CN112247153B - Preparation method of metal-fullerene composite nano powder - Google Patents

Preparation method of metal-fullerene composite nano powder Download PDF

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CN112247153B
CN112247153B CN202011083264.XA CN202011083264A CN112247153B CN 112247153 B CN112247153 B CN 112247153B CN 202011083264 A CN202011083264 A CN 202011083264A CN 112247153 B CN112247153 B CN 112247153B
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metal
film
fullerene
fullerene composite
substrate
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CN112247153A (en
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孙永青
陈益钢
张永春
李智安
蔺峰
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Inner Mongolia Carbon Valley Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • C23C14/0005—Separation of the coating from the substrate
    • 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
    • C23C14/0605—Carbon
    • 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
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
    • 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
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material

Abstract

The invention relates to a preparation method of metal-fullerene composite nano powder, which comprises the following preparation steps: s1, respectively heating fullerene and metal in a vacuum environment, and jointly depositing the formed vapor on an organic substrate, and controlling the resistance value of a deposited layer to be not less than 10KΩ, thereby obtaining a metal-fullerene composite film grown in a discontinuous island mode; s2: dissolving an organic matrix deposited with a metal-fullerene composite film by using a solvent, filtering and drying after the organic matrix is completely dissolved, thus obtaining uniform metal-fullerene composite nano powder; wherein, the metal is a metal which can be stably existing in the air, and the organic matrix is an organic film. The preparation method is simple, no impurity is introduced, the material limit is small, and the metal-fullerene composite nano powder prepared by the preparation method is relatively uniform.

