CN108969803B - Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof - Google Patents

Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof Download PDF

Info

Publication number
CN108969803B
CN108969803B CN201810826811.5A CN201810826811A CN108969803B CN 108969803 B CN108969803 B CN 108969803B CN 201810826811 A CN201810826811 A CN 201810826811A CN 108969803 B CN108969803 B CN 108969803B
Authority
CN
China
Prior art keywords
magnesium alloy
aluminum
zinc
source
magnesium oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810826811.5A
Other languages
Chinese (zh)
Other versions
CN108969803A (en
Inventor
刘宣勇
彭峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201810826811.5A priority Critical patent/CN108969803B/en
Publication of CN108969803A publication Critical patent/CN108969803A/en
Application granted granted Critical
Publication of CN108969803B publication Critical patent/CN108969803B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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
    • C23C18/02—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 by thermal decomposition
    • C23C18/12—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 by thermal decomposition characterised by the deposition of inorganic material other than metallic 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention relates to a medical degradable surface modified magnesium alloy with corrosion resistance, osteogenesis differentiation promotion and antibacterial property and a preparation method thereof. The surface of a surface modified magnesium alloy material for bone tissue repair comprises the following components: the magnesium oxide layer is generated in situ and provided with micron-sized holes, and the nanoscale Mg-Zn-Al layered double-metal hydroxide layer is generated in situ in the holes and on the surface of the magnesium oxide layer.

