CN112121234A - Controllable and durable anti-infection orthopedic implant and preparation method thereof - Google Patents
Controllable and durable anti-infection orthopedic implant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of medical instruments, in particular to a controllable and durable anti-infection orthopedic implant and a preparation method thereof, which are used for treating bone fracture, bone injury, bone defect, bone nails, bone plates, intramedullary nails and other orthopedic medical instruments and have the characteristics of controllable and durable anti-infection. The copper-containing material and the substance which can generate Reactive Oxygen Species (ROS) under certain conditions are fixed/dispersed in the polymer coating on the surface of the orthopedic implant in a certain way, so that the anti-infection function of the orthopedic implant can be realized. After the orthopedic implant with controllable and lasting anti-infection function is implanted into a body, the anti-infection function of the implant can be regulated and controlled in a lighting mode, and complications caused by infection are inhibited. The functional material in the anti-infection coating acts through chemical power and photodynamic, and the functional material plays a catalytic role in the action process and is basically not consumed, so that the anti-infection function can be expressed for a long time.
Description
Technical Field
The invention relates to the field of medical instruments, in particular to a controllable and durable anti-infection orthopedic implant and a preparation method thereof, which are used for treating bone fracture, bone injury, bone defect, bone nails, bone plates, intramedullary nails and other orthopedic medical instruments and have the characteristics of controllable and durable anti-infection.
Background
Orthopedic wounds are generally large wounds, and the wounds can involve bone tissues and soft tissues such as peripheral muscles, nerves and skin. Therefore, the repair surgery for orthopedic wounds is difficult, the postoperative infection problem is common, once the implant in the orthopedics department causes infection, the infected implant needs to be taken out and replaced by another surgery, and the body and mind of a patient are injured greatly. Therefore, the problem of anti-infection of the orthopedic implant is a problem which needs to be solved urgently at present. Research on antibacterial orthopedic implants has been relatively late, mainly focusing on achieving anti-infection properties of orthopedic implants by using implant substrates with anti-infection functionality.
At present, researches on copper-containing stainless steel, copper-containing titanium alloy, copper-containing cobalt-based alloy, silver-containing titanium alloy, degradable magnesium alloy and copper-containing degradable magnesium alloy in the aspect of orthopedic implants are increasing. The antibacterial function of copper, silver, magnesium and other elements is utilized to reduce the risk of infection after the implantation of the orthopedic implant. In addition, research on preparing the antibacterial coating on the surface of the orthopedic implant is gradually carried out, and a coating design approach of carrying slow-release antibiotics on a device is mostly adopted. Such as: the published Chinese patent application CN 107261202A discloses a method for preparing an antibacterial biological composite coating on the surface of a titanium metal orthopedic implant, wherein the coating is designed by firstly preparing a nanotube morphology by a copper anodic oxidation method, and then depositing bone active substances hydroxyapatite and antibiotics in a carbon nanotube by a secondary deposition technology so as to have double effects of biological activity and antibacterial property. Other materials with antibacterial components are also prepared on the surface of the orthopedic implant. Such as: the granted and published Chinese patent application CN 101642587A discloses an orthopaedic metal implant carrying slow-release antibiotics and a preparation method thereof, which improve the anti-infection capability of the orthopaedic metal implant. However, most of the existing anti-infection coatings utilize antibiotic components doped in the coatings, and the antibiotic components are continuously diffused and released to sterilize surrounding bacteria, so that drug resistance is formed after long-term use, and the anti-infection function of the device is lost. Therefore, current antibacterial coatings only provide anti-infection properties to orthopedic implants in a short period of time.
It has been proved that copper is a material with antibacterial property, and divalent copper ions have bactericidal effect because bacteria are alive in the metabolic process under aerobic conditionSexual oxygen (ROS) and hydrogen peroxide (H)2O2) The divalent copper ions can sequentially generate a series of reactions to generate hydroxyl radicals with strong oxidizing property, thereby playing a role in sterilization. However, the ROS generated by the metabolism of bacteria is very limited, so the invention proposes that a copper compound with long-acting bactericidal action is matched with a photocatalyst material for use, and simultaneously plays the roles of chemical power and photodynamic to realize the bactericidal effect of 1+1 greater than 2. When the coating with the copper ions and the photocatalyst material is prepared on the surface of the orthopedic implant, ROS can be generated by irradiation of light after the coating is implanted into a human body, so that the anti-infection process of the coating is accelerated, and the orthopedic implant has the characteristics of high efficiency and lasting anti-infection.
