CN106521272A - Corrosion-resistant biological magnesium alloy, and preparation method thereof - Google Patents

Corrosion-resistant biological magnesium alloy, and preparation method thereof Download PDF

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CN106521272A
CN106521272A CN201610947204.5A CN201610947204A CN106521272A CN 106521272 A CN106521272 A CN 106521272A CN 201610947204 A CN201610947204 A CN 201610947204A CN 106521272 A CN106521272 A CN 106521272A
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magnesium alloy
medical
pure
magnesium
corrosion
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CN106521272B (en
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刘轲
马可
杜文博
王朝辉
李淑波
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Beijing University of Technology
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Beijing University of Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Abstract

The invention discloses a corrosion-resistant medical wrought magnesium alloy, and belongs to the field of biomedical metal materials. The corrosion-resistant medical wrought magnesium alloy comprises, by mass, 1 to 4% of Sn, 0.01 to 1% of Mn, 0.05 to 1% of Zn, and the balance Mg. The invention also discloses a method used for preparing the corrosion-resistant medical wrought magnesium alloy. The preparation method comprises following steps: raw materials are weighed at the above ratio, are subjected to polishing, and are delivered into a high purity graphite crucible; a mixed gas of SF6 and N2 is taken as a protective gas, and alloy smelting is carried out in a well-type resistance furnace; an obtained melt is stirred, is allowed to stand, and is subjected to casting so as to obtain a cast ingot; and extrusion alloy rods with excellent performance are obtained via extrusion. According to the preparation method, microalloying is adopted to prepare the rare earth element-free corrosion-resistant medical magnesium alloy, the rare earth element-free corrosion-resistant medical magnesium alloy possesses excellent biocompatibility and mechanical properties, and a problem that degradation rate of medical magnesium alloy in application process is too high is solved.

Description

A kind of anti-corrosion Biological magnesium alloy and preparation method thereof
Technical field:
The invention belongs to biomedical metallic material field, and in particular to a kind of bio-medical deformation of Mg-Zn-Mn-Sn systems Magnesium alloy and preparation method thereof.
Background technology
Bio-medical material is for diagnosing, treating, repair or replacing tissue or organ or promote the one of its function Class hi tech and new material.Accelerate with Chinese society aging population, in, the increase of young wound, the injection of new and high technology, with And people is improved with economic development to the attention rate of own health, bio-medical material industry is by high speed development.At present, applied Mainly include in clinical bio-medical material:Medical metal material, medical macromolecular materials, medical ceramic material, Yi Jishang State the bio-medical composition of different materials preparation.In above-mentioned several medical materials, during medical metal material is clinic The class Srgery grafting material being most widely used.Which has higher intensity.Good toughness, counter-bending fatigue strength and Excellent machine-shaping property, with the irreplaceable premium properties of other types medical material.
Traditional medical metal material is mainly stainless steel, titanium alloy, cochrome etc., and which is all present in use necessarily Defect.Such as cause metal ion to come off due to corroding or wearing and tearing and cause inflammation.Titanium alloy and cochrome elastic modelling quantity and day So the elastic modelling quantity difference of bone is too big, as causing stress-shielding effect during orthopaedics implant, is unfavorable for symphysis, easily Cause secondary fracture.Further, since these materials in vivo can not enter degraded, need second operation to take out, increased medical treatment into Originally the pain of patient has been increased.Therefore, for the defect of existing biological implantation material, exploitation new medical metal implant material is needed There is good biocompatibility, excellent mechanical property, and can degrade automatically and be absorbed by the body.Magnesium alloy materials are precisely Meet a class new medical metal material of these application requirements.
Magnesium alloy has advantages below as medical metal material:(1) with good biocompatibility, it is nontoxic can be in people Degrade in vivo, its catabolite will not produce harm to human body.(2) elastic modelling quantity of magnesium alloy is 45GPa or so, with people's bone Elastic modelling quantity is close to, and can effectively mitigate " stress-shielding effect " as orthopaedics implant.(3) with higher specific strength and Specific stiffness, and good processability, disclosure satisfy that the requirement of medical embedded material.(4) aboundresources, it is cheap.Therefore, magnesium Alloy has broad application prospects as degradable medical metal material.But magnesium alloy there is also some defects, limit Its some application as medical material.The key factor that wherein restriction magnesium alloy is used is exactly poor corrosion resistance, especially Which is to contain Cl-In the medium of ion, its corrosion rate can be accelerated.Used as implantation material, Corrosion Behaviors of Magnesium Alloys is too fast to be caused Liberation of hydrogen speed is larger, vivo environment pH value quickly raises generation abnormal response, will also cause mechanical performance to decline and can not meet work For the requirement of orthopaedics implant mechanical property.