Description

Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof
Technical Field
The invention relates to a biomedical degradable surface modified magnesium alloy and a method thereof, in particular to a modification method for constructing a micron-sized magnesium oxide structure on the surface of a material through micro-arc oxidation and then further constructing a nano-sized Mg-Zn-Al layered double hydroxide on the surface by hydrothermal treatment, belonging to the technical field of surface modification of metal materials.
Background
At present, most of bone tissue repair materials used clinically are non-degradable metals, such as titanium alloy, nickel-titanium alloy, stainless steel, and the like. If the non-degradable implant is left in the body, rejection reaction to human tissues may occur, and the diseased region is problematic again, which may directly affect the retreatment. If the patient is taken out after the second operation, the patient is stressed economically and mentally. The degradable high polymer materials in the current market have too low elastic modulus and insufficient mechanical strength, and are difficult to perfectly replace bone tissues. The magnesium alloy has good mechanical property and elastic modulus which are very close to those of bone tissues, and the magnesium alloy has biodegradability and can be completely degraded in vivo, and degradation products can be discharged out of the body along with metabolism of the human body. Therefore, magnesium alloys are considered as next-generation biomedical metal materials. In conclusion, the development of the medical magnesium alloy material suitable for bone tissue repair has important prospect and social significance.
The disadvantages of magnesium alloys as medical materials are too low electrochemical potential and too high corrosion rate. The rapid corrosion can lead to premature loss of mechanical properties of the magnesium alloy on the one hand, and can also cause drastic changes in pH of tissue fluid around the implant, inflammatory reactions, and the like on the other hand. Currently, two major problems often faced by commonly used Ti alloy bone implants are: poor osteoinductive properties and susceptibility to infection. Magnesium alloys considered as next-generation biomedical metal materials may also face both of these problems if they are put into clinical use. Therefore, designing the magnesium alloy surface with good corrosion resistance and simultaneously having the functions of promoting bone differentiation and antibacterial property has important practical significance, and is also the key and difficult point of the surface modification research of the medical magnesium alloy.
Disclosure of Invention
In order to solve the problems that the degradation rate of the existing medical degradable magnesium alloy serving as a bone tissue repair material is too high, the possible osteoinduction is poor, the infection is easy and the like, the invention provides a surface modified magnesium alloy material with corrosion resistance, osteogenic differentiation promotion and antibacterial property and a preparation method thereof, so as to meet the clinical requirements on the degradation rate, osteogenic differentiation and antibacterial property of the magnesium alloy.
The first invention provides a surface-modified magnesium alloy material for bone tissue repair, the surface of the surface-modified magnesium alloy material having: the magnesium oxide layer is generated in situ and provided with micron-sized holes, and the nanoscale Mg-Zn-Al layered double-metal hydroxide layer is generated in situ in the holes and on the surface of the magnesium oxide layer.
According to the first invention, the magnesium oxide layer covers the surface of the magnesium alloy, and is firmly combined with the base material (magnesium alloy), so that the corrosion resistance of the magnesium alloy can be effectively improved, the Mg-Zn-Al layered double-metal hydroxide layer can be used for sealing holes of the magnesium oxide layer, so that the corrosion resistance of the magnesium alloy is further improved, and meanwhile, the functional element Zn is introduced into the surface of the material, so that the functions of bone differentiation, antibacterial property and the like can be endowed to the surface of the material. As the Mg-Zn-Al layered double hydroxide structure is more stable than that of the Mg-Al layered double hydroxide, and the amount of chloride ions which can be stored among the layers is more, the concentration of the chloride ions around the coating can be better reduced through an ion exchange mechanism, so that the corrosion resistance of the coating is further improved.
The magnesium alloy with the micro-nano structure surface provided by the invention has good corrosion resistance, and is beneficial to the adhesion and proliferation of mouse bone marrow mesenchymal stem cells on the surface of a material. In addition, ALP activity of the mouse bone marrow mesenchymal stem cells on the surface of the modified material is obviously improved, and the surface of the modified material shows antibacterial property to staphylococcus aureus. The invention can be widely applied to magnesium alloy medical instruments related to bone tissue repair.
Preferably, the magnesium oxide layer is obtained by oxidizing the surface of the magnesium alloy by a micro-arc oxidation technology. The micro-arc oxidation technology can be used for simply and conveniently constructing the micron-sized magnesium oxide coating on the surface of the magnesium alloy. The magnesium oxide prepared by micro-arc oxidation belongs to electrochemical in-situ preparation, so that the coating is harder and is more firmly combined with the matrix material, and the corrosion resistance of the magnesium alloy can be effectively improved.
Preferably, the magnesium oxide layer contains fluorine. After the fluorine element is introduced, the overall corrosion resistance and the coating stability of the magnesium oxide layer are better. The micro-arc oxidation coating has better stability, and is more beneficial to in-situ preparation of the Mg-Zn-Al layered double-metal hydroxide layer on the surface of the magnesium alloy subjected to micro-arc oxidation through hydrothermal treatment.
