CN110541098A - corrosion-resistant biological magnesium-indium alloy and preparation method and application thereof - Google Patents

corrosion-resistant biological magnesium-indium alloy and preparation method and application thereof Download PDF

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CN110541098A
CN110541098A CN201911007810.9A CN201911007810A CN110541098A CN 110541098 A CN110541098 A CN 110541098A CN 201911007810 A CN201911007810 A CN 201911007810A CN 110541098 A CN110541098 A CN 110541098A
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indium
corrosion
powder
alloy
magnesium
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帅词俊
高成德
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Central South University
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Central South University
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • 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
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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention discloses a corrosion-resistant biological magnesium-indium alloy and a preparation method and application thereof. In the magnesium-indium alloy, the mass percentage of indium is 0.5-1.5 wt%. The preparation method comprises the following steps: the raw materials are firstly prepared according to the design components, and then the corrosion-resistant biological magnesium alloy is prepared by ball milling mixing and selective laser melting. According to the invention, indium is dissolved in the biological magnesium alloy through selective laser melting, on one hand, the indium element is a high hydrogen evolution overpotential metal, and the resistance of hydrogen evolution reaction is larger, so that corrosion is slowed down; on the other hand, the extremely high solid solubility and relatively high electrode potential of indium in magnesium can obviously reduce the corrosion sensitivity of magnesium alloy; moreover, indium hydroxide can be filled in loose magnesium hydroxide gaps, the integrity and the sealing performance of a corrosion product film on the surface of the alloy are improved, and the corrosion of body fluid is hindered, so that the corrosion resistance of the biological magnesium alloy is improved.