In sum, solving the too fast problem of Corrosion Behaviors of Magnesium Alloys speed will become pass of the magnesium alloy as implantation materials application Key.And study and show:The alloying and deformation processing of magnesium can significantly improve the decay resistance of magnesium alloy.Therefore, select The elements such as Zn, Mn, Sn with preferable biocompatibility, organize to carry using microalloying and by extrusion process crystal grain thinning The decay resistance of high magnesium alloy, so as to meet requirement of the magnesium alloy as medical material to corrosive nature.This is closed to improving magnesium Gold is significant in the application of bio-medical field.
The content of the invention
It is an object of the invention to provide a kind of anti-corrosion bio-medical wrought magnesium alloy and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of bio-medical wrought magnesium alloy, it is characterised in that the magnesium alloy each component and its weight/mass percentage composition are:Sn 1-4%, Mn 0.01-1%, Zn 0.05-1%, remaining is Mg and inevitable impurity element.
In the magnesium alloy, component Zn, Mn, Sn and weight/mass percentage composition shared by inevitable impurity element are not more than 5%.
Above-mentioned bio-medical wrought magnesium alloy constituent is mutually strip phase.
The preparation method of the medical magnesium alloy is comprised the following steps:
(1) raw material prepares:Experiment raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin (99.99wt.%) with Mg-Mn intermediate alloys (preferred Mg-7.4wt.%Mn intermediate alloys);By raw material surface grinder buffing Cleaning, removes oxide on surface, to reduce the generation of melting impurity.
(2) melting:Pure graphite crucible is placed in resistance furnace and is preheated, after furnace temperature rises to 300-500 DEG C, be passed through in stove N2And SF6Mixed gas;Wherein, N2And SF6Flow volume ratio be 100:1;Pure magnesium ingot is put after logical protective gas 5-10min Enter crucible, furnace temperature risen to into 680-760 DEG C, treat that pure magnesium ingot is completely melt, according to pure zinc, Mg-Mn intermediate alloys, pure tin order Addition melting;Often add a kind of raw material, stand, finally after 5-8min being stirred at the uniform velocity, counterclockwise after raw material are completely melt Melt temperature is down to into 720 DEG C, insulation 30min is stood.Whole fusion process is continually fed into N2+SF6Hybrid protection gas, prevent The only oxidation or burning of magnesium alloy fused mass.
(3) cast:Skim, liquation is subsequently at the uniform velocity poured into the metal die of preheating, the demoulding after solidification obtains magnesium alloy casting Ingot, the preheating temperature of metal die is 200 DEG C, to prevent to aoxidize or burning during casting, protection is passed through in mould first Gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle.
(4) extrusion process:The magnesium alloy ingot that step (3) is obtained is preheated at 300-400 DEG C, then under preheating temperature Extruding, extrusion speed is 0.5-2.5mm/s, and extrusion ratio is 10:1.
During preparation, the addition of pure zinc need to additionally increase by 10% as scaling loss.
, up to 180MPa-300MPa, elongation percentage is up to 12%-20% for magnesium alloy mechanical properties of the present invention.In Hank ' Corrosion rate in s simulated body fluids is 0.2mm/y-0.8mm/y.
Can be used as orthopaedics implant application:Such as nail, hone lamella etc..Apply also for Blood vessel stent product.
The beneficial effects of the present invention is:
1. magnesium alloy of the present invention has preferable biocompatibility.Sn, Zn, Mn alloy element of addition is function of human body Requisite element, and using milligram ammonia theory preparing alloy.The catabolite work harmless to the human body of the magnesium alloy With can be fully absorbed by human body.
2. magnesium alloy of the present invention has excellent decay resistance.The raw material of molten alloy are high purity material, entirely Fusion process is carried out completely under a shielding gas, it is to avoid unnecessary impurity and oxide enter melt, improves the pure of alloy Degree, so as to be conducive to carrying heavy alloyed decay resistance.The addition of micro Mn elements can remove other heavy metal elements and avoid Generate harmful intergranular compound to put forward heavy alloyed corrosion resistance.By extrusion-processing technology, refining alloy grain structure, hence it is evident that Improve the decay resistance of magnesium alloy.