Preferably, the Mg-Zn-Al layered double metal hydroxide layer is obtained by subjecting a magnesium alloy in which the magnesium oxide layer is formed in situ to hydrothermal treatment in an alkaline solution containing an aluminum source and a zinc source.
The second invention provides a preparation method of a surface modified magnesium alloy material, which comprises the following steps: (1) constructing a micron-sized magnesium oxide layer on the surface of the magnesium alloy by adopting a micro-arc oxidation technology; and (2) carrying out hydrothermal treatment on the product obtained in the step (1) in an alkaline solution containing an aluminum source and a zinc source, so as to construct a nanoscale Mg-Zn-Al layered double-metal hydroxide layer on the surface of the micron-sized magnesium oxide layer.
According to the second invention, the micro-scale magnesium oxide coating can be simply and conveniently constructed on the surface of the magnesium alloy through the micro-arc oxidation technology. The magnesium oxide prepared by micro-arc oxidation belongs to electrochemical in-situ preparation, the coating is hard and is firmly combined with the matrix material, and the corrosion resistance of the magnesium alloy can be effectively improved. The magnesium oxide coating has a porous structure due to the arc discharge. In order to further improve the corrosion resistance and endow the magnesium oxide with special biological performance, a hydrothermal method is used for constructing nano-scale Mg-Zn-Al LDH on the surface of the magnesium oxide to seal the hole of the magnesium oxide layer, and meanwhile, a functional element Zn is introduced to the surface of the material. The Mg-Zn-Al LDH prepared by the hydrothermal method belongs to chemical in-situ preparation, can be filled with a hole structure of magnesium oxide, further improves the corrosion resistance of the magnesium alloy, and simultaneously can further endow the surface of the material with functions of promoting bone differentiation, resisting bacteria and the like and further improves the corrosion resistance as the Mg-Zn-Al LDH can release Zn ions.
Preferably, the electrolyte for micro-arc oxidation is 0.1-0.5M sodium hydroxide or potassium hydroxide, 0.02-0.08M sodium silicate or sodium glycerophosphate, and 0.1-0.2M potassium fluoride or ammonium fluoride. With this electrolyte, fluorine can be introduced into the magnesium oxide layer.
Preferably, the current of the micro-arc oxidation is 1-1.5A, the positive-negative frequency ratio is 2-3, the duty ratio is 5-15%, the frequency is 600-800, and the reaction cut-off voltage is 330-400V.
Preferably, in the hydrothermal treatment, the pH of the alkaline solution containing the aluminum source and the zinc source is 10 to 13.
Preferably, the aluminum source is a soluble aluminum salt, preferably at least one of aluminum nitrate, aluminum sulfate and aluminum acetate.
Preferably, the zinc source is a soluble zinc source, preferably at least one of zinc nitrate, zinc chloride and zinc acetate.
Preferably, in the alkaline solution containing the aluminum source and the zinc source, the concentration of aluminum ions is 0.02-0.06M, and the ratio of the concentration of aluminum ions to the concentration of zinc ions is 1: (0.0025 to 0.025).
Preferably, the treatment temperature of the hydrothermal treatment is 100-150 ℃ and the treatment time is 10-24 hours.
The third invention provides application of any one of the surface modified magnesium alloy materials in preparation of bone tissue repair materials.
Drawings
In FIG. 1, (a), (b), and (c) are SEM images of samples processed in examples 1, 2, and 3, respectively.
Figure 2 is an XRD pattern of the samples treated in examples 1, 2 and 3.
FIG. 3 shows the amount of hydrogen evolved in a 0.35 wt% NaCl solution for magnesium alloy and samples treated in examples 1, 2 and 3.
FIG. 4 is the adhesion of mouse bone marrow mesenchymal stem cells on magnesium alloy and samples treated in examples 1, 2, and 3.
FIG. 5 is the proliferation rate of mouse mesenchymal stem cells on samples treated in examples 1, 2 and 3.
FIG. 6 shows alkaline phosphatase activity of mouse bone marrow mesenchymal stem cells after incubation for 7 days on the surface of samples treated in examples 1, 2 and 3.
FIG. 7 shows the results of plating 1 day after incubation of Staphylococcus aureus on the sample surface (a) and the bacterial inhibition rate calculated from plating (b).
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Aiming at the application requirement of medical degradable magnesium alloy in the field of bone tissue repair materials, disclosed herein is a surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and a preparation method thereof.
The surface of the surface modified magnesium alloy material provided by the embodiment of the invention has a micro-nano composite structure, and the surface modified magnesium alloy material comprises the following components: the magnesium oxide layer is generated in situ and provided with micron-sized holes, and the nanoscale Mg-Zn-Al layered double-metal hydroxide layer is generated in situ in the holes and on the surface of the magnesium oxide layer.
The magnesium alloy is an alloy formed by adding other elements by taking magnesium as a matrix. Including but not limited to aluminum, zinc, zirconium, and the like. Because the invention mainly aims at the problem of poor corrosion resistance of the clinically used magnesium alloy, the magnesium alloy in the invention is preferably medical magnesium alloy, including but not limited to any one of magnesium alloys with the models of ZK60, JDBM, AZ31, AZ61 and AZ 91.
The magnesium oxide layer may act as a corrosion resistance. Preferably, the magnesium oxide layer is obtained by oxidizing the surface of the magnesium alloy by a micro-arc oxidation technology. The magnesium oxide prepared by micro-arc oxidation belongs to electrochemical in-situ preparation, so that the prepared magnesium oxide layer is hard and is firmly combined with a matrix material, and the corrosion resistance of the magnesium alloy can be effectively improved.
The aperture of the holes of the magnesium oxide layer can be 0.4-1.2 μm. The thickness of the magnesium oxide layer can be 4-6 μm.