Description

Corrosion-resistant biological magnesium-indium alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomedical material preparation, and particularly relates to a corrosion-resistant biological magnesium-indium alloy, and a preparation method and application thereof.
Background
In recent years, a new generation of medical metal materials, which mainly represent biodegradable magnesium alloys, is becoming a research hotspot of orthopedic implant materials. The biological magnesium alloy has density and elastic modulus close to those of human bones, and magnesium is used as a nutrient element necessary for human bodies and can promote the formation of new bones. More importantly, the biological magnesium alloy is easy to corrode in human body environment, can be completely degraded as an implant in vivo, and avoids secondary operation. However, because the standard potential is very low, the degradation rate of the biological magnesium alloy in the human body environment is too fast, and the structural integrity is easily lost; at the same time, the gases produced by degradation and the elevated pH may also produce inflammation. Therefore, the improvement of the degradation performance of the biological magnesium alloy is a difficult problem which needs to be solved urgently as a degradable implant.
alloying is well known to be an effective way to improve corrosion resistance of magnesium alloys. It has been reported that alloying rare earth element yttrium in magnesium alloy can refine the second phase of magnesium alloy, reduce galvanic corrosion and improve corrosion resistance of magnesium alloy. However, the solid solubility of the commonly used alloying elements in the magnesium matrix is limited, so that a new second phase is easily formed to cause galvanic corrosion.
The indium has the characteristics of low melting point, excellent ductility, stable chemical properties and the like, has higher hydrogen evolution overpotential, can inhibit hydrogen generation, and has high solid solubility in a magnesium matrix, so that the corrosion resistance of the magnesium alloy is expected to be remarkably improved. At present, research aiming at improving the corrosion resistance of magnesium alloy by indium focuses on a surface coating method, and a layer of protective coating is generated on the surface of the magnesium alloy by plating indium on the surface of the magnesium alloy. Although the protective coating can protect the magnesium alloy in the early stage of degradation, the magnesium alloy matrix is corroded by the solution and quickly corroded after the magnesium alloy matrix is peeled off.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a corrosion-resistant biological magnesium-indium alloy and a preparation method and application thereof. The magnesium-indium alloy designed and prepared by the invention is an integral material, on one hand, indium is a high hydrogen evolution overpotential metal, the resistance of hydrogen evolution reaction is larger, and the corrosion of the alloy surface is not easy to carry out, thereby slowing down the corrosion; on the other hand, the extremely high solid solubility and relatively high electrode potential of indium in magnesium can obviously reduce the corrosion sensitivity of magnesium alloy; in addition, indium element in the corrosion product exists in the form of indium hydroxide, and the indium hydroxide can be filled in loose magnesium hydroxide gaps, so that the integrity and the sealing property of the corrosion product film layer on the surface of the alloy are improved, the corrosion of body fluid is hindered, and the corrosion resistance of the magnesium alloy is improved.
The invention relates to a corrosion-resistant biological magnesium-indium alloy, wherein the mass percentage of indium in the magnesium-indium alloy is 0.5-1.5 wt%. In the magnesium-indium alloy designed by the invention, indium is completely dissolved in the alloy.
The invention provides a method for preparing a corrosion-resistant biological magnesium-indium alloy, which comprises the following steps:
(1) Placing indium powder and powder A in a specific ratio in a ball mill, controlling the rotating speed of the ball mill to be 200-400rad/min under protective atmosphere, and ball milling for 4-8 hours to obtain mixed powder; wherein the mass percent of the indium powder in the mixed powder is 0.5-1.5 wt%; the powder A comprises magnesium alloy powder and/or magnesium metal powder;
(2) The mixed powder is used as a raw material, and the corrosion-resistant biological magnesium-indium alloy is prepared by selective laser melting in a protective atmosphere; in the preparation process, the scanning distance is controlled to be 0.05-0.15mm, the powder spreading thickness is controlled to be 0.05-0.15mm, the laser power is controlled to be 60-90W, and the scanning speed is 100-; the diameter of the light spot is 40-100 μm.
