CN115287637A - Oxidation-resistant copper material and light or ray induction preparation method thereof - Google Patents
Oxidation-resistant copper material and light or ray induction preparation method thereof Download PDFInfo
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- CN115287637A CN115287637A CN202210716249.7A CN202210716249A CN115287637A CN 115287637 A CN115287637 A CN 115287637A CN 202210716249 A CN202210716249 A CN 202210716249A CN 115287637 A CN115287637 A CN 115287637A
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- copper material
- formate
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
Abstract
The invention discloses an oxidation-resistant copper material and a light or ray induction preparation method thereof, wherein the method comprises the following steps: providing a copper material, wherein the copper material adopts copper materials with various sizes; preparing a surface-modified antioxidant copper material by utilizing sunlight or industrial electron beam or gamma-ray irradiation at normal temperature and normal pressure; the method comprises the following steps: putting the copper material into carbon dioxide or formate aqueous solution; adding a certain amount of auxiliary agent or photocatalyst; taking out the copper material after a period of photoreaction or irradiation; and washing and drying to complete the anti-oxidation treatment of the copper material. The invention has the beneficial effects that: the intermediate can be effectively adsorbed on the copper surface to finally form surface-modified oxidation-resistant copper, can effectively improve the oxidation resistance of the copper material in corrosive environments such as saline-alkali environment and the like, can not reduce the intrinsic heat conduction and electric conductivity of the copper material, does not need heating and pressurizing in the treatment process, and has wide light source selection range.
Description
Technical Field
The invention relates to an oxidation-resistant copper material and a light or ray induction preparation method thereof, in particular to an oxidation-resistant copper material and a light or ray induction preparation method thereof, belonging to the technical field of metal functional material preparation.
Background
The prior copper material oxidation resistance technology mainly comprises surface coating, electrochemical protection, chemical passivation and the like. The surface of the copper-based composite coating is coated with modified copper materials such as imidazole, polyhydric alcohol, mercaptan, long-chain amino and long-chain carboxylic acid, and a two-dimensional graphene or boron nitride nanosheet coating is developed recently, so that the stability of copper in a thermal oxidation environment can be obviously improved in a short time. However, surface coating inevitably results in coating wear and peeling, severely limiting service life, and localized defects formed that accelerate interface corrosion.
In order to solve the problem, chinese patent publication No. CN107460464A discloses a surface treatment method for copper-containing materials, wherein the surface of copper is passivated by using formate, and the oxidation resistance of the treated copper under alkaline and thermal oxidation conditions is obviously enhanced, and the method is suitable for various copper materials such as copper nano powder, nano wires, foam copper, copper foil and the like.
However, the method needs to be realized under the condition of high-temperature and high-pressure sealing, the cost is high, and the scale is limited, so that an oxidation-resistant copper material and a light or ray induced preparation method thereof are provided.
Disclosure of Invention
The invention aims to solve the problems and provide an oxidation-resistant copper material and a light or ray induction preparation method thereof, which can effectively improve the oxidation resistance of the copper material in the corrosive environment of saline alkali and the like without reducing the intrinsic heat conduction and electric conductivity of the copper material, are suitable for various light sources, copper materials in various shapes such as copper foils, foam copper, copper radiating frames and the like, and have the advantages of simple preparation process, high efficiency, energy conservation and easy mass production.
The invention realizes the aim through the following technical scheme, and a light or ray induction preparation method of an oxidation-resistant copper material comprises the following steps:
providing a copper material, wherein the copper material adopts copper materials with various sizes; preparing a surface-modified oxidation-resistant copper material by utilizing sunlight or industrial electron beam or gamma-ray irradiation at normal temperature and normal pressure;
the method comprises the following steps:
s1, placing a copper material in a carbon dioxide or formate aqueous solution;
s2, adding a certain amount of auxiliary agent or photocatalyst;
s3, taking out the copper material after a period of photoreaction or irradiation;
and S4, washing and drying to complete the anti-oxidation treatment of the copper material.
Preferably, the formate comprises at least one of lithium formate, sodium formate, magnesium formate, aluminum trimethyl carbonate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, barium formate, beryllium formate, nickel formate, cobalt formate and manganese formate, and the concentration of formate is 0.1-1 mol/L.
Preferably, the concentration of the carbon dioxide in the water is 0.034-0.8 mol/L.