Mg-Zn-Al layered double hydroxide (Mg-Zn-Al LDH for short) refers to a hydrotalcite-like structure consisting of a positively charged Mg-Zn-Al hydroxide layer and a negatively charged anion layer, and the chemical composition of the hydrotalcite-like structure can be expressed as [ M [ ]2+ 1-xM3+ x(OH)2][An-]x/n·zH2O, wherein M2+Is Mg2+And Zn2+，M3+Is Al3+，An-Can be CO3 2-、Cl-、SO4 2-And the like. x can be 0.17 to 0.34. Mg (magnesium)2+And Zn2+May be 1: (0.5 to 3), preferably 1: 2.8. the atomic ratio of Zn in the Mg-Zn-Al LDH can be 3.62-9.12%. If the Zn content is too low, it is difficult to exert its antibacterial action, and if it is too high, it is liable to cause cytotoxicity.
The Mg-Zn-Al layered double metal hydroxide layer can be obtained by subjecting a magnesium alloy in which the magnesium oxide layer is formed in situ to hydrothermal treatment in an alkaline solution containing an aluminum source and a zinc source.
The Mg-Zn-Al layered double-metal hydroxide layer can be composed of a plurality of nano sheets. The nano sheet can have a radial dimension of 800-1400 nm and a thickness of 100-150 nm. The Mg-Zn-Al layered double metal hydroxide layer may cover substantially the entire magnesium oxide layer. The thickness of the entire Mg-Zn-Al layered double hydroxide can be 2 to 5 μm.
Hereinafter, a method for producing a surface-modified magnesium alloy material (magnesium alloy surface modification method) of the present invention will be described as an example.
The magnesium alloy material (such as a magnesium alloy sheet) may be subjected to a cleaning pretreatment before modification, such as removal of a surface oxide layer with sandpaper, ultrasonic cleaning with absolute ethanol, and drying at room temperature.
The micro-arc oxidation technology is adopted to construct a micron-sized corrosion-resistant magnesium oxide coating on the surface of the magnesium alloy material. And oxidizing the surface of the magnesium alloy by adopting a micro-arc oxidation technology to obtain the magnesium oxide coating with micron-sized holes uniformly distributed. After micro-arc oxidation, a large amount of deionized water can be used for cleaning the surface of the material subjected to micro-arc oxidation treatment.
The electrolyte for micro-arc oxidation can be 0.1-0.5M sodium hydroxide or potassium hydroxide, 0.02-0.08M sodium silicate or sodium glycerophosphate, and 0.1-0.2M potassium fluoride or ammonium fluoride. The current of the micro-arc oxidation can be 0.8-1.5A, the positive-negative frequency ratio can be 2-3, the duty ratio can be 5-15%, and the frequency can be 600-800. The reaction cut-off voltage can be 330-400V.
And then, constructing the nano-scale Mg-Zn-Al LDH on the surface of the micron-scale corrosion-resistant coating by adopting a hydrothermal method, further improving the corrosion resistance of the coating, and simultaneously endowing the surface of the material with functions of promoting osteogenic differentiation, antibacterial property and the like.
In the hydrothermal treatment, the hydrothermal solution may be an alkaline solution containing an aluminum source and a zinc source. The aluminum source in the hydrothermal solution may be a soluble aluminum salt, and is preferably at least one of aluminum nitrate, aluminum sulfate, aluminum acetate, and the like. The zinc source in the hydrothermal solution may be a soluble zinc source, and is preferably at least one of zinc nitrate, zinc chloride and zinc acetate.
In the hydrothermal solution, the concentration of the aluminum source can be 0.02-0.06M. In the hydrothermal solution, the ratio of the molar concentration of aluminum ions to the molar concentration of zinc ions may be 1: (0.0025 to 0.025). Within this range, the greater the molar concentration of zinc ions, the higher the Zn content in the resulting coating, the more advantageous it is to resist corrosion, promote bone differentiation and resist bacteria. When the Zn concentration in the hydrothermal solution exceeds this range (i.e., the Zn concentration increases again), the zinc content in the coating cannot be increased further. This is because hydrothermal solution is an alkaline environment, and when the concentration of zinc ions is too high, it will precipitate in the form of zinc hydroxide or zinc oxide, so that it is not possible to provide a higher zinc ion concentration environment for the alkaline thermal environment. In one example, 0.02 to 0.06M of an aluminum source solution (e.g., an aluminum nitrate solution) and 0.5 to 5M of a zinc source solution (e.g., a zinc nitrate solution) are mixed and made alkaline to obtain an alkaline solution containing the aluminum source and the zinc source. Wherein the volume ratio of the aluminum source solution to the zinc source solution can be (30-70): (0.01-1), preferably (30-70): (0.01-0.1).
The hydrothermal solution has a pH of 10-13 and can be obtained by adding an alkali such as sodium hydroxide and/or potassium hydroxide.
The hydrothermal reaction temperature can be 100-150 ℃. The hydrothermal reaction time can be 10-24 hours.
After the nano-scale layered double hydroxide is constructed on the surface of the magnesium alloy subjected to micro-arc oxidation treatment by adopting a hydrothermal technology, a large amount of deionized water can be used for washing and drying.
The magnesium alloy surface obtained by the method consists of magnesium oxide with a pore structure and flaky Mg-Zn-Al LDH. The hole-shaped magnesium oxide is micron-sized, and the flaky Mg-Zn-Al LDH is nano-sized. The magnesium oxide prepared by micro-arc oxidation belongs to electrochemical in-situ preparation, the coating is hard and is firmly combined with the matrix material, and the corrosion resistance of the magnesium alloy can be effectively improved. The Mg-Zn-Al LDH prepared by the hydrothermal method belongs to chemical in-situ preparation, can fill the hole structure of magnesium oxide, and further improves the corrosion resistance of the magnesium alloy. Meanwhile, the Mg-Zn-Al LDH can release Zn ions, so that the functions of bone differentiation promotion, antibacterial property and the like on the surface of the material can be further endowed.