Preferably, the mass percentage of the indium powder in the mixed powder is 1.0 to 1.5 wt%, and more preferably 1.5 wt%.
Preferably, the laser power is 70-85W; the scanning speed is 150-300 mm/min; the diameter of the light spot is 65-85 μm; the scanning interval is 0.08-0.13 mm; the powder spreading thickness is 0.1-0.2 mm; the rotating speed of the ball mill is 250-350 rad/min; the ball milling time is 5-7 hours.
More preferably, the laser power is 80W; the scanning speed is 200 mm/min; the diameter of the light spot is 80 μm; the scanning distance is 0.1 mm; the powder spreading thickness is 0.1 mm; the rotating speed of the ball mill is 300 rad/min; the ball milling time was 6 hours.
Furthermore, the particle size of the powder A is 20-50 μm.
Further, the magnesium alloy powder includes a biological magnesium alloy powder.
further, the particle size of the indium powder is 5 to 10 μm.
Principles and advantages
according to the invention, the corrosion-resistant biological magnesium-indium alloy integral material is prepared by adopting the selective laser melting process and taking indium powder and biological magnesium alloy powder as raw materials for the first time, after the indium element is added, on one hand, the indium element is a high hydrogen evolution overpotential metal, and the alloy surface corrosion with larger resistance to hydrogen evolution reaction is not easy to carry out, so that the corrosion is slowed down; on the other hand, the extremely high solid solubility of indium in magnesium (about 30% at room temperature) and the relatively high electrode potential (-0.34Vvs-2.37V) can significantly reduce the corrosion sensitivity of magnesium alloy; indium ions in the corrosion products exist in the form of + 3-valent indium hydroxide, and the indium hydroxide can be filled in loose magnesium hydroxide gaps, so that the integrity and the sealing property of the corrosion product film on the surface of the alloy are improved, the intrusion of body fluid is hindered, and the degradation performance of the biological magnesium alloy is improved.
according to the invention, indium powder and magnesium alloy powder are mixed by ball milling, and through the optimized selection of ball milling process and parameters, the agglomeration of indium powder is avoided and the dispersion of indium powder is promoted, and then the biological magnesium-indium alloy can be rapidly solidified and formed by utilizing the extremely high cooling rate of the selective laser melting process. When the ball milling process parameters are not in the selected range, the agglomeration phenomenon of indium powder is serious, indium phase residue exists in the prepared alloy, and the residual indium not only can generate stress concentration at a crystal boundary to deteriorate the mechanical property of the alloy, but also can aggravate galvanic corrosion and deteriorate the degradation property of the alloy; or impurities are introduced to damage the biocompatibility of the biological magnesium alloy, thereby deteriorating the mechanical property and the degradation process of the magnesium alloy. When the melting process parameters of the laser selective area are not in the selected range, the indium powder is not completely dissolved, more large-size indium phase residues still exist in a crystal boundary, the mechanical property and the degradation property of the alloy are damaged, or the adverse phenomena of powder vaporization and burning loss and the like are caused, and the forming quality and the performance of the biological magnesium-indium alloy are influenced.
Compared with the prior art, the invention adopts indium powder with higher and lower contents to carry out comparison experiments, and finds that when the content of indium is too high, the cytotoxicity of the magnesium-indium alloy can be obviously increased, the biocompatibility of the magnesium-indium alloy is reduced, and when the content of indium is higher, a new second phase can be formed, galvanic corrosion is generated, and the degradation performance of the alloy is deteriorated; when the content of indium is too low, the corrosion potential of the alloy is difficult to effectively increase, a compact protective film is formed, corrosion medium erosion cannot be effectively prevented, and the improvement effect on the degradation resistance of the magnesium alloy is not obvious.
In conclusion, the raw material particle size, the ball milling process parameters, the selective laser melting process parameters and other parameters are not selected at will, but are crystallized through numerous tests and creative labor of the inventor. Meanwhile, the appropriate amount of indium can adjust the effects of grain refinement and product protection layers, so that the degradation speed of the biological magnesium alloy is adjusted, and the material designed by the invention is used as an implant and has more favorable advantages.
