization temperature of the nanocrystals, does not generate obvious agglomeration and grain growth of the nanocrystals, and can realize circuit connection in medium-high temperature electronic devices.
4. The composite material provided by the invention has a high-density nanowire structure, high conductivity, good irradiation resistance, high-temperature heat stability, chemical stability and flexible bending property, and can be spread on the surface of an object with any curvature.
5. The composite material can be prepared in a large area, can be used for electronic devices and sensor materials working at medium and high temperature, and can also be used as a protective layer material for the irradiation damage field.
Drawings
Fig. 1 (a) is a schematic diagram of a three-layer structure of a composite nanofiber. In the figure, a shell material layer 1, a nanocrystalline layer 2 and a carbon nanotube film tube bundle matrix 3 are shown.
Fig. 1 (b) is a flow chart of the preparation of a composite material.
FIG. 2 (a) is a transmission electron micrograph of a magnetron sputter deposited CNTs/Cu composite film sample.
FIG. 2 (b) is a transmission electron micrograph of a magnetron sputter deposited CNTs/Cu composite film sample after 400 ℃ annealing.
FIG. 3 (a) is a transmission electron micrograph of an amorphous C/Cu/CNTs composite.
FIG. 3 (b) is a transmission electron micrograph of an amorphous C/Cu/CNTs composite after 400 ℃ annealing.
Detailed Description
As shown in fig. 1 (a), the composite material comprises an ultrathin carbon nanotube film bundle matrix 3 and a nanocrystalline layer 2 uniformly deposited on the surface of the carbon nanotube film bundle matrix 3, wherein a cladding material layer 1 with high stability, high strength and high melting point is deposited by using a physical and chemical vapor deposition technology, a pyrolysis organic matter technology and the like, so that a three-layer composite three-dimensional network composite material with a nanoscale fiber structure, high conductivity and structural stability is formed.
The preparation method comprises the following steps: uniformly depositing nano-crystals on a CNTs substrate at the temperature of 20-800 ℃ under the pressure of 0.1-3 Pa by using a physical or chemical vapor deposition method, and depositing a high-melting-point cladding material layer by using the technologies of physical or chemical vapor deposition, cracking organic matters and the like. Self-supporting Carbon Nanotubes (CNTs) are used as a matrix, and nanocrystalline and a high-strength high-melting-point cladding material layer are uniformly attached to the surface of the matrix. The invention combines physical and vapor deposition techniques, and can be used for various nanocrystalline thin film materials, such as: cu, ni, fe, nb, W, etc., and their alloys or nonmetallic nanocrystals.
The CNTs matrix, the nanocrystalline and the cladding material are well combined at the interface, and the phenomenon of interface detachment or cracking does not occur under the condition of repeated bending and vibration. The composite material has good structural thermal stability, and can still keep the initial morphology above the recrystallization temperature of the nanocrystals, and the nanocrystals do not obviously agglomerate and grow up. The composite material has good performance of resisting high-energy particle irradiation damage, and no observable structural instability occurs after the composite material is irradiated by high-energy particles (such as He, ni, fe ions and the like) with the energy of 50 keV-5 MeV for 1 dpa-10 dpa at the temperature of 25-500 ℃. The composite material can realize large-area preparation of reel-to-reel, can be used for circuit connection of medium-high temperature electronic devices, and can also be used as a protective layer material to be applied to the field of irradiation damage.
The core idea of the invention is that by introducing a uniform high-melting-point cladding material with higher stability in the processes of physical or chemical vapor deposition and cracking of organic matters, the grain boundary trench effect of the composite material at high temperature is inhibited, and the atomic diffusion of atoms at the interface of the cladding material and the nanocrystalline material is inhibited. The surface energy, the interface energy and the grain boundary energy of the interface between the shell material and the nanocrystalline material can be regulated, so that the structural stability of the nanocrystalline under the high-temperature or strong ion irradiation condition is maintained, and the practical application of the shell material in medium-high temperature electronic devices is realized. The composite material will enable a "roll-to-roll" large scale preparation, which can be used as a large coating material, for example: as a nuclear reactor shielding coating material, the service life of the nuclear reactor is prolonged, and the economy, reliability, perpetual motion performance and safety of the nuclear reactor are improved.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Examples
Referring to fig. 1 (b), the amorphous carbon (C)/Cu/CNTs composite material is used in this example, and the preparation process is as follows: preparing a metal bracket, transferring a self-supporting CNTs film, depositing a nanocrystalline layer and depositing a crust layer, wherein the preparation method comprises the following specific steps:
(S1) self-supporting CNTs substrate preparation:
preparing a metal bracket, wherein the bracket is made of brass alloy, and carrying out ultrasonic cleaning treatment on the surface solution, and the specific cleaning steps are as follows: firstly, ultrasonically cleaning with acetone for 40min, then ultrasonically cleaning with absolute ethyl alcohol for 40min, and finally washing with acetone, absolute ethyl alcohol and deionized water in sequence, and drying; and then transferring the CNTs film substrate to a metal bracket to form a suspension state.