Compared with the prior art, the invention has the following beneficial effects.
1) After the magnesium alloy surface is modified by the method, the corrosion resistance of the alloy is obviously improved; 2) due to the existence of Mg-Zn-Al LDH, the mouse bone marrow stem cells are easier to adhere and proliferate on the surface of the material; 3) the alkaline phosphatase activity of the mouse bone marrow stem cells on the surface of the material is improved; 4) the Zn-doped modified material has the inhibition rate of more than 80 percent on staphylococcus aureus.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
And (3) removing an oxide layer on the surface of an AZ31 magnesium alloy sheet with the thickness of 2mm and the diameter of 10mm by using 1000-mesh SiC sand paper, and then ultrasonically cleaning by using alcohol. And then micro-arc oxidation treatment is carried out, wherein the electrolyte is 0.1M of potassium hydroxide, 0.04M of sodium silicate and 0.2M of potassium fluoride, the current is 0.8A, the positive-negative frequency ratio is 2, the duty ratio is 10%, and the frequency is 800. The reaction cut-off voltage was 360V. Then, hydrothermal treatment was carried out at 120 ℃ in 50mL of 0.02M aluminum nitrate solution, and the pH was adjusted to 12.8 with sodium hydroxide or potassium hydroxide for 12 hours. The resulting sample was labeled PEO/LDH.
FIG. 1 (a) is a scanning electron microscope image of the surface morphology of the magnesium alloy obtained by the modification treatment of this example. As can be seen from the figure, the surface after treatment is a layer of compact nano-sheet structure, and the holes generated in the micro-arc oxidation process are basically filled with the nano-sheet structure. Fig. 2 shows the XRD pattern of the sample surface after treatment in this example. As can be seen from the figure, the structure of the surface of the treated material is pure Mg-Al LDH, and because the flaky magnesium-aluminum layered double-metal hydroxide layer belongs to the nanometer level, the magnesium oxide covered by the flaky magnesium-aluminum layered double-metal hydroxide layer is also detected.
Example 2
And (3) removing an oxide layer on the surface of an AZ31 magnesium alloy sheet with the thickness of 2mm and the diameter of 10mm by using 1000-mesh SiC sand paper, and then ultrasonically cleaning by using alcohol. And then micro-arc oxidation treatment is carried out, wherein the electrolyte is 0.1M of potassium hydroxide, 0.04M of sodium silicate and 0.2M of potassium fluoride, the current is 0.8A, the positive-negative frequency ratio is 2, the duty ratio is 10%, and the frequency is 800. The reaction cut-off voltage was 360V. Then, hydrothermal treatment was carried out at 120 ℃ in 50mL of 0.02M aluminum nitrate solution, 10. mu.L of zinc nitrate (5M) was added, and the pH was adjusted to 12.8 with sodium hydroxide or potassium hydroxide for 12 hours. The obtained sample is marked as Zn-1 #.
FIG. 1 (b) is a scanning electron microscope image of the surface morphology of the magnesium alloy obtained by the modification treatment of this example. As can be seen from the figure, the surface after treatment is a layer of compact nano-sheet structure, and the holes generated in the micro-arc oxidation process are basically filled with the nano-sheet structure. Fig. 2 shows the XRD pattern of the sample surface after treatment in this example. As can be seen from the figure, the structure of the surface of the treated material is pure Mg-Zn-Al LDH, and the atomic ratio of Zn is 3.62% by X-ray photoelectron spectroscopy (XPS, PHI-5000C ESCA system Perkinelmer, USA). Since the lamellar magnesium-zinc-aluminum layered bimetallic hydroxide layer is relatively thin, the magnesium oxide covered by it is also detected.
Example 3
And (3) removing an oxide layer on the surface of an AZ31 magnesium alloy sheet with the thickness of 2mm and the diameter of 10mm by using 1000-mesh SiC sand paper, and then ultrasonically cleaning by using alcohol. And then micro-arc oxidation treatment is carried out, wherein the electrolyte is 0.1M of potassium hydroxide, 0.04M of sodium silicate and 0.2M of potassium fluoride, the current is 0.8A, the positive-negative frequency ratio is 2, the duty ratio is 10%, and the frequency is 800. The reaction cut-off voltage was 360V. Then, the reaction was carried out by hydrothermal treatment at 120 ℃ in 50mL of 0.02M aluminum nitrate solution and 100. mu.L of zinc nitrate (5M) was added, and then the pH was adjusted to 12.8 with sodium hydroxide or potassium hydroxide for 12 hours. The obtained sample is marked as Zn-2 #.
FIG. 1 (c) is a scanning electron microscope image of the surface morphology of the magnesium alloy obtained by the modification treatment of this example. As can be seen from the figure, the surface after treatment is a layer of compact nano-sheet structure, and the holes generated in the micro-arc oxidation process are basically filled with the nano-sheet structure. Fig. 2 shows the XRD pattern of the sample surface after treatment in this example. As can be seen from the figure, the structure of the surface of the treated material is pure Mg-Zn-Al LDH, and the atomic ratio of Zn is 9.12%. Since the lamellar magnesium-zinc-aluminum layered bimetallic hydroxide layer is relatively thin, the magnesium oxide covered by it is also detected.
Example 4 Hydrogen evolution
The unmodified samples and the samples obtained in examples 1, 2 and 3 were subjected to a hydrogen evolution test. Samples were soaked in 0.35 wt% NaCl solution (400mL), 4 samples per group, and the amount of hydrogen released during degradation of the samples was collected using an inverted funnel. The whole test procedure was carried out at a constant temperature of 37 ℃.
FIG. 3 is a graph showing the results of hydrogen evolution obtained by the reforming treatment in the above examples. It can be seen from the figure that the samples treated by the treatments 1, 2 and 3 have much reduced hydrogen evolution compared with the AZ31 magnesium alloy. The samples obtained after the treatments of examples 2 and 3 showed further reduced hydrogen evolution compared to the sample of example 1. The above results indicate that the corrosion resistance of Mg-Zn-Al LDH is better than that of Mg-Al LDH.