Detailed Description
The present invention will be further described with reference to specific examples.
example 1
Indium powder and AZ61 powder are used as raw materials, the indium powder and the AZ61 powder are weighed according to the mass ratio of 0.15:9.85, the raw materials are placed in a ball mill, the rotating speed is set to be 300rad/min under the protective atmosphere, the ball milling time is 6 hours, and the uniformly dispersed indium/AZ 61 mixed powder is obtained. Under the protection atmosphere, under the parameters of 80W of laser power, 200mm/min of scanning speed, 80 mu m of spot diameter, 0.1mm of scanning interval and 0.1mm of powder spreading thickness, the biological magnesium-indium alloy is prepared by utilizing the selective laser melting process.
tests show that the grain size is obviously refined, and no indium residue exists; the corrosion potential of the magnesium-indium alloy is-1.23 mVSCE, and the corrosion rate is 0.22 mm/y.
Example 2
indium powder and AZ61 powder are used as raw materials, the indium powder and the AZ61 powder are weighed according to the mass ratio of 0.1:9.9, the raw materials are placed in a ball mill, the rotating speed is set to be 300rad/min under the protective atmosphere, the ball milling time is 6 hours, and the uniformly dispersed indium/AZ 61 mixed powder is obtained. Under the protection atmosphere, under the parameters of 80W of laser power, 200mm/min of scanning speed, 80 mu m of spot diameter, 0.1mm of scanning interval and 0.1mm of powder spreading thickness, the biological magnesium-indium alloy is prepared by utilizing the selective laser melting process.
Tests show that the grain size is obviously refined, and no indium residue exists; the corrosion potential of the magnesium-indium alloy is-1.33 mVSCE, and the corrosion rate is 0.25 mm/y.
Example 3
Indium powder and AZ61 powder are used as raw materials, the indium powder and the AZ61 powder are weighed according to the mass ratio of 0.15:9.85, the raw materials are placed in a ball mill, the rotating speed is set to be 250rad/min under the protective atmosphere, the ball milling time is 5 hours, and the uniformly dispersed indium/AZ 61 mixed powder is obtained. Under the protection atmosphere, under the parameters of 80W of laser power, 200mm/min of scanning speed, 80 mu m of spot diameter, 0.1mm of scanning interval and 0.1mm of powder spreading thickness, the biological magnesium-indium alloy is prepared by utilizing the selective laser melting process.
Tests show that the grain size is obviously refined, and no indium residue exists; the corrosion potential of the Mg-in alloy is-1.38 mVSCE, and the corrosion current is 0.28 mm/y.
Example 4
indium powder and AZ61 powder are used as raw materials, the indium powder and the AZ61 powder are weighed according to the mass ratio of 0.15:9.85, the raw materials are placed in a ball mill, the rotating speed is set to be 300rad/min under the protective atmosphere, the ball milling time is 6 hours, and the uniformly dispersed indium/AZ 61 mixed powder is obtained. Under the protection atmosphere, under the parameters of 75W of laser power, 250mm/min of scanning speed, 70 mu m of spot diameter, 0.1mm of scanning interval and 0.1mm of powder spreading thickness, the biological magnesium-indium alloy is prepared by utilizing the selective laser melting process.
Tests show that the grain size is obviously refined, and no indium residue exists; the corrosion potential of the magnesium-indium alloy is-1.32 mVSCE, and the corrosion current is 0.3 mm/y.
in the process of developing the technology of the invention, the following schemes (such as comparative example 1, comparative example 2 and comparative example 3) are also tried, but the performance of the obtained product is far worse than that of the examples.
Comparative example 1
the other conditions were the same as in example 1 except that the indium powder content was 0.1% by weight, and the corrosion potential of the resulting product was found to be-1.50 mVSCE and the corrosion rate was 1.2mm/y by the test.
Comparative example 2
The other conditions were the same as those in example 1 except that the laser power was 30W, the scanning speed was 50mm/min, and the spot diameter was 150 μm; the performance of the obtained product is detected, the corrosion potential is reduced to-1.43 mVSCE, and the corrosion rate is 2.3 mm/y.
comparative example 3
the other conditions are consistent with those of the embodiment 1, the rotating speed during ball milling is 50rad/min, and the ball milling time is 1 h; the performance of the obtained product is detected, and an indium phase is found to remain in the grain boundary, which proves that the indium is not completely dissolved, the corrosion potential is-1.47 mVSCE, and the corrosion rate is 2.80 mm/y.