(S2) mounting a metal bracket:
fixing the metal bracket carrying CNTs after cleaning in the step (S1) on a sample stage of a magnetron sputtering deposition device, and adhering the metal bracket by using conductive silver adhesive to ensure that the bracket and the sample stage are in good thermal contact, and the distance between the metal bracket and a target is 10cm.
(S3) performing high-temperature treatment on the CNTs substrate in a high-vacuum environment:
in a magnetron sputtering deposition system: background vacuum degree 2X 10 -5 Pa, introducing high-purity argon with the flow of 40sccm (volume purity is 99.999%), and heating the CNTs substrate at 600 ℃ for 1-2 h to sufficiently remove impurity atoms adsorbed on the surface.
(S4) depositing Cu nanocrystals:
the growth conditions of the nano Cu film are as follows: the sputtering target is commercial Cu target (purity is 99.999 wt%) and background vacuum degree is 2×10 -5 Pa, high-purity argon (volume purity is 99.999%) with working gas of 0.5Pa, growth temperature range of 30 ℃, deposition rate of 3.6 mu m/h, deposition power of 265W, and metal bracket rotation speed of 10 rpm, thus obtaining the CNTs/Cu composite film deposited by magnetron sputtering, see (a) of FIG. 2.
(S5) depositing amorphous C:
amorphous C is prepared by high-energy ion cracking organic matter, and in high vacuum environment, background vacuum degree is 2×10 -5 Pa, deposition temperature range is 30 ℃, and helium ion of 300keV is utilized for cracking for 1.5h. After the deposition is completed, an amorphous C/Cu/CNTs composite material is formed, and the surface morphology of the amorphous C/Cu/CNTs composite material is shown in figure 3 (a).
By adopting the method, the uniform high-melting-point amorphous C material is introduced in the process of physical or chemical vapor deposition and cracking of the organic matters, the grain boundary trench effect of the composite material at high temperature is inhibited, and the atomic diffusion of atoms at the interface of the amorphous C-nanocrystalline material is inhibited. As shown in fig. 2 (b), a transmission electron microscope photograph of a magnetron sputtering deposited CNTs/Cu composite film sample after annealing at 400 ℃ for 3 hours; as shown in FIG. 3 (b), the amorphous C/Cu/CNTs composite material is subjected to thermal insulation for 3h at 400 ℃ and then is subjected to transmission electron microscopy. As can be seen from fig. 2 (b) and fig. 3 (b), the amorphous C material can regulate and control the surface energy, interface energy and grain boundary energy at the interface between the amorphous C material and the nanocrystalline material, so as to maintain the structural stability of the amorphous C material under the high-temperature or strong-ion irradiation condition, and realize the practical application of the amorphous C material in medium-high-temperature electronic devices. The composite material will enable a "roll-to-roll" large scale preparation, which can be used as a large coating material, for example: as a nuclear reactor shielding coating material, the service life of the nuclear reactor is prolonged, and the economy, reliability, perpetual motion performance and safety of the nuclear reactor are improved.
The cladding material/nanocrystalline/Carbon Nanotubes (CNTs) composite material and the preparation method thereof provided by the invention are described in detail. The principles and embodiments of the present invention have been described with reference to specific examples, which are provided to facilitate understanding of the methods and core concepts of the present invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and such modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (8)

1. A cladding material/nanocrystalline/carbon nanotube composite structure material is characterized in that a self-supporting carbon nanotube substrate is of a single-wall carbon nanotube film tube bundle structure, nanocrystalline is uniformly deposited on the surface of the self-supporting carbon nanotube substrate by a physical vapor deposition technology or a chemical vapor deposition technology, and then a cladding material layer is deposited by the physical vapor deposition technology, the chemical vapor deposition technology or a pyrolysis organic vapor technology, so that a three-layer composite three-dimensional network composite material with a nanoscale fiber structure, high conductivity and structural stability is formed; wherein, the volume fraction of the carbon nano tube film tube bundle substrate is 5-30%;
the thickness of the deposited cladding material layer is 1-50 nm, the thickness of the cladding material layer is uniform and can be continuously regulated and controlled, and the cladding material is amorphous Al 2 O 3 Or amorphous carbon;
the interface combination among the carbon nano tube substrate, the nano crystal and the cladding material layer is good, and the interface detachment or cracking phenomenon does not occur under the repeated bending and vibration conditions; the composite material has good structural thermal stability, and can still keep the initial morphology above the recrystallization temperature of the nanocrystals, and the nanocrystals do not have obvious agglomeration and grain growth; the composite material has higher flexibility, is spread on the surface of an object with any curvature, realizes large-scale preparation of reel-to-reel, and is cut into any size by laser processing;
the uniform high-melting-point cladding material with higher stability is introduced in the processes of physical or chemical vapor deposition and cracking of organic matters, so that the grain boundary trench effect of the composite material at high temperature is inhibited, and the atomic diffusion of atoms at the interface of the cladding material and the nanocrystalline material is inhibited; the surface energy, the interface energy and the grain boundary energy of the interface between the shell material and the nanocrystalline material are regulated and controlled, so that the structural stability of the nanocrystalline under the high-temperature or strong ion irradiation condition is maintained, and the practical application of the shell material in medium-high temperature electronic devices is realized.