Description

Preparation method of metal-fullerene composite nano powder
Technical Field
The invention relates to the field of fullerenes, in particular to a preparation method of metal-fullerene composite nano powder.
Background
Due to C 60 Has a unique space structure ofThere are many excellent properties such as: superconducting, high-voltage resistant, chemical corrosion resistant and the like, thereby having potential application prospect in the fields of light, electricity, magnetism and the like. However, the fullerene exists in the form of powder or compound. The nano powder can be used as a filler of a coating and can be used as a powder for 3D printing by compounding metal and fullerene to form an atom-molecule level composite nano material, so that more special properties can be given to metal nano particles. The novel nano powder formed by compounding metal/fullerene can lead the fullerene to show wider application prospect. Currently, the metal and fullerene are compounded by mechanical ball milling, chemical plating, electroplating, sol-gel method and the like.
The mechanical ball milling method is to put metal powder and additive (such as fullerene powder) into a ball milling tank together, and add grinding medium (such as steel ball, zirconium bead, etc.), and in the cyclic reciprocating motion of the ball milling tank, the grinding medium continuously impacts the powder particles so as to achieve the purpose of uniform mixing. However, this mixing does not achieve an atomic-molecular level of mixing, the metal powder and the fullerene powder remain in contact with the particles, there are distinct particle interfaces, and a large amount of impurities are introduced during the ball milling process, and sources of impurities include milling media, milling tanks, and solvents.
Electroless plating refers to a technique of depositing a metal plating layer on the surface of an enhanced phase by an autocatalytic oxidation-reduction reaction of a metal salt and a reducing agent in the same solution without an applied current. The enhancement phase needs to be pretreated before electroless plating, generally comprises surface cleaning treatment, roughening treatment and activation sensitization treatment, and then plating is carried out in corresponding plating solution.
Electroplating is a process in which a thin layer of metal or alloy is deposited electrochemically on the surface of a substrate. When in electroplating, the plating piece is connected with the negative electrode of the direct current power supply, the metal to be plated and the positive electrode of the direct current power supply are connected in the electroplating solution containing ions to be plated, and metal can be separated out from the negative electrode, so that a new plating layer is formed by depositing on the plating piece.
The sol-gel method is to utilize wet chemical synthesis method to react soluble metal compound, such as inorganic salt or alkoxide, with water in certain solvent, to hydrolyze and polycondensate to gel gradually, and to dry and sinter to realize the surface metallization of the superfine reinforcing body. The key problems are the control of water addition, sol concentration, catalyst selection and other factors.
Theoretically, three methods, namely electroless plating, electroplating and sol-gel method, can realize the mixing of atomic-molecular level, but have unavoidable limitations of material types, such as that some high-activity metals cannot be prepared, and a large amount of impurities are introduced in the process.
Disclosure of Invention
The invention provides a preparation method of metal-fullerene composite nano powder, which is simple, free of impurity introduction, small in material limit and applicable to high-activity metals such as aluminum, silver and the like, in order to make up the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the metal-fullerene composite nano powder comprises the following preparation steps: s1, respectively heating fullerene and metal in a vacuum environment, and jointly depositing the formed vapor on an organic substrate, and controlling the resistance value of a deposited layer to be not less than 10KΩ, thereby obtaining a metal-fullerene composite film grown in a discontinuous island mode; the control mode of the resistance value is various, specifically, the deposition time can be controlled by measuring the resistance value of the composite film on line, and then the thickness of the composite film can be controlled, for example, if a winding film plating machine is adopted, the control of the thickness of the composite film can be realized according to the control of the winding speed, so that the composite film with the resistance value compounding requirement can be obtained;
s2: dissolving an organic matrix deposited with a metal-fullerene composite film by using a solvent, filtering and drying after the organic matrix is completely dissolved, thus obtaining uniform metal-fullerene composite nano powder; among them, metals that can exist stably in the air are used.
When the resistance value of the obtained metal-fullerene composite film is between 10KΩ and 1MΩ, uniform lamellar nano powder can be obtained, the lamellar thickness is about 70 nm-100 nm, and the lamellar length (width) is 100 nm-300 nm. Preferably, when the resistance value of the obtained metal-fullerene composite film is above 1MΩ, extremely uniform approximately spherical nano-powder can be obtained, with a diameter of less than 60 nm.
Alternatively, the metal may be one or more of aluminum, iron, chromium, titanium, and silver.
Alternatively, acetone is used as the solvent.
Alternatively, in S1, the vacuum degree is not more than 5×10 -4 Pa, the purity of the obtained nano powder can be ensured.
In order to increase the loading capacity of the prepared metal-fullerene composite nano powder, the preparation method comprises the following steps of specifically, in S1, the organic matrix comprises a first matrix and a second matrix, during the preparation, firstly, depositing a layer of metal-fullerene composite film on the first matrix, then spraying a monomer of the second matrix in a vapor state on the surface of the metal-fullerene composite film, irradiating a spraying area with ultraviolet rays or electron beams to polymerize the monomer to form a second matrix with a certain thickness, thereby achieving the purpose of isolating an upper metal-fullerene composite film, then, continuing depositing a layer of metal-fullerene composite film on the surface of the second matrix, and repeating the process for a plurality of times, thus obtaining the stacked structure of the metal-fullerene composite film and the second matrix alternately.
Optionally, the first substrate and the second substrate are respectively organic thin films, and at least the second substrate in the first substrate and the second substrate has the following selection requirements: the monomer forming the organic film can be firstly condensed into a liquefied film under the vacuum condition, and then a polymer is formed, and the action principle is as follows: when the film is liquefied by ultraviolet rays or electron beams, the organic monomers in the liquefied film are excited to carry out polymerization reaction, and finally a second matrix capable of completely isolating the metal-fullerene composite film is formed.