3. magnesium alloy of the present invention has good mechanical property.Zn and Mn have solution strengthening effect.In addition, Sn easily and Other alloying elements or metal impurities form compound, can further strengthen solid solution strengthening effect.By extrusion-processing technology, energy The crystal grain of enough notable refining alloys, puies forward heavy alloyed yield strength.
4. the present invention is by rational design of alloy and extrusion-processing technology, obtained Mg-Sn-Zn-Mn systems magnesium The degradation rate and mechanical property of alloy is adjustable, disclosure satisfy that magnesium alloy as medical embedded material to its corrosive nature and machinery The requirement of performance.
5. this preparation method has the advantages that the cost of raw material is low, preparation process is simple is easy to operate.
Description of the drawings
Fig. 1 is the optics metallograph of magnesium alloy in embodiment 1.
Fig. 2 is the stress-strain diagram of magnesium alloy in embodiment 1.
Fig. 3 is the polarization curve of magnesium alloy in embodiment 1.
Specific embodiment:
The present invention is further illustrated below in conjunction with specific case study on implementation, it is noted that:Following case study on implementation is served only for The specific implementation method of the bright present invention, can not limit rights protection scope of the present invention.
Embodiment 1
The preparation of as cast condition Mg-4.0wt%Sn-0.2wt%Mn-0.2wt%Zn magnesium alloy
1) raw material prepares:Test raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%) and (burn by 10% Damage and calculate), pure tin (99.99wt.%) and Mg-7.4wt.%Mn intermediate alloys (by the calculating of 30% scaling loss), and raw material are used Grinder buffing removes oxide on surface.
2) melting:To prevent the oxidation or burning of magnesium alloy fused mass, whole fusion process to be continually fed into N2+SF6Mixing protect Shield gas, wherein, N2And SF6Flow-rate ratio be 100:1;
A) crucible, Slag Tool, stirring rod and mould are dried in 200 DEG C of baking ovens stand-by;
B) crucible handled well is put in resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, is passed through shielding gas Body;
C) the high-purity magnesium ingot polished is added after being passed through protective gas 5-8min, while furnace temperature rises to 760 DEG C;
D) after magnesium ingot is completely melt, high purity zinc is added, after zinc is completely melt, 5min, furnace temperature is stirred at the uniform velocity, counterclockwise 740 DEG C are reduced to, and Mg-7.4wt.%Mn intermediate alloys are added after insulation 15min, are treated that Mg-7.4wt.%Mn intermediate alloys melt completely Stir 5min after change at the uniform velocity, counterclockwise, pure tin grain is added after 740 DEG C of insulation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise Stirring 5min;
E) furnace temperature is set to 720 DEG C, stands 30min, skims.
3) cast:Crucible is taken out, is cast;To prevent to aoxidize or burning during casting, first it is passed through in casting mold Protective gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle, after liquation at the uniform velocity to be poured into 200 DEG C of preheatings Metal die, the demoulding after solidification obtains alloy cast ingot.
4) extrusion process:The magnesium alloy ingot that 3) alloy preparation process obtains is processed intoExtrusion ingot, then Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, is subsequently extruded under preheating temperature, extrusion speed is 0.5- 2.5mm/s, extrusion ratio are 10:1.
5) in Hank ' s simulated body fluids, alloy corrosion speed is 0.8mm/y.
Embodiment 2:
The preparation of as cast condition Mg-3.0wt%Sn-0.01wt%Mn-0.5wt%Zn magnesium alloy
1) raw material prepares:Test raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%) and (burn by 10% Damage and calculate), pure tin (99.99wt.%) and Mg-7.4wt.%Mn intermediate alloys, and by raw material grinder buffing removing surface Oxide.
2) melting:To prevent the oxidation or burning of magnesium alloy fused mass, whole fusion process to be continually fed into N2+SF6Mixing protect Shield gas, wherein, N2And SF6Flow-rate ratio be 100:1;
A) crucible, Slag Tool, stirring rod and mould are dried in 200 DEG C of baking ovens stand-by;
B) crucible handled well is put in resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, is passed through shielding gas Body;
C) the high-purity magnesium ingot polished is added after being passed through protective gas 5-8min, while furnace temperature rises to 760 DEG C;
D) after magnesium ingot is completely melt, high purity zinc is added, after zinc is completely melt, 5min, furnace temperature is stirred at the uniform velocity, counterclockwise 740 DEG C are reduced to, and Mg-7.4wt.%Mn intermediate alloys are added after insulation 15min, are treated that Mg-7.4wt.%Mn intermediate alloys melt completely Stir 5min after change at the uniform velocity, counterclockwise, pure tin grain is added after 740 DEG C of insulation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise Stirring 5min;
E) furnace temperature is set to 720 DEG C, stands 30min, skims.