2. The cladding material/nanocrystal/carbon nanotube composite structure material according to claim 1, wherein the bundle of carbon nanotube film is composed of bundle-like carbon nanotubes with a random orientation distribution and a diameter of 2 to 20nm, and the length of the carbon nanotubes in the carbon nanotube film is 5 to 50 μm.
3. The cladding material/nanocrystalline/carbon nanotube composite structure material according to claim 1, wherein the deposited nanocrystals are Al, cu, ni, fe, nb, W high purity metal or alloy or non-metallic nanocrystalline materials; for Cu or Ni high-purity metal nanocrystalline, the composite material has higher conductivity, and the conductivity in the range of 25 ℃ to 600 ℃ is 1 multiplied by 10 6 ～5×10 6 S·m -1 。
4. The cladding material/nanocrystal/carbon nanotube composite structure material according to claim 1, wherein the nanocrystals deposited on the surface of the carbon nanotubes are uniform in thickness, the nanocrystals are randomly oriented, the grain size is 10-300 nm, the grain size in the direction perpendicular to the axis of the carbon tube is 30-500 nm, and the thickness and the grain size of the nanocrystals can be continuously controlled.
5. The cladding material/nanocrystalline/carbon nanotube composite structure material according to claim 1, wherein the composite material has good resistance to irradiation damage by high-energy particles, and no observable structural destabilization occurs after irradiation of 1dpa to 10dpa dose by 50keV to 5MeV high-energy particles at 25 ℃ to 500 ℃, and the high-energy particles are He ions, ni ions or Fe ions.
6. A method for preparing the cladding material/nanocrystalline/carbon nanotube composite structure material according to any one of claims 1 to 5, comprising the following specific steps:
(S1) self-supporting carbon nanotube substrate preparation:
preparing a metal bracket, wherein the bracket material is a high-heat-conductivity high-temperature-resistant material, and Mo, ti, cu or alloy materials thereof are adopted; carrying out ultrasonic cleaning treatment on a surface solution, wherein the cleaning solution comprises acetone, alcohol and deionized water, and then transferring the carbon nanotube film substrate onto a metal bracket to form a suspension state;
(S2) mounting a metal bracket:
fixing the metal bracket carrying the carbon nano tube after cleaning in the step (S1) on a sample stage of a thin film deposition device, and adhering the metal bracket by using conductive silver adhesive to ensure that the bracket and the sample stage are in good thermal contact, wherein the distance between the metal bracket and a deposition target is 5-20 cm;
(S3) carrying out high-temperature treatment on the carbon nano tube substrate in a high-vacuum environment:
in a magnetron sputtering deposition system: background vacuum degree (1-3). Times.10 -5 Pa, introducing high-purity argon with the flow of 30-50 sccm, and performing heating treatment at 500-800 ℃ on the carbon nano tube substrate for 1-2 h to sufficiently remove impurity atoms adsorbed on the surface;
(S4) depositing metal nanocrystals:
single-target or multi-target sputtering is carried out in a magnetron sputtering deposition system, pure metal or alloy nanocrystalline is deposited, and the growth conditions are as follows: the sputtering target material is commercial block high-purity target material, and the background vacuum degree is (1-3) multiplied by 10 -5 Pa, working gas of 0.1-3 Pa, high purity argon, growth temperature of 20-800 ℃, deposition rate of 0.1-5 mu m/h, deposition power of 10-300W, and rotation speed of the metal bracket of 1-20 rpm, thus forming the nanocrystalline/carbon nanotube composite material;
(S5) uniformly depositing a high-stability cladding material layer:
the cladding material has the characteristics of high strength, high melting point, chemical inertness and high temperature stability, and adopts amorphous Al 2 O 3 Or amorphous carbon material, and thus can dynamically stabilize the inner layer of the nanocrystalline material.
7. The method for producing a clad material/nanocrystal/carbon nanotube composite structure material according to claim 6, wherein, in the step (S4), after magnetron sputtering deposition, annealing is performed at 100 to 800 ℃ for a holding time of 1 to 10 h; in the step (S5), after the high-stability cladding material layer is uniformly deposited, annealing is carried out under the conditions of 100-800 ℃ and the heat preservation time of 1-10 h.
8. The method for producing a clad material/nanocrystal/carbon nanotube composite structure material according to claim 6, wherein in step (S5):
amorphous Al 2 O 3 Deposition is carried out by adopting an atomic layer deposition system, and the precursor is commercial Al (CH) 3 ) 3 The working gas is high-purity argon with the pressure of 0.1-1 MPa, the deposition temperature range is 50-300 ℃, and the deposition rate is 0.1-1 nm/min;
amorphous carbon is prepared by a method of cracking organic matters by high-energy ions, and the background vacuum degree is 1-3 multiplied by 10 in a high vacuum environment -5 Pa, the deposition temperature range is 20-800 ℃, and helium ions of 200-400 keV are utilized for cracking 1-15 h.
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