Disclosure of Invention
The invention aims to provide a controllable and durable anti-infection orthopedic implant and a preparation method thereof, wherein a controllable and durable anti-infection coating is prepared on the surface of the orthopedic implant, the anti-infection behavior of the coating is realized by the synergistic effect of photodynamic and chemical kinetics principles, the coating with the functions of light control and durable anti-infection is introduced on the surface of the orthopedic implant, the controllable and durable anti-infection performance is realized, and the problems that the conventional orthopedic implant is easy to cause implantable bacterial infection, secondary operation replacement of the implant and the like are solved.
The technical scheme of the invention is as follows:
a controllable and durable anti-infection orthopaedic implant is characterized in that a coating with anti-infection function is prepared on the surface of the orthopaedic implant, and the functional substance in the coating is a copper-containing material and a substance capable of generating Reactive Oxygen Species (ROS).
The controllable and durable anti-infection orthopaedic implant has an anti-infection coating, wherein the copper-containing material and the substance capable of generating active oxygen are dispersed in the coating material in a physical blending mode or are combined on the surface of the coating material through chemical bonding or electrostatic action, and the copper-containing material and the substance capable of generating active oxygen are compatible with the coating material.
The controllable and durable anti-infection orthopedic implant has the advantages that in the coating with the anti-infection function, the mole percentage of a copper-containing material is within the range of 1 per thousand-50%, the mole percentage of an active oxygen substance can be generated within the range of 1 per thousand-50%, and the balance is a water-absorbing polymer coating material which is all components except the two functional materials.
The controllable and durable anti-infection orthopedic implant comprises a copper-containing material, a copper-carrying polymer and a coating, wherein the copper-containing material is one or two of a divalent copper salt and a copper-carrying polymer, the copper-carrying polymer is formed by chemically bonding divalent copper ions to polymer small molecules, the copper-containing material is uniformly distributed in the coating in the form of metal-polymer chain segments or in the form of metal inorganic salt, and the size of the copper-containing inorganic salt ranges from 100nm to 10 mu m.
The controllable and durable anti-infection orthopedic implant has the advantages that the polymer micromolecules with divalent copper ions capable of being chemically bonded are one or more than two of chitosan oligosaccharide, alginate, amino acid, starch, cyclodextrin, cellulose, collagen, micromolecule protein, polyalcohol, amine and polyester, and the divalent copper salt is one or more than two of basic copper sulfate, copper chloride, copper hydroxide, copper acetate, copper amino acid and copper quinoline.
The controllable and durable anti-infection orthopedic implant can generate active oxygen substances as an infrared photocatalyst material, and the infrared photocatalyst material is one or more than two of perovskite, molybdenum disulfide, cadmium sulfide and cadmium stannide.
The preparation method of the controllable and durable anti-infection orthopedic implant comprises the following steps:
the method comprises the following steps: preparing a solution of a copper-containing material;
step two: adding an active oxygen generating material to a solution of a copper containing material to produce a coating solution containing the copper containing material and the active oxygen generating material;
step three: and preparing the coating solution with the anti-infection function on the surface of the orthopedic implant by adopting spraying or dip coating equipment.
In the first step, when the copper-containing material is a copper-carrying polymer, a solution of the copper-containing material is prepared by adopting a chemical grafting method, and the preparation method comprises the following steps:
(1) preparing a copper salt aqueous solution with the mass volume concentration of 1-200 mg/mL;
(2) preparing a micromolecular polymer matrix solution with the mass volume concentration of 5-1000 mg/mL, wherein the solvent is an organic solvent, and the type of the organic solvent is determined according to the characteristics of the adopted polymer matrix;
(3) adding a copper salt aqueous solution into a micromolecular polymer matrix solution, wherein the mass ratio of the copper salt aqueous solution to the micromolecular polymer matrix solution is 1: 1-1: and 10, fully stirring and reacting for 1-24 hours to obtain the copper-containing material solution.
In the second step, the molar ratio of the active oxygen material to the copper-containing material is 1: 10-10: 1, uniformly suspending active oxygen generating materials in a copper-containing material solution by mechanical stirring or magnetic stirring for 1-10 hours to form an anti-infection coating solution.