Claims (10)

1. a corrosion-resistant biological magnesium-indium alloy is characterized in that: in the magnesium-indium alloy, the mass percentage of indium is 0.5-1.5 wt%.
2. A preparation method of corrosion-resistant biological magnesium-indium alloy is characterized by comprising the following steps: the method comprises the following steps:
(1) Placing indium powder and powder A in a specific ratio in a ball mill, controlling the rotating speed of the ball mill to be 200-400rad/min under protective atmosphere, and ball milling for 4-8 hours to obtain mixed powder; wherein the mass percent of the indium powder in the mixed powder is 0.5-1.5 wt%; the powder A comprises magnesium alloy powder and/or magnesium metal powder;
(2) The mixed powder is used as a raw material, and the corrosion-resistant biological magnesium-indium alloy is prepared by selective laser melting in a protective atmosphere; in the preparation process, the scanning distance is controlled to be 0.05-0.15mm, the powder spreading thickness is controlled to be 0.05-0.15mm, the laser power is controlled to be 60-90W, the scanning speed is 100-500mm/min, and the spot diameter is 40-100 mu m.
3. The corrosion-resistant biological magnesium-indium alloy and the preparation method thereof according to claim 2, characterized in that:
The laser power is 70-85W;
The scanning speed is 150-300 mm/min;
The diameter of the light spot is 65-85 μm;
The scanning interval is 0.08-0.13 mm;
The powder spreading thickness is 0.07-0.13 mm;
The rotating speed of the ball mill is 250-350 rad/min;
The ball milling time is 5-7 hours.
4. The corrosion-resistant biological magnesium-indium alloy and the preparation method thereof according to claim 3, wherein the corrosion-resistant biological magnesium-indium alloy comprises the following components in percentage by weight:
The laser power is 80W;
The scanning speed is 200 mm/min;
The diameter of the light spot is 80 μm;
The scanning distance is 0.1 mm;
the powder spreading thickness is 0.1 mm;
The rotating speed of the ball mill is 300 rad/min;
the ball milling time was 6 hours.
5. the corrosion-resistant biological magnesium-indium alloy and the preparation method thereof according to claim 2, characterized in that: the mass percentage of the indium powder in the mixed powder is 1.0-1.5 wt%.
6. The corrosion-resistant biological magnesium-indium alloy and the preparation method thereof according to claim 5, wherein the corrosion-resistant biological magnesium-indium alloy comprises the following components: the mass percentage of indium powder in the mixed powder was 1.5 wt%.
7. The corrosion-resistant biological magnesium indium alloy and the preparation method thereof according to any one of claims 2 to 6, wherein: the particle size of powder A is 20-50 μm.
8. The corrosion-resistant biological magnesium indium alloy and the preparation method thereof according to any one of claims 2 to 6, wherein: the magnesium alloy powder includes a biological magnesium alloy powder.
9. the corrosion-resistant biological magnesium indium alloy and the preparation method thereof according to any one of claims 2 to 6, wherein: the particle size of the indium powder is 5 to 10 μm.
10. Use of a corrosion resistant bio-mg-in alloy according to claim 1, wherein: the applications include its use as biomedical materials.
CN201911007810.9A 2019-10-22 2019-10-22 corrosion-resistant biological magnesium-indium alloy and preparation method and application thereof Pending CN110541098A (en)

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Publication number Priority date Publication date Assignee Title
CN111394631A (en) * 2020-05-25 2020-07-10 太原理工大学 Magnesium alloy and preparation method thereof
CN112760536A (en) * 2020-02-19 2021-05-07 中南大学 Negative electrode material magnesium alloy and preparation method thereof

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CN103484699A (en) * 2013-09-10 2014-01-01 中南大学 Sealed smelting casting method for magnesium-based intermediate alloy containing low-melting point metal element
CN107466237A (en) * 2015-02-17 2017-12-12 首尔大学校产学协力团 The method of the degradation rate of biodegradable magnesium and control biodegradable magnesium
CN107739939A (en) * 2017-10-26 2018-02-27 中南大学 A kind of Biological magnesium alloy with anti-microbial property and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090171452A1 (en) * 2005-11-16 2009-07-02 Akiko Yamamoto Magnesium-Based Biodegradable Metallic Material
CN101702923B (en) * 2007-05-28 2013-05-01 阿克罗斯塔克英属维尔京群岛公司 Magnesium-based alloy
CN102802689A (en) * 2009-10-30 2012-11-28 阿克罗斯塔克英属维尔京群岛托尔托拉公司 Biodegradable implantable medical devices formed from super - pure magnesium-based material
CN103484699A (en) * 2013-09-10 2014-01-01 中南大学 Sealed smelting casting method for magnesium-based intermediate alloy containing low-melting point metal element
CN107466237A (en) * 2015-02-17 2017-12-12 首尔大学校产学协力团 The method of the degradation rate of biodegradable magnesium and control biodegradable magnesium
CN107739939A (en) * 2017-10-26 2018-02-27 中南大学 A kind of Biological magnesium alloy with anti-microbial property and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112760536A (en) * 2020-02-19 2021-05-07 中南大学 Negative electrode material magnesium alloy and preparation method thereof
CN111394631A (en) * 2020-05-25 2020-07-10 太原理工大学 Magnesium alloy and preparation method thereof

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