CN108411173A - A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof - Google Patents

A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof Download PDF

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CN108411173A
CN108411173A CN201810272939.1A CN201810272939A CN108411173A CN 108411173 A CN108411173 A CN 108411173A CN 201810272939 A CN201810272939 A CN 201810272939A CN 108411173 A CN108411173 A CN 108411173A
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magnesium
magnesium alloy
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张扬