3) cast:Crucible is taken out, is cast;To prevent to aoxidize or burning during casting, first it is passed through in casting mold Protective gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle, after liquation at the uniform velocity to be poured into 200 DEG C of preheatings Metal die, the demoulding after solidification obtains alloy cast ingot.
4) extrusion process:The magnesium alloy ingot that 3) alloy preparation process obtains is processed intoExtrusion ingot, then Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, is subsequently extruded under preheating temperature, extrusion speed is 0.5- 2.5mm/s, extrusion ratio are 10:1.
5) in Hank ' s simulated body fluids, alloy corrosion speed is 0.5mm/y.
Embodiment 3:
The preparation of as cast condition Mg-1.0wt%Sn-1wt%Mn-0.05wt%Zn magnesium alloy
1) raw material prepares:Test raw material are respectively pure magnesium (99.9wt.%) 820g, pure zinc (99.99wt.%) 10.9g (calculating by 10% scaling loss), pure tin (99.99wt.%) 0.54g (calculating by 30% scaling loss) and Mg-7.4wt.%Mn intermediate alloys 174.9g (is calculated by 30% scaling loss), and raw material are removed oxide on surface with grinder buffing.
2) melting:To prevent the oxidation or burning of magnesium alloy fused mass, whole fusion process to be continually fed into N2+SF6Mixing protect Shield gas, wherein, N2And SF6Flow-rate ratio be 100:1;
A) crucible, Slag Tool, stirring rod and mould are dried in 200 DEG C of baking ovens stand-by;
B) crucible handled well is put in resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, is passed through shielding gas Body;
C) the high-purity magnesium ingot polished is added after being passed through protective gas 5-8min, while furnace temperature rises to 760 DEG C;
D) after magnesium ingot is completely melt, high purity zinc is added, after zinc is completely melt, 5min, furnace temperature is stirred at the uniform velocity, counterclockwise 740 DEG C are reduced to, and Mg-7.4wt.%Mn intermediate alloys are added after insulation 15min, are treated that Mg-7.4wt.%Mn intermediate alloys melt completely Stir 5min after change at the uniform velocity, counterclockwise, pure tin grain is added after 740 DEG C of insulation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise Stirring 5min;
E) furnace temperature is set to 720 DEG C, stands 30min, skims.
3) cast:Crucible is taken out, is cast;To prevent to aoxidize or burning during casting, first it is passed through in casting mold Protective gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle, after liquation at the uniform velocity to be poured into 200 DEG C of preheatings Metal die, the demoulding after solidification obtains alloy cast ingot.
4) extrusion process:The magnesium alloy ingot that 3) alloy preparation process obtains is processed intoExtrusion ingot, then Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, is subsequently extruded under preheating temperature, extrusion speed is 0.5- 2.5mm/s, extrusion ratio are 10:1.
5) in Hank ' s simulated body fluids, alloy corrosion speed is 0.40mm/y.
Embodiment 4:
The preparation of as cast condition Mg-2.0wt%Sn-0.5wt%Mn-1wt%Zn magnesium alloy
1) raw material prepares:Test raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin (99.99wt.%) with Mg-7.4wt.%Mn intermediate alloys, and raw material are removed into oxide on surface with grinder buffing.
2) melting:To prevent the oxidation or burning of magnesium alloy fused mass, whole fusion process to be continually fed into N2+SF6Mixing protect Shield gas, wherein, N2And SF6Flow-rate ratio be 100:1;
A) crucible, Slag Tool, stirring rod and mould are dried in 200 DEG C of baking ovens stand-by;
B) crucible handled well is put in resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, is passed through shielding gas Body;
C) the high-purity magnesium ingot polished is added after being passed through protective gas 5-8min, while furnace temperature rises to 760 DEG C;
D) after magnesium ingot is completely melt, high purity zinc is added, after zinc is completely melt, 5min, furnace temperature is stirred at the uniform velocity, counterclockwise 740 DEG C are reduced to, and Mg-7.4wt.%Mn intermediate alloys are added after insulation 15min, are treated that Mg-7.4wt.%Mn intermediate alloys melt completely Stir 5min after change at the uniform velocity, counterclockwise, pure tin grain is added after 740 DEG C of insulation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise Stirring 5min;
E) furnace temperature is set to 720 DEG C, stands 30min, skims.