Preferably, the auxiliary agent comprises at least one of dodecylamine or oleylamine or n-octylamine or n-tridecylamine or dodecyl dimethyl tertiary amine or octadecyl amine.
Preferably, the photocatalyst refers to semiconductors with band gap widths suitable for ultraviolet light or visible light catalysis, and comprises TiO 2 、CdS、MoS 2 、ZnS、ZnO、SrO 2 、WO 3 、Bi 2 WO 6 、BiOCl、Cu 2 O、CdSe、SnO 2 And g-C 3 N 4 And non-metal photocatalysts, but not limited thereto.
Preferably, the visible, ultraviolet or daylight reaction time should be greater than 4 hours.
Preferably, the total absorbed dose of the industrial electron beam and gamma-rays should be greater than 15kGy.
Preferably, the reaction process can be carried out by introducing nitrogen and sealing, and can also be carried out by opening under normal pressure air.
An oxidation-resistant copper material comprises an oxidation-resistant copper material with a surface modified by irradiation of sunlight or industrial electron beams or gamma-rays;
the copper material includes copper foil, copper powder, copper wire, copper heat dissipation frame, and foam copper, but not limited thereto.
The invention has the beneficial effects that: after the copper material is placed in carbon dioxide or formate aqueous solution for photoreaction or irradiation for a certain time, the water radiolysis reaction of high-energy rays or semiconductor photoreaction generates a free radical intermediate, the intermediate can be effectively adsorbed on the copper surface and finally forms surface-modified antioxidant copper, the oxidation resistance of the copper material in corrosive environments such as saline alkali and the like can be effectively improved, and the intrinsic heat conduction and electric conductivity of the copper material can not be reduced;
the treatment process of the invention does not need heating and pressurizing, has wide light source selection range, and is suitable for the scale corrosion prevention of copper materials with various shapes, such as copper foil, foam copper, copper radiating frames and the like.
Drawings
FIG. 1a is an SEM image of an original copper foil of the present invention and its immersion in different environments;
FIG. 1b is an SEM picture of an antioxidant copper foil prepared by gamma-ray irradiation of the present invention after being soaked in different environments;
FIG. 1c is an XRD spectrum of the original copper foil of the present invention after being treated with gamma-ray irradiation and the copper foil being immersed in a 0.1mol/L NaOH solution for 24 hours;
FIG. 2 is an optical photograph of the original copper foam and the treated copper foam after gamma-ray irradiation in 0.1mol/L NaOH solution for different periods of time;
FIG. 3a is an SEM image of the antioxidant copper foil prepared by ultraviolet light reaction of the present invention after being soaked in different environments;
FIG. 3b shows the corrosion rate of the copper foil in 0.1mol/L NaOH solution after the UV reaction of the present invention for different time periods;
FIG. 4a is a graph showing the corrosion rate of copper foil in 0.1mol/L NaOH solution after visible light reaction for various periods of time in accordance with the present invention;
FIG. 4b is an SEM picture of the oxidation resistant copper foil prepared by visible light reaction of the present invention after being soaked in different environments;
FIG. 5 is an optical photograph of the original copper foil and the copper foil after the industrial electron beam irradiation treatment of the present invention after being soaked in 0.1mol/L NaOH solution for 24 hours;
FIG. 6 is an optical photograph of the copper material after immersion in 0.1mol/L NaOH solution for 24h after the present invention has not been treated and has been treated by the solar reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The embodiment of the invention discloses an oxidation-resistant copper material and a light or ray induction preparation method thereof.
The method comprises the following steps:
providing a copper material, wherein the copper material adopts copper materials with various sizes; preparing a surface-modified antioxidant copper material by utilizing sunlight or industrial electron beam or gamma-ray irradiation at normal temperature and normal pressure;
the method comprises the following steps:
s1, placing a copper material in a carbon dioxide or formate aqueous solution;
s2, adding a certain amount of auxiliary agent or photocatalyst;
s3, taking out the copper material after a period of photoreaction or irradiation;
and S4, washing and drying to complete the anti-oxidation treatment of the copper material.
The formate comprises at least one of lithium formate, sodium formate, magnesium formate, aluminum trimethyl carbonate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, barium formate, beryllium formate, nickel formate, cobalt formate and manganese formate, and the concentration of formate is 0.1-1 mol/L.
The concentration of the carbon dioxide in the water is 0.034-0.8 mol/L.