Example 5 adhesion
The influence of the magnesium alloy material obtained by the modification treatment in the above examples 1, 2 and 3 on the adhesion and spreading of the mouse bone marrow stem cells is evaluated by adopting the in vitro culture and fluorescent staining experiment of the mouse bone marrow mesenchymal stem cells. The specific method is as follows.
1) Placing the sample subjected to ultraviolet sterilization for 12h into a 24-well culture plate, and dripping 1mL of the culture plate with the density of 5 × 10 into each well4cell/mL cell suspension.
2) Place the cell culture plate in 5% CO2Incubating at 36.5 ℃ in a cell culture box with saturated humidity.
3) After 1, 4 and 24 hours of incubation, cells were stained with rhodamine and DAPI and observed with a laser confocal microscope (CLSM).
FIG. 4 shows the results of adhesion test of the magnesium alloys modified in the above modified examples 1, 2 and 3 and the unmodified magnesium alloy to mouse bone marrow stem cells. It can be seen from the figure that after 24 hours of culture, none of the cells spread on top of AZ 31. After 4 hours of incubation, the cells had begun to appear polygonal pseudopodia (cells indicated by arrows in the figure) on the surface of the Zn-1# and Zn-2# samples, while they remained round on the surface of the PEO/LDH samples. After 24 hours of culture, the cells were mainly elongated on the surface of the PEO/LDH sample, and spread more widely and over a larger area on the surface of the Zn-1# and Zn-2# samples. The above results indicate that LDH coating after zinc doping is more beneficial to the early adhesion and spreading of mouse bone marrow stem cells.
Example 6 proliferation
The effect of the samples obtained after the treatments of examples 1, 2 and 3 above on the activity of stem cells was evaluated using an in vitro culture experiment of mouse bone marrow stem cells. Using Almarblue (AlamarBlue)TMAbD serotec Ltd, UK) kits detect the proliferation of cells on the surface of materials. The method is as follows.
1) Placing the sample subjected to ultraviolet sterilization for 12 hours into a 24-well culture plate, and dripping 1mL of the sample with the density of 5 × 10 into each well4cell/mL cell suspension.
2) Placing the cell culture plate at 36.5 deg.C and 5% CO2And incubating in a cell culture box with saturated humidity.
3) After culturing the cells for 1, 3 and 5 days, the original culture medium was aspirated, the plates were replaced with new ones, and Almarblue (AlamarBlue) containing 10% Almarblue was addedTM) Fresh culture solution of stain, after the culture plate was placed in an incubator for 2 hours, 100. mu.L of culture solution was taken out from each well and put into a 96-well plate.
5) The intensity of the emitted light at 590nm of each well under excitation light having a wavelength of 560nm was measured using a microplate reader (BIO-TEK, ELX 800). The light intensity is positively correlated with the number of cells.
FIG. 5 shows the results of the experiment of this example. As shown, there was no significant difference in the proliferation rate of stem cells on the surface of the three groups of samples at days 1 and 3. After 5 days of culture, the proliferation rate of the stem cells on the surface of the Zn-2# sample is obviously higher than that of the other two groups. The above results show that the release of zinc ions does not affect the activity of stem cells, and by the fifth day, the corrosion resistance of Zn-2# sample is the best, so the surface of the material is more beneficial to the proliferation of stem cells.
Example 7
The effect of the samples obtained after the treatments of examples 1, 2 and 3 above on the alkaline phosphatase activity of stem cells was evaluated using an in vitro culture experiment of mouse bone marrow stem cells. The method is as follows.
1) Placing the sample subjected to ultraviolet sterilization for 12 hours into a 24-well culture plate, and dripping 1mL of the sample with the density of 5 × 10 into each well4cell/mL cell suspension.
2) Placing the cell culture plate at 36.5 deg.C and 5% CO2And incubating in a cell culture box with saturated humidity.
3) After 7 days of incubation, the alkaline phosphatase activity of the stem cells was detected with an alkaline phosphatase kit.
As shown in FIG. 6, the alkaline phosphatase activity of the stem cells on the surface of Zn-1# and Zn-2# samples was higher than that on the surface of PEO/LDH samples due to the release of Zn ions.
Example 8
The antibacterial properties of the samples obtained after the treatments of examples 1, 2 and 3 above were evaluated using gram-positive staphylococcus aureus. The method is as follows.
1) Placing the sample subjected to ultraviolet sterilization for 12 hours into a 24-well culture plate, and dripping 0.8mL of the sample with the density of 10 into each well7cfu/mL of the bacterial solution was cultured at 37 ℃ for 24 hours.
2) The sample was transferred to a 5mL centrifuge tube, 4mL of physiological saline was added, and the cells on the surface of the sample were shaken off by vigorous shaking on a shaker for 60 s.
3) Diluting the bacterial liquid by 10 times with normal saline, uniformly coating 100 mu L of diluted bacterial liquid on a standard agar plate, and continuously culturing for 18 hours.
4) The agar plate was photographed using a gel imaging system, and the antibacterial rate of the sample was calculated by counting the colonies on the agar plate.
The experimental results of this example are shown in FIG. 7. It can be seen from (a) in fig. 7 that the sample after zinc doping shows a significant inhibitory effect on staphylococcus aureus. As shown in fig. 7 (b), the inhibition rate of staphylococcus aureus was 80% or more in the sample after zinc doping compared to the sample without zinc doping.
The results of the above examples 4-8 show that the corrosion resistance of the Mg-Zn-Al LDH composite coating is obviously improved, and the surface of the material is more beneficial to the early adhesion and the later proliferation of stem cells. In addition, the Mg-Zn-Al LDH composite coating is more beneficial to osteogenic differentiation of stem cells and endows the material with good antibacterial property.