3) cast:Crucible is taken out, is cast;To prevent to aoxidize or burning during casting, first it is passed through in casting mold Protective gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle, after liquation at the uniform velocity to be poured into 200 DEG C of preheatings Metal die, the demoulding after solidification obtains alloy cast ingot.
4) extrusion process:The magnesium alloy ingot that 3) alloy preparation process obtains is processed intoExtrusion ingot, then Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, is subsequently extruded under preheating temperature, extrusion speed is 0.5- 2.5mm/s, extrusion ratio are 10:1.
5) in Hank ' s simulated body fluids, alloy corrosion speed is 0.35mm/y.
Embodiment 5
The preparation of as cast condition Mg-1.0wt%Sn-0.2wt%Mn-1wt%Zn magnesium alloy
3) raw material prepares:Test raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin (99.99wt.%) with Mg-7.4wt.%Mn intermediate alloys, and raw material are removed into oxide on surface with grinder buffing.
4) melting:To prevent the oxidation or burning of magnesium alloy fused mass, whole fusion process to be continually fed into N2+SF6Mixing protect Shield gas, wherein, N2And SF6Flow-rate ratio be 100:1;
F) crucible, Slag Tool, stirring rod and mould are dried in 200 DEG C of baking ovens stand-by;
G) crucible handled well is put in resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, is passed through shielding gas Body;
H) the high-purity magnesium ingot polished is added after being passed through protective gas 5-8min, while furnace temperature rises to 760 DEG C;
I) after magnesium ingot is completely melt, high purity zinc is added, after zinc is completely melt, 5min, furnace temperature is stirred at the uniform velocity, counterclockwise 740 DEG C are reduced to, and Mg-7.4wt.%Mn intermediate alloys are added after insulation 15min, are treated that Mg-7.4wt.%Mn intermediate alloys melt completely Stir 5min after change at the uniform velocity, counterclockwise, pure tin grain is added after 740 DEG C of insulation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise Stirring 5min;
J) furnace temperature is set to 720 DEG C, stands 30min, skims.
6) cast:Crucible is taken out, is cast;To prevent to aoxidize or burning during casting, first it is passed through in casting mold Protective gas, is protected toward continuous conveying protective gas at liquid stream in casting cycle, after liquation at the uniform velocity to be poured into 200 DEG C of preheatings Metal die, the demoulding after solidification obtains alloy cast ingot.
7) extrusion process:The magnesium alloy ingot that 3) alloy preparation process obtains is processed intoExtrusion ingot, then Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, is subsequently extruded under preheating temperature, extrusion speed is 0.5- 2.5mm/s, extrusion ratio are 10:1.
8) in Hank ' s simulated body fluids, alloy corrosion speed is 0.2mm/y.
Embodiment 2-5 has optics metallograph similar to Example 1, stress-strain diagram, polarization curve, magnesium alloy , up to 180MPa-300MPa, elongation percentage is up to 12%-20% for mechanical properties.
Although having listed in detail here and having illustrated to be preferable to carry out case, skilled person will appreciate that, can not take off The modes such as various improvement, addition, replacement are carried out in the case of the marrow of the present invention, these contents are all identified as belonging to right will Ask within limited the scope of the present invention.

Claims (10)

1. a kind of bio-medical wrought magnesium alloy, it is characterised in that the magnesium alloy each component and its weight/mass percentage composition are:Sn 1-4%, Mn 0.01-1%, Zn 0.05-1%, remaining is Mg and inevitable impurity element.
2. according to a kind of bio-medical wrought magnesium alloy described in claim 1, it is characterised in that component in the magnesium alloy Zn, Mn, Sn and weight/mass percentage composition shared by inevitable impurity element are not more than 5%.
3. according to a kind of bio-medical wrought magnesium alloy described in claim 1, it is characterised in that bio-medical wrought magnesium alloy Constituent is mutually strip phase.