Preferably, the first substrate is one of a polypropylene film, a polyethylene film and a polyacrylic acid film; the second matrix adopts one of a polyacrylic acid film, a polymethacrylic acid film and a polypropylene film.
More preferably, the first substrate is a polypropylene film or a polyethylene film; the second matrix adopts the polyacrylic acid film, so that the cost is lower, the thickness of the polyacrylic acid film is not less than 5nm, and the aim of completely isolating two adjacent metal-fullerene composite films can be achieved.
Preferably, the irradiation temperature is 25 degrees or less, and the irradiation dose is a conventional dose.
The invention adopts the structure and has the advantages that:
1. the preparation method controls the thickness of the metal-fullerene composite film by controlling the conductivity of the metal-fullerene composite film, and easily realizes the control of the particle size and the control of the particle uniformity of the metal-fullerene nano powder.
2. The metal-fullerene nano powder obtained by the preparation method of the invention has no impurity introduction.
3. The preparation method provided by the invention has small metal limit, and can be applied to not only inactive metals but also high-activity metals such as aluminum, silver and the like.
4. The preparation method can achieve the atomic-molecular level mixing of the metal and the fullerene, and the specific metal atoms and carbon atoms on the fullerene molecules can be combined in a covalent bond or ionic bond mode. Whereas the atomic-molecular level mixing has the following advantages: fully exerts the performance advantages of fullerene molecules, such as strength, elasticity, chemical stability and the like; the fullerene macromolecule patterns are prevented from being mixed, and because the bonding force between molecules is usually weak, after the macromolecule groups are mixed with metal, the interior of the macromolecule groups is a place which is easy to damage, namely a place which is easy to lose efficacy; the use amount of the fullerene raw material can be greatly reduced.
Drawings
FIG. 1 is a TEM image of example 1 of the present invention;
fig. 2 is a TEM image of example 2 of the present invention.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present invention will be described in detail below with reference to the following detailed description and the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced otherwise than as described herein, and thus the scope of the present application is not limited by the specific embodiments disclosed below.
The preparation method of the metal-fullerene composite nano powder adopts a winding film plating machine to prepare the metal-fullerene composite nano powder, and specifically comprises the following steps:
(1) An organic film coiled material is arranged in a coiling type coating machine and used as an organic base material;
(2) And placing high-purity metal and high-purity fullerene powder at the evaporation source of the coating machine. The evaporation source corresponding to the metal may be a resistive heating source, an inductive heating source, a focused electron beam heating source, or the like. The heating source corresponding to the fullerene powder adopts a resistance type heating source.
(3) Starting a vacuum pumping system to pump the vacuum cavity to high vacuum;
(4) Starting an evaporation power supply, and adjusting input power to form stable metal vapor and fullerene vapor at an evaporation source, wherein the two vapors are jointly deposited on a substrate; according to the film thickness control requirement, the winding speed of the organic film base material is regulated;
(5) And taking out the organic film coiled material after the evaporation coating is finished, crushing, soaking by using an organic solvent, and filtering after the organic film is completely dissolved, thus obtaining the required metal/fullerene mixed nano material.
Ultrasonic dispersion can be assisted in the dissolution process, so that the separation of the nano particles and the base material can be accelerated.
Example 1
In the preparation process, a PE film is used as an organic substrate, and the vacuum degree of the back of the vacuum cavity is 5 multiplied by 10 < -4 > Pa; the parameter conditions are as follows: the rotating speed of the PE film is 5 m/min, and the temperature of the PE film is 25 ℃; the heating temperature of the aluminum source is 750 ℃; the heating temperature of the fullerene is 500 ℃; the PE film reciprocates for 10 times, and the resistance value of the composite film is measured to be 1.5 megaohms; taking out the composite film, immersing in acetone, filtering to obtain powder after the substrate is completely dissolved, and carrying out a scanning electron microscope test on the powder to obtain the powder with the diameter of about 50 nanometers, wherein the nano particles in the obtained aluminum-fullerene composite film are completely non-adhered, and the nano powder which is extremely uniform and similar to a sphere can be obtained through subsequent dissolution and removal of an organic matrix, and the specific view is shown in figure 1.
Example 2
In the preparation process, a PE film is used as a substrate, and the vacuum degree of the back of the vacuum cavity is 5 multiplied by 10 < -4 > Pa; parameter conditions: the rotating speed of the PE film is 5 m/min, and the temperature of the PE film is 25 ℃; the heating temperature of the aluminum source is 750 ℃; the heating temperature of the fullerene is 500 ℃; the PE film reciprocates for 20 times, and the resistance value of the composite film is 700 kiloohms; taking out the composite film, immersing in acetone, filtering to obtain powder after the substrate is completely dissolved, and carrying out a scanning electron microscope test on the powder, wherein the particle size of the powder is about 230 nanometers, and particularly shown in figure 2, the nano powder is relatively uniform lamellar nano powder, the thickness of the flake is about 70-100 nanometers, and the length (width) of the flake is 100-300 nanometers.
Example 3
In the preparation process, the PE film is used as a substrate, and the vacuum degree of the back of the vacuum cavity is 5 multiplied by 10 < -4 > Pa. Parameter conditions: the rotation speed of the PE film is 5 m/min, and the temperature of the PE film is 25 ℃. The heating temperature of the aluminum source is 750 ℃, and the heating temperature of the fullerene is 500 ℃; the PE film reciprocates for 100 times, and the resistance value of the composite film is 6 kiloohms; and taking out the composite membrane, immersing the composite membrane into acetone, and obtaining powder after the substrate is completely dissolved.
The above embodiments are not to be taken as limiting the scope of the invention, and any alternatives or modifications to the embodiments of the invention will be apparent to those skilled in the art and are intended to fall within the scope of the invention. The present invention is not described in detail in the following, but is well known to those skilled in the art.