The preparation method of the controllable and durable anti-infection orthopedic implant comprises the third step of forming an anti-infection coating with photodynamic and chemical power after coating the surface of the orthopedic implant with an anti-infection coating solution and drying, wherein the thickness of the anti-infection coating is 100 nm-30 mu m.
The design idea of the invention is as follows:
in the course of studying the antibacterial and antiviral effects of copper ions and cuprous compounds, it was discovered that cupric ions are bactericidal because bacteria produce reactive oxygen species (ROS, e.g., superoxide anion radical O) during the metabolism under aerobic conditions2·–) And hydrogen peroxide (H)2O2) The divalent copper ions can generate a series of reactions in succession to generate hydroxyl radicals (OH) with strong oxidizing property, and the reaction formula is as follows:
Cu2++O2·-＝Cu++O2 (1)
Cu++H2O2＝Cu2++OH-+·OH (2)
H2O2+O2·-＝O2+OH-+·OH (3)
however, the oxygen metabolism of bacteria produces very limited amounts of active oxygen, and even if copper-containing materials are added to the coating, the anti-infective effect is very limited. Therefore, the invention designs a coating material containing copper ions and a compound capable of generating ROS (material with photocatalyst property), the generation amount of active oxygen can be realized by irradiation of light, the coating is prepared on the surface of the orthopedic implant, and the controllable and lasting anti-infection effect can be realized by applying light. The anti-infection coating on the surface of the orthopedic implant and the action schematic diagram are shown in figure 1.
The invention has the characteristics and beneficial effects that:
1. the controllable and durable anti-infection orthopedic implant is characterized in that a compound containing copper ions and a compound capable of generating ROS are matched for use and compounded into a coating material, and the controllable and durable anti-infection effect is realized through light irradiation.
2. The controllable and durable bacteria killing method of the invention utilizes the continuous existence of copper ions and photocatalyst materials which can generate active oxygen on the surface of the orthopedic implant to continuously generate active free radicals with strong oxidizing property under the illumination condition, thereby killing bacteria and removing bacterial biomembranes. In addition, copper ions and nano powder are not consumed in the reaction, so that the long-acting anti-infection effect can be realized.
3. The controllable and durable anti-infection orthopedic implant can start and accelerate the antibacterial activity of materials through the irradiation of light, can greatly improve the anti-infection effect, and reduces the physical and psychological pain and economic loss of patients caused by the infection of the orthopedic implant.
Drawings
FIG. 1 is a schematic view of the anti-infection coating on the surface of the orthopedic implant and the function thereof.
FIG. 2 results of antimicrobial evaluation of anti-infective coatings.
Detailed Description
In a specific implementation, fig. 1 illustrates the general idea of the invention. The copper-containing material and the substance (material with photocatalyst property) capable of generating Reactive Oxygen Species (ROS) under certain conditions are fixed/dispersed in the polymer coating carrier on the surface of the orthopedic implant in a certain mode, so that the anti-infection function of the orthopedic implant can be realized. In the coating with the anti-infection function, the mole percentage of the copper-containing material is in the range of 1 per thousand to 50 percent (preferably 2 to 10 percent), the mole percentage of the active oxygen substance can be generated in the range of 1 per thousand to 50 percent (preferably 2 to 10 percent), and the balance is a water-absorbing polymer coating material which is all components except the two functional materials. The copper-containing material is one or two of a cupric salt and a copper-carrying polymer, the copper-carrying polymer is formed by chemically bonding cupric ions to polymer small molecules, and the copper-containing material is uniformly distributed in the coating in the form of metal-polymer chain segments or in the form of metal inorganic salt, and the size of the copper-containing inorganic salt is in the range of 100 nm-10 mu m (preferably 100 nm-1 mu m).
The fixing mode of the functionalized material on the orthopedic implant comprises chemical grafting, physical blending, electrostatic interaction and the like. After the controllable and durable anti-infection orthopedic implant is implanted into a body, the anti-infection function of the implant can be regulated and controlled in an infrared illumination mode, and complications caused by infection are inhibited. The functional material in the anti-infection coating acts through chemical power and photodynamic, and the functional material plays a catalytic role in the action process and is basically not consumed, so that the anti-infection function is realized.