The auxiliary agent comprises at least one of laurylamine, oleylamine, n-octylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine.
The photocatalyst refers to semiconductors with various band gap widths suitable for ultraviolet light or visible light catalysis, including TiO 2 、CdS、MoS 2 、ZnS、ZnO、SrO 2 、WO 3 、Bi 2 WO 6 、BiOCl、Cu 2 O、CdSe、SnO 2 And g-C 3 N 4 And non-metal photocatalysts, but not limited thereto.
The reaction time of visible light, ultraviolet light or sunlight is more than 4h.
The total absorbed dose of industrial electron beam and gamma-ray should be greater than 15kGy.
The reaction process can be carried out by introducing nitrogen and sealing, and can also be carried out by opening under normal pressure air.
An oxidation-resistant copper material comprises an oxidation-resistant copper material with a surface modified by irradiation of sunlight or industrial electron beams or gamma-rays;
the copper material includes copper foil, copper powder, copper wire, copper heat dissipation frame, and foam copper, but not limited thereto.
After the copper material is placed in carbon dioxide or formate aqueous solution for photoreaction or irradiation for a certain time, the water radiolysis reaction of high-energy rays or semiconductor photoreaction generates a free radical intermediate, the intermediate can be effectively adsorbed on the copper surface and finally forms surface-modified antioxidant copper, the oxidation resistance of the copper material in corrosive environments such as saline alkali and the like can be effectively improved, and the intrinsic heat conduction and electric conductivity of the copper material can not be reduced;
the treatment process of the invention does not need heating and pressurizing, has wide light source selection range, and is suitable for the scale corrosion prevention of copper materials with various shapes, such as copper foil, foam copper, copper radiating frames and the like.
The first embodiment is as follows:
preparing an antioxidant copper foil and an antioxidant copper foam by utilizing gamma-ray irradiation;
cutting a piece of copper foil with the area of 1.5cm multiplied by 1.5cm and the thickness of 25 mu m and a piece of foam copper with the area of 1.5cm multiplied by 3.0cm and the thickness of 1.8mm, carrying out ultrasonic washing for 5min in 1mol/L phosphoric acid, acetone, ethanol and water in sequence to remove surface oxides and organic impurities, and drying for later use.
200mg of sodium formate, 100 mu L of dodecylamine and 10mL of deionized water are added into a container, and ultrasonic treatment is carried out for 30min to uniformly disperse the system. Placing the dried copper foil in the container, introducing nitrogen for 10min, sealing, and standing at room temperature 60 Co radioactive source radiation field (activity is 1.95X 10) 14 Bq, located at the university of Chinese science and technology) at the position with the dosage rate of 52.9Gy/min (alanine dosimeter calibration), the irradiation is carried out for 8.5h, and the total absorbed dose is about 27kGy.
And after the irradiation is finished, taking the copper foil out of the container and washing the copper foil with deionized water to obtain the surface-modified antioxidant copper foil.
The resistivity of the obtained oxidation-resistant copper foil is measured to be 1.71 multiplied by 10 -8 Omega. M, and resistivity of the original copper foil (1.76X 10) -8 Ω · m) are very close. As shown in FIG. 1, the obtained oxidation-resistant copper foil and the original copper foil were immersed in a 0.1mol/L NaOH solution and 50mmol/L Na solution at the same time 2 S solution, 30% H 2 O 2 Solution and 5% NaCl solution after a period of time, both oxidation species and morphological changes appeared in SEM pictures of the original copper foil (FIG. 1 a), the macroscopic color turned black; the obtained oxidation resistant copper foil has no obvious change of appearance in an SEM picture (figure 1 b), still maintains metallic luster, and an XRD spectrogram has no oxide corresponding peak (figure 1 c), and comparison shows that the treated copper foil has oxidation resistance in the four environments.
Meanwhile, after the antioxidant copper foil is soaked in 0.1mol/L NaOH solution for 31 days, the conductivity of the antioxidant copper foil is still maintained to be 1.76 multiplied by 10 -8 Ω · m, at which point the original copper foil is non-conductive and the resistivity cannot be measured. FIG. 2 is a graph comparing the shapes of the original copper foam and the antioxidant copper foam after soaking in 0.1mol/L NaOH solution for 31d, wherein the original copper foam becomes dark black, and the antioxidant copper foam still keeps the metal color, which shows that the treated copper foam has excellent antioxidant performance.