4. the method for preparing the bio-medical wrought magnesium alloy described in any one of claim 1-3, it is characterised in that
(1) raw material prepares:Experiment raw material are respectively pure magnesium, pure zinc, pure tin and Mg-Mn intermediate alloys;Raw material surface is used Grinder buffing is cleared up, and removes oxide on surface, to reduce the generation of melting impurity;
(2) melting:Pure graphite crucible is placed in resistance furnace and is preheated, after furnace temperature rises to 300-500 DEG C, N is passed through in stove2With SF6Mixed gas;Wherein, N2And SF6Flow volume ratio be 100:1;Pure magnesium ingot is put into into earthenware after logical protective gas 5-10min Furnace temperature is risen to 680-760 DEG C by crucible, treats that pure magnesium ingot is completely melt, is added according to the order of pure zinc, Mg-Mn intermediate alloys, pure tin Melting;Often add a kind of raw material, stand after 5-8min being stirred at the uniform velocity, counterclockwise after raw material are completely melt, finally will be molten Temperature is down to 720 DEG C, stands insulation 30min;Whole fusion process is continually fed into N2+SF6Hybrid protection gas, prevent magnesium The oxidation or burning of alloy melt;
(3) cast:Skim, liquation is subsequently at the uniform velocity poured into the metal die of preheating, the demoulding after solidification obtains magnesium alloy ingot, gold The preheating temperature of category mould is 200 DEG C, to prevent to aoxidize or burning during casting, is first passed through protective gas in mould, Protected toward continuous conveying protective gas at liquid stream in casting cycle;
(4) extrusion process:The magnesium alloy ingot that step (3) is obtained is preheated at 300-400 DEG C, is then squeezed under preheating temperature Pressure, extrusion speed is 0.5-2.5mm/s, and extrusion ratio is 10:1.
5. according to the method for claim 4, it is characterised in that Mg-Mn intermediate alloys are Mg-7.4wt.%Mn intermediate alloys, pure Purity 99.9wt.% of magnesium, purity 99.99wt.% of pure zinc, purity 99.99wt.% of pure tin.
6. according to the method for claim 4, it is characterised in that during preparation, the addition of pure zinc need to additionally increase by 10% As scaling loss.
7. according to the method for claim 4, it is characterised in that gained magnesium alloy mechanical properties reach 180MPa-300MPa, prolong Rate is stretched up to 12%-20%.
8. according to the method for claim 4, it is characterised in that corrosion rate of the gained magnesium alloy in Hank ' s simulated body fluids be 0.2mm/y-0.8mm/y。
9. the application of the bio-medical wrought magnesium alloy described in any one of claim 1-3, it is characterised in that be implanted into as orthopaedics Thing application.
10. the application of the bio-medical wrought magnesium alloy described in any one of claim 1-3, it is characterised in that be applied to medical Angiocarpy bracket product.
CN201610947204.5A 2016-10-26 2016-10-26 A kind of anti-corrosion Biological magnesium alloy and preparation method thereof Active CN106521272B (en)

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CN109161769A (en) * 2018-10-30 2019-01-08 北京科技大学 A kind of functional quickly solvable rare earth magnesium alloy material and preparation method thereof
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CN112410615A (en) * 2020-10-13 2021-02-26 桂林理工大学 Biodegradable medical zinc-tin alloy, preparation method and application thereof
CN114075629A (en) * 2021-10-25 2022-02-22 江苏理工学院 Degradable superfine crystal biological magnesium alloy and preparation method thereof
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WO2019017307A1 (en) * 2017-07-18 2019-01-24 国立研究開発法人物質・材料研究機構 Magnesium-based alloy wrought product and method for producing same
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CN109161769A (en) * 2018-10-30 2019-01-08 北京科技大学 A kind of functional quickly solvable rare earth magnesium alloy material and preparation method thereof
CN109161769B (en) * 2018-10-30 2022-11-22 北京科技大学 Functional rapidly-soluble rare earth magnesium alloy material and preparation method thereof
CN109112377A (en) * 2018-11-09 2019-01-01 吉林大学 A kind of anti-corrosion biological medical magnesium alloy and its preparation method and application
CN109295366A (en) * 2018-12-03 2019-02-01 北京工业大学 A kind of room temperature height forming magnesium alloy plate and preparation method thereof
CN112410615A (en) * 2020-10-13 2021-02-26 桂林理工大学 Biodegradable medical zinc-tin alloy, preparation method and application thereof
CN114075629A (en) * 2021-10-25 2022-02-22 江苏理工学院 Degradable superfine crystal biological magnesium alloy and preparation method thereof
WO2023080056A1 (en) * 2021-11-05 2023-05-11 国立研究開発法人物質・材料研究機構 Magnesium-based alloy extension material
CN114164370A (en) * 2021-12-09 2022-03-11 辽宁科技大学 Mg-based biological material based on high-entropy alloy theory and preparation method and application thereof
CN114164370B (en) * 2021-12-09 2022-05-27 辽宁科技大学 Mg-based biological material based on high-entropy alloy theory and preparation method and application thereof

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