Claims (9)

1. A surface-modified magnesium alloy material for bone tissue repair, characterized in that the surface of the surface-modified magnesium alloy material has: the in-situ generated magnesium oxide layer is provided with micron-sized holes and contains fluorine elements, and the in-situ generated Mg-Zn-Al layered double-metal hydroxide layer is in the holes and on the surface of the magnesium oxide layer; wherein the atomic ratio of Zn in the Mg-Zn-Al layered double-metal hydroxide layer is 3.62-9.12%; the magnesium oxide layer is obtained by oxidizing the surface of the magnesium alloy through a micro-arc oxidation technology.
2. The surface-modified magnesium alloy material according to claim 1, wherein the Mg-Zn-Al layered double metal hydroxide layer is obtained by subjecting a magnesium alloy in which the magnesium oxide layer is formed in situ to hydrothermal treatment in an alkaline solution containing an aluminum source and a zinc source.
3. A method for producing the surface-modified magnesium alloy material according to claim 1 or 2, characterized by comprising the steps of:
(1) constructing a micron-sized magnesium oxide layer on the surface of the magnesium alloy by adopting a micro-arc oxidation technology; and
(2) and (2) carrying out hydrothermal treatment on the product obtained in the step (1) in an alkaline solution containing an aluminum source and a zinc source, so as to construct a nanoscale Mg-Zn-Al layered double-metal hydroxide layer on the surface of the micron-sized magnesium oxide layer.
4. The preparation method according to claim 3, wherein the electrolyte for micro-arc oxidation comprises 0.1-0.5M sodium hydroxide or potassium hydroxide, 0.02-0.08M sodium silicate or sodium glycerophosphate, and 0.1-0.2M potassium fluoride or ammonium fluoride, the current is 0.5-1.5A, the positive-negative frequency ratio is 2-3, the duty ratio is 5-15%, the frequency is 600-800, and the reaction cut-off voltage is 330-400V.
5. The method according to claim 4, wherein the alkaline solution containing an aluminum source and a zinc source has a pH of 10 to 13 in the hydrothermal treatment, wherein the aluminum source is a soluble aluminum salt, and the zinc source is a soluble zinc source.
6. The preparation method according to claim 5, wherein the aluminum source is at least one of aluminum nitrate, aluminum sulfate and aluminum acetate, and the zinc source is at least one of zinc nitrate, zinc chloride and zinc acetate.
7. The method according to claim 5, wherein the alkaline solution containing the aluminum source and the zinc source has an aluminum ion concentration of 0.02 to 0.06M and a ratio of the aluminum ion concentration to the zinc ion concentration of 1: (0.0025 to 0.025).
8. The method according to any one of claims 3 to 7, wherein the hydrothermal treatment is carried out at a treatment temperature of 100 to 150 ℃ for 10 to 24 hours.
9. Use of the surface-modified magnesium alloy material according to claim 1 or 2 in the preparation of a bone tissue repair material.
CN201810826811.5A 2018-07-25 2018-07-25 Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof Active CN108969803B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810826811.5A CN108969803B (en) 2018-07-25 2018-07-25 Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810826811.5A CN108969803B (en) 2018-07-25 2018-07-25 Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108969803A CN108969803A (en) 2018-12-11
CN108969803B true CN108969803B (en) 2021-08-31