Example two:
preparing an antioxidant copper foil by using ultraviolet light reaction;
cutting a piece of copper foil with an area of 1.5cm × 1.5cm and a thickness of 25 μm, ultrasonic washing in 1mol/L phosphoric acid, acetone, ethanol, and water for 5min to remove surface oxide and organic impurities, and drying for use.
Adding 50mg commercial TiO into a quartz bottle 2 P25, 200mg of sodium formate, 100 mu L of dodecylamine and 10mL of deionized water, and performing ultrasonic treatment for 30min to uniformly disperse the system.
Placing the dried copper foil in the quartz bottle, introducing nitrogen for 10min, sealing, and placing under ultraviolet light at room temperature (λ =365nm, average intensity of 100mW · cm) -2 ) The irradiation was carried out for 12 hours. After the irradiation is finished, the copper foil is taken out of the container and washed by deionized waterAnd obtaining the surface-modified antioxidant copper foil.
The resistivity of the obtained oxidation resistant copper foil is measured to be 1.85 multiplied by 10 -8 Omega.m. After the obtained antioxidant copper foil and the original copper foil are immersed in the four solutions for a period of time, the shape of the obtained antioxidant copper foil is not obviously changed in an SEM picture (figure 3 a), and the metallic luster is still kept, which shows that the copper foil after the ultraviolet light reaction treatment has the antioxidant performance in the four environments. FIG. 3b shows that the corrosion rate of copper foil in 0.1mol/L NaOH solution increases from 646.5 μm. Yr -1 Gradually decreases to 4.57 mu m yr -1 And explaining the ultraviolet light treatment process to gradually modify the surface of the copper foil and finally realize the oxidation resistance.
Example three:
preparing an antioxidant copper foil by visible light reaction;
cutting a piece of copper foil with an area of 1.5cm × 1.5cm and a thickness of 25 μm, ultrasonic washing in 1mol/L phosphoric acid, acetone, ethanol and water for 5min to remove surface oxides and organic impurities, and drying for later use.
Adding 50mg g-C into a quartz bottle 3 N 4 200mg of sodium formate, 100 mu L of laurylamine and 10mL of deionized water, and performing ultrasonic treatment for 30min to uniformly disperse the system.
Placing the dried copper foil in the quartz bottle, introducing nitrogen for 10min, sealing, and placing under visible light (lambda) at room temperature>420nm, average intensity of 100mW cm -2 ) The irradiation was carried out for 12 hours.
And after the irradiation is finished, taking the copper foil out of the container and washing the copper foil by deionized water to obtain the surface-modified antioxidant copper foil.
The resistivity of the obtained oxidation-resistant copper foil is measured to be 1.81 multiplied by 10 -8 Omega.m, and the corrosion rate of the copper foil in 0.1mol/LNaOH solution is from 646.5 mu m.yr -1 Reduced to 2.95 μm. Yr -1 (FIG. 4 a). After the obtained oxidation-resistant copper foil and the original copper foil are immersed into the four solutions for a period of time, the appearance of the oxidation-resistant copper foil in an SEM picture is not obviously changed (figure 4 b), and the metal luster is kept, which indicates that the treated copper foil has oxidation resistance in the four environments.
Example four:
preparing an antioxidant copper foil by industrial electron beam irradiation;
and (3) taking a copper foil with the length of 10m, the width of 25cm and the thickness of 25 mu m, carrying out ultrasonic washing on the copper foil in 1mol/L phosphoric acid, acetone, ethanol and water for 5min in sequence to remove surface oxides and organic impurities, and drying for later use. 100g of sodium formate, 50mL of dodecylamine and 5L of deionized water are added into a container, and the system is uniformly dispersed by ultrasonic treatment for 30 min.
Adding the solution into a liquid tank, and fixing the dried copper foil on a bundling roll. And starting to collect the copper foil, passing the copper foil through an industrial electron beam (200 keV) protected by nitrogen at a constant speed, wherein the dose rate is 300Gy/s, and the total absorbed dose is 27kGy.
And after the irradiation is finished, taking down the copper foil from the bundling roll and washing the copper foil by using deionized water to obtain the surface-modified antioxidant copper foil. Placing the original copper foil and the processed copper foil in 0.1mol/L NaOH solution to be soaked for 24h, and then comparing the surface appearances of the original copper foil and the processed copper foil, wherein as shown in figure 5, the surface part of the original copper foil is blackened and gray lines appear, which indicates that oxidation has occurred; the treated copper foil completely keeps the metal color, which shows that the anti-oxidation treatment process is uniform and the anti-oxidation performance is good.