Claims (8)

1. The preparation method of the metal-fullerene composite nano powder is characterized by comprising the following preparation steps: s1, respectively heating fullerene and metal in a vacuum environment, and jointly depositing the formed vapor on an organic substrate, and controlling the resistance value of a deposited layer to be not less than 10KΩ, thereby obtaining a metal-fullerene composite film grown in a discontinuous island mode;
s2: dissolving an organic matrix deposited with a metal-fullerene composite film by using a solvent, filtering and drying after the organic matrix is completely dissolved, thus obtaining uniform metal-fullerene composite nano powder;
wherein, the metal is a metal which can be stably existing in the air, the organic matrix is an organic film, the organic matrix comprises a first matrix and a second matrix, and the first matrix is one of a polypropylene film, a polyethylene film and a polyacrylic film; the second matrix adopts one of a polyacrylic acid film, a polymethacrylic acid film and a polypropylene film;
during preparation, a layer of metal-fullerene composite film is deposited on a first substrate, then a monomer of a second substrate in a steam state is sprayed on the surface of the metal-fullerene composite film, and ultraviolet rays or electron beams are used for irradiating a spraying area to polymerize the monomer to form a second substrate with a certain thickness, so that the aim of isolating an upper layer of metal-fullerene composite film is fulfilled, and then a layer of metal-fullerene composite film is continuously deposited on the surface of the second substrate, and the metal-fullerene composite film and the second substrate are alternately stacked for multiple times.
2. The method for preparing metal-fullerene composite nano-powder according to claim 1, wherein in S1, the resistance value of the deposited layer is controlled to be not less than 1mΩ.
3. The method for preparing metal-fullerene composite nano-powder according to claim 1, wherein the metal is one or more of aluminum, iron, chromium, titanium and silver.
4. The method for preparing metal-fullerene composite nano-powder according to claim 1, wherein the solvent is acetone.
5. The method for preparing metal-fullerene composite nano-powder according to claim 1, wherein in S1, the vacuum degree is not more than 5 x 10 -4 Pa。
6. The method for preparing metal-fullerene composite nano powder according to claim 1, wherein the first substrate and the second substrate are organic thin films respectively, and at least the second substrate of the two is selected from the following requirements: the monomer forming the organic thin film can be coagulated into a liquefied film under vacuum and then a polymer is formed.
7. The method for preparing metal-fullerene composite nano-powder according to claim 1, wherein the first substrate is a polypropylene film or a polyethylene film; the second matrix adopts a polyacrylic acid film, and the thickness of the polyacrylic acid film is not less than 5nm.
8. The method for producing a metal-fullerene composite nano-powder according to claim 1, wherein the irradiation temperature is 25 degrees or less.
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