Family

ID=64551037

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810826811.5A Active CN108969803B (en) 2018-07-25 2018-07-25 Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108969803B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109735887B (en) * 2019-03-21 2021-03-30 福州大学 Preparation method of magnesium alloy magnesium-manganese hydrotalcite/micro-arc oxidation corrosion-resistant coating
CN113638026B (en) * 2021-07-30 2022-06-10 江苏科技大学 Magnesium alloy surface MAO-LDH biological composite membrane layer and preparation method and application thereof
CN113755926B (en) * 2021-09-24 2024-03-15 天津理工大学 Method for preparing composite coating with high corrosion resistance and antibacterial property and photo-thermal property on surface of medical magnesium alloy

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220480A (en) * 2007-11-28 2008-07-16 中国科学院上海硅酸盐研究所 Corrosion resistant Al-Mg alloy protecting film and preparation thereof
CN103614717A (en) * 2013-10-30 2014-03-05 曾荣昌 Corrosion resistant film prepared by magnesium alloy surface hydrothermal method and preparation technology thereof
CN104619431A (en) * 2012-04-17 2015-05-13 凯密特尔有限责任公司 Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide
CN106693044A (en) * 2016-12-29 2017-05-24 山东科技大学 Method for preparing glutamate intercalation hydrotalcite medicinal magnesium alloy coating
CN106702238A (en) * 2017-02-17 2017-05-24 中国科学院上海硅酸盐研究所 Surface modified magnesium alloy material as well as preparation method thereof and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001295609B8 (en) * 2000-10-11 2007-05-10 Chemetall Gmbh Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way
US8277833B2 (en) * 2008-06-25 2012-10-02 Boston Scientific Scimed, Inc. Medical devices having surface coatings

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220480A (en) * 2007-11-28 2008-07-16 中国科学院上海硅酸盐研究所 Corrosion resistant Al-Mg alloy protecting film and preparation thereof
CN104619431A (en) * 2012-04-17 2015-05-13 凯密特尔有限责任公司 Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide
CN103614717A (en) * 2013-10-30 2014-03-05 曾荣昌 Corrosion resistant film prepared by magnesium alloy surface hydrothermal method and preparation technology thereof
CN106693044A (en) * 2016-12-29 2017-05-24 山东科技大学 Method for preparing glutamate intercalation hydrotalcite medicinal magnesium alloy coating
CN106702238A (en) * 2017-02-17 2017-05-24 中国科学院上海硅酸盐研究所 Surface modified magnesium alloy material as well as preparation method thereof and application thereof

Also Published As

Publication number Publication date
CN108969803A (en) 2018-12-11

Similar Documents

Publication Publication Date Title
Guo et al. Enhanced corrosion resistance and biocompatibility of biodegradable magnesium alloy modified by calcium phosphate/collagen coating
Lin et al. A functionalized TiO2/Mg2TiO4 nano-layer on biodegradable magnesium implant enables superior bone-implant integration and bacterial disinfection
Zhang et al. The dual function of Cu-doped TiO 2 coatings on titanium for application in percutaneous implants
Erakovic et al. Corrosion stability and bioactivity in simulated body fluid of silver/hydroxyapatite and silver/hydroxyapatite/lignin coatings on titanium obtained by electrophoretic deposition
CN108969803B (en) Medical degradable surface modified magnesium alloy with corrosion resistance, osteogenic differentiation promotion and antibacterial property and preparation method thereof
CN103110981B (en) Method for preparing antibacterial active titanium oxide nanotube array composite coating material
CN106702238B (en) Modified magnesium alloy materials in a kind of surface and its preparation method and application
Shao et al. A titanium surface modified with zinc-containing nanowires: Enhancing biocompatibility and antibacterial property in vitro
Xiong et al. Degradation behavior of n-MAO/EPD bio-ceramic composite coatings on magnesium alloy in simulated body fluid
Mousa et al. One-step anodization deposition of anticorrosive bioceramic compounds on AZ31B magnesium alloy for biomedical application
CN106567062B (en) With modified magnesium alloy materials in the surface of good corrosion and biocompatibility and its preparation method and application
Shimabukuro et al. Investigation of antibacterial effect of copper introduced titanium surface by electrochemical treatment against facultative anaerobic bacteria
Liang et al. In vitro and in vivo antibacterial performance of Zr & O PIII magnesium alloys with high concentration of oxygen vacancies
CN107829123B (en) Aluminum alloy with double-layer coating on surface and preparation method and application thereof
Molaei et al. Tailoring the biological response of zirconium implants using zirconia bioceramic coatings: A systematic review
Hu et al. The formation mechanism and bio-corrosion properties of Ag/HA composite conversion coating on the extruded Mg-2Zn-1Mn-0.5 Ca alloy for bone implant application
Hang et al. Preparation, characterization, corrosion behavior and cytocompatibility of NiTiO3 nanosheets hydrothermally synthesized on biomedical NiTi alloy
Chen et al. Degradation behavior, biocompatibility and antibacterial activity of plasma electrolytic oxidation treated zinc substrates
CN104274863B (en) A kind of magnesium alloy/conversion film composite biological material
Sukuroglu Investigation of antibacterial susceptibility of Ag-doped oxide coatings onto AZ91 magnesium alloy by microarc oxidation method
Aydin et al. Antimicrobial properties and corrosion behavior of TiO2NTs electrodes modified with Ag and ZnO nanorod in simulated body fluid solution
Li et al. rBMSC and bacterial responses to isoelastic carbon fiber-reinforced poly (ether-ether-ketone) modified by zirconium implantation
Li et al. Preparation, corrosion behavior and biocompatibility of MgFe-layered double hydroxides and calcium hydroxyapatite composite films on 316L stainless steel
CN107190255A (en) A kind of super-hydrophobic magnesium or magnesium alloy materials and its preparation method and application
Ling et al. Wettability transition of superhydrophobic myristic acid/dodecyl mercaptan/Cu@ ZIF-8/HA coating modified magnesium alloy driven by visible light for antibacterial and osteogenic applications

Legal Events

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