The present invention will be explained in further detail below by way of examples and figures.
Example 1:
first, a solution of copper-containing material is prepared:
(1) preparing a copper sulfate aqueous solution with the mass volume concentration of 10 mg/mL;
(2) dissolving a micromolecular chitosan oligosaccharide polymer in 1 wt% acetic acid aqueous solution to prepare micromolecular chitosan oligosaccharide polymer matrix solution with mass volume concentration of 50 mg/mL;
(3) adding a copper sulfate aqueous solution into a micromolecular chitosan oligosaccharide polymer matrix solution, wherein the mass ratio of the copper sulfate aqueous solution to the micromolecular chitosan oligosaccharide polymer matrix solution is 1: 2, fully stirring and reacting for 12 hours to obtain the copper-containing material solution.
Secondly, a stock solution of a material that can generate active oxygen under certain conditions is prepared:
adding molybdenum disulfide into the solution containing the copper material in a molar ratio of 1:1 with copper sulfate, and uniformly suspending the molybdenum disulfide in the solution containing the copper material by mechanical stirring or magnetic stirring for 2 hours to form the anti-infection coating solution.
Finally, preparing the anti-infection coating:
and preparing the anti-infection coating solution on the surface of the orthopedic implant by adopting spraying or dip-coating equipment, and drying to obtain the controllable and durable anti-infection orthopedic implant. Is marked as a photodynamic + chemodynamic anti-infective coating, and the thickness of the coating is 10 mu m.
In the coating with the anti-infection function, the mol percent of the copper-containing material is 10 percent, the mol percent of the active oxygen substance can be generated is 10 percent, and the rest is the coating material of the shell oligosaccharide-based polymer with water absorption.
Comparative example 1:
1. preparation of a solution of copper-containing material:
(1) preparing a copper sulfate aqueous solution with the mass volume concentration of 10 mg/mL;
(2) dissolving a micromolecular chitosan oligosaccharide polymer in 1 wt% acetic acid aqueous solution to prepare micromolecular chitosan oligosaccharide polymer matrix solution with mass volume concentration of 50 mg/mL;
(3) adding the copper sulfate aqueous solution into the micromolecular chitosan oligosaccharide polymer matrix solution, fully stirring and reacting for 12 hours to obtain the solution containing the copper material.
2. Preparing an anti-infection coating:
and preparing the coating solution containing the copper material on the surface of the orthopedic implant by adopting spraying or dip-coating equipment, and drying to obtain the orthopedic implant. Is marked as a chemical dynamic anti-infection coating, and the thickness of the coating is 10 mu m.
Comparative example 2:
1. preparing a stock solution of a material that can generate active oxygen under certain conditions:
(1) dissolving a micromolecular chitosan oligosaccharide polymer in 1 wt% acetic acid aqueous solution to prepare micromolecular chitosan oligosaccharide polymer matrix solution with mass volume concentration of 50 mg/mL;
(2) adding molybdenum disulfide into a micromolecular chitosan oligosaccharide polymer matrix solution, wherein the mass ratio of the molybdenum disulfide is 5%, and mechanically stirring or magnetically stirring for 2 hours to uniformly suspend the molybdenum disulfide in the polymer solution to form a material coating solution for generating active oxygen.
2. Preparing an anti-infection coating:
preparing the coating solution of the material for generating active oxygen on the surface of the orthopedic implant by adopting spraying or dip-coating equipment, and drying to obtain the orthopedic implant, which is marked as a photodynamic anti-infection coating with the thickness of 10 mu m.
The orthopedic implants prepared in example 1, comparative example 1 and comparative example 2 were evaluated in the antibacterial test under the infrared illumination condition, and the results of the antibacterial test are shown in fig. 2 with the orthopedic implants without coating treatment as the control group. As can be seen from fig. 2, the killing ability of the photodynamic + chemokinetic anti-infective coating against bacteria is much higher than that of the chemokinetic anti-infective coating and the photodynamic anti-infective coating. The results show that the technology disclosed by the invention has an outstanding anti-infection function and has obvious beneficial effects.