Example five: natural sunlight reaction preparation anti-oxidation copper foil and anti-oxidation copper heat dissipation frame
A copper heat dissipation frame (with the diameter of a pin column being 1.6mm and the distance between the pin columns being 3.4 mm) with the area of 8cm multiplied by 8cm is taken, a copper foil with the area of 25cm multiplied by 30cm and the thickness of 25 mu m is cut, ultrasonic washing is carried out for 5min in 1mol/L phosphoric acid, acetone, ethanol and water in sequence to remove surface oxides and organic impurities, and drying is carried out for standby.
Adding 5 g-C into the self-made PMMA container 3 N 4 20g of sodium formate, 10mL of dodecylamine and 1L of deionized water, and performing ultrasonic treatment for 30min to uniformly disperse the system.
Immersing the lower part of the dried copper foil and the copper heat dissipation frame into the solution, introducing nitrogen for 30min, sealing, and standing at 20 deg.C in natural sunlight (average intensity of 78mW cm) -2 ) The irradiation was carried out for 6h.
And after the irradiation is finished, taking the copper foil and the copper radiating frame out of the container, and washing the copper foil and the copper radiating frame by using deionized water to obtain the surface-modified antioxidant copper material.
After the treated copper foil is soaked in 0.1mol/L NaOH solution for 24 hours, the part soaked in the solution is not oxidized during sunlight treatment, and the part not soaked is obviously oxidized.
The same contrast phenomenon is also seen in the copper heat dissipation frame, which shows that the sunlight reaction can also perform effective antioxidant treatment on the surface of the copper material.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A light or ray induction preparation method of an oxidation-resistant copper material is characterized by comprising the following steps:
providing a copper material, wherein the copper material adopts copper materials with various sizes; preparing a surface-modified antioxidant copper material by utilizing sunlight or industrial electron beam or gamma-ray irradiation at normal temperature and normal pressure;
the method comprises the following steps:
s1, placing a copper material in a carbon dioxide or formate aqueous solution;
s2, adding a certain amount of auxiliary agent or photocatalyst;
s3, taking out the copper material after a period of photoreaction or irradiation;
and S4, washing and drying to complete the anti-oxidation treatment of the copper material.
2. The light or radiation induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the formate comprises at least one of lithium formate, sodium formate, magnesium formate, aluminum trimethyl formate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, barium formate, beryllium formate, nickel formate, cobalt formate and manganese formate, and the concentration of formate is 0.1-1 mol/L.
3. The light-or radiation-induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the concentration of the carbon dioxide in water is 0.034-0.8 mol/L.
4. The light or radiation induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the auxiliary agent comprises at least one of laurylamine, oleylamine, n-octylamine, n-tridecylamine, dodecyl dimethyl tertiary amine or octadecyl amine.
5. The light or radiation induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the photocatalyst refers to semiconductors with various band gap widths suitable for ultraviolet light or visible light catalysis, including TiO 2 、CdS、MoS 2 、ZnS、ZnO、SrO 2 、WO 3 、Bi 2 WO 6 、BiOCl、Cu 2 O、CdSe、SnO 2 And g-C 3 N 4 And non-metal photocatalysts, but not limited thereto.
6. The light-or radiation-induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the reaction time of the visible light, the ultraviolet light or the sunlight is more than 4h.
7. The light-or radiation-induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the total absorbed dose of the industrial electron beam and the gamma-ray is more than 15kGy.
8. The light-or radiation-induced preparation method of an oxidation-resistant copper material according to claim 1, characterized in that: the reaction process can be carried out by introducing nitrogen and sealing, and can also be carried out by opening under normal pressure air.
9. An oxidation-resistant copper material, based on an oxidation-resistant copper material and a light-or radiation-induced production method thereof according to any one of claims 1 to 8, an oxidation-resistant copper material is proposed, characterized in that: comprises preparing surface-modified antioxidant copper material by irradiation of sunlight or industrial electron beam or gamma-ray;
the copper material includes copper foil, copper powder, copper wire, copper heat dissipation frame, and foam copper, but not limited thereto.
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