Example 2:
first, a solution of copper-containing material is prepared:
(1) preparing a copper chloride aqueous solution with the mass volume concentration of 100 mg/mL;
(2) dissolving a micromolecular sodium alginate polymer in 1 wt% acetic acid aqueous solution to prepare micromolecular sodium alginate polymer matrix solution with mass volume concentration of 100 mg/mL;
(3) adding a copper chloride aqueous solution into a micromolecular sodium alginate polymer matrix solution, wherein the mass ratio of the copper chloride aqueous solution to the micromolecular sodium alginate polymer matrix solution is 1: 2, fully stirring and reacting for 12 hours to obtain the copper-containing material solution.
Secondly, a stock solution of a material that can generate active oxygen under certain conditions is prepared:
adding the perovskite into the solution containing the copper material at a molar ratio of 4:1 to copper chloride, and uniformly suspending the perovskite in the solution containing the copper material by mechanical stirring or magnetic stirring for 2 hours to form the coating solution with anti-infection property.
Finally, preparing the anti-infection coating:
and preparing the anti-infection coating solution on the surface of the orthopedic implant by adopting spraying or dip-coating equipment, and drying to obtain the controllable and durable anti-infection orthopedic implant. Is marked as a photodynamic + chemodynamic anti-infective coating, and has the thickness of 20 mu m.
In the coating with the anti-infection function, the mol percent of the copper-containing material is 5 percent, the mol percent of the active oxygen substance can be generated is 20 percent, and the balance is the coating material of the sodium alginate crosslinked polymer with water absorption.
The orthopedic implant prepared in example 2 was evaluated in an antibacterial test under infrared illumination, and the results of the antibacterial test using the orthopedic implant without coating treatment as a control group show that the killing ability of the photodynamic + chemokinetic anti-infective coating against bacteria is much higher than that of the chemokinetic anti-infective coating and the photodynamic anti-infective coating.
Example 3:
first, a solution of copper-containing material is prepared:
(1) preparing a copper acetate aqueous solution with the mass volume concentration of 20 mg/mL;
(2) dissolving a micromolecular cyclodextrin polymer in 1 wt% acetic acid aqueous solution to prepare micromolecular cyclodextrin polymer matrix solution with mass volume concentration of 50 mg/mL;
(3) adding a copper acetate aqueous solution into a micromolecular cyclodextrin polymer matrix solution, wherein the mass ratio of the copper chloride aqueous solution to the micromolecular cyclodextrin polymer matrix solution is 1: 4, fully stirring and reacting for 24 hours to obtain the copper-containing material solution.
Secondly, a stock solution of a material that can generate active oxygen under certain conditions is prepared:
adding cadmium sulfide and copper acetate into the solution containing the copper material according to the molar ratio of 1:10, and uniformly suspending the cadmium sulfide in the solution containing the copper material by mechanical stirring or magnetic stirring for 2 hours to form the anti-infection coating solution.
Finally, preparing the anti-infection coating:
and preparing the anti-infection coating solution on the surface of the orthopedic implant by adopting spraying or dip-coating equipment, and drying to obtain the controllable and durable anti-infection orthopedic implant. The coating is marked as a photodynamic and chemical power anti-infection coating, and the thickness of the coating is 100 nm.
In the coating with the anti-infection function, the mol percent of the copper-containing material is 4 percent, the mol percent of the active oxygen substance can be generated is 40 percent, and the balance is the cyclodextrin cross-linked polymer coating material with water absorption.
The orthopedic implant prepared in example 3 was evaluated in an antibacterial test under infrared illumination, and the results of the antibacterial test using the orthopedic implant without coating treatment as a control group show that the killing ability of the photodynamic + chemokinetic anti-infective coating against bacteria is much higher than that of the chemokinetic anti-infective coating and the photodynamic anti-infective coating.
Claims (10)
1. An orthopedic implant with controllable and durable anti-infection function is characterized in that a coating with anti-infection function is prepared on the surface of the orthopedic implant, and the functional substances in the coating are copper-containing materials and can generate Reactive Oxygen Species (ROS).
2. A controllable and durable anti-infective implant for orthopedics according to claim 1, characterized in that the coating with anti-infective function comprises a copper-containing material and a substance capable of generating reactive oxygen species, which are both compatible with the coating material, dispersed in the coating material in the form of physical blend or bonded to the surface of the coating material by chemical bonding or electrostatic interaction.
3. A controllable, durable anti-infective orthopaedic implant according to claim 1, wherein the coating with anti-infective function comprises copper-containing material in a molar percentage in the range of 1% to 50%, active oxygen species in a molar percentage in the range of 1% to 50%, and a water-absorbing polymeric coating material as the remainder, the material being all constituents other than the two functional materials.
4. A controllable, durable anti-infective orthopaedic implant according to claim 1, 2 or 3, wherein the copper-containing material is one or both of a divalent copper salt and a copper-carrying polymer, the copper-carrying polymer being a divalent copper ion chemically bonded to a small polymer molecule, and the copper-containing material is uniformly distributed in the coating in the form of metal-polymer segments or in the form of a metal inorganic salt, wherein the size of the copper-containing inorganic salt is in the range of 100nm to 10 μm.
5. The orthopedic implant with controllable and lasting anti-infection function according to claim 4, wherein the small polymer molecule capable of chemically bonding divalent copper ions is one or more of chitosan oligosaccharide, alginate, amino acid, starch, cyclodextrin, cellulose, collagen, small molecule protein, polyalcohol, amine and polyester, and the divalent copper salt is one or more of basic copper sulfate, copper chloride, copper hydroxide, copper acetate, copper amino acid and copper quinoline.
6. An orthopaedic implant with controllable and persistent infection resistance according to claim 1, 2 or 3, wherein the substance capable of generating reactive oxygen species is an infrared photocatalyst material, and the infrared photocatalyst material is one or more of perovskite, molybdenum disulfide, cadmium sulfide and cadmium stannate.
7. A method for preparing an orthopaedic implant with controlled, long-lasting infection resistance according to claim 1, comprising the steps of:
the method comprises the following steps: preparing a solution of a copper-containing material;
step two: adding an active oxygen generating material to a solution of a copper containing material to produce a coating solution containing the copper containing material and the active oxygen generating material;
step three: and preparing the coating solution with the anti-infection function on the surface of the orthopedic implant by adopting spraying or dip coating equipment.
8. A method for preparing an orthopaedic implant with controlled and sustained infection resistance according to claim 7, wherein in the first step, when the copper-containing material is a copper-carrying polymer, a solution of the copper-containing material is prepared by chemical grafting, comprising the following steps:
(1) preparing a copper salt aqueous solution with the mass volume concentration of 1-200 mg/mL;
(2) preparing a micromolecular polymer matrix solution with the mass volume concentration of 5-1000 mg/mL, wherein the solvent is an organic solvent, and the type of the organic solvent is determined according to the characteristics of the adopted polymer matrix;
(3) adding a copper salt aqueous solution into a micromolecular polymer matrix solution, wherein the mass ratio of the copper salt aqueous solution to the micromolecular polymer matrix solution is 1: 1-1: and 10, fully stirring and reacting for 1-24 hours to obtain the copper-containing material solution.
9. A method for preparing an orthopaedic implant with controlled and sustained resistance to infection according to claim 7, wherein in step two, a molar ratio of active oxygen material to copper-containing material of 1: 10-10: 1, uniformly suspending active oxygen generating materials in a copper-containing material solution by mechanical stirring or magnetic stirring for 1-10 hours to form an anti-infection coating solution.
10. A process for preparing an orthopaedic implant with controllable and durable anti-infective activity according to claim 7, wherein the coating solution for coating the surface of orthopaedic implant with anti-infective activity is dried to form an anti-infective coating with photodynamic and chemico-kinetic properties and thickness of 100 nm-30 μm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010849162.8A CN112121234A (en) | 2020-08-21 | 2020-08-21 | Controllable and durable anti-infection orthopedic implant and preparation method thereof |
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| CN202010849162.8A CN112121234A (en) | 2020-08-21 | 2020-08-21 | Controllable and durable anti-infection orthopedic implant and preparation method thereof |
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| CN202010849162.8A Pending CN112121234A (en) | 2020-08-21 | 2020-08-21 | Controllable and durable anti-infection orthopedic implant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045476A (en) * | 2021-11-11 | 2022-02-15 | 重庆大学 | Copper-magnesium composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045476A (en) * | 2021-11-11 | 2022-02-15 | 重庆大学 | Copper-magnesium composite material and preparation method and application thereof |
| CN114045476B (en) * | 2021-11-11 | 2023-10-20 | 重庆大学 | Copper-magnesium composite material and preparation method and application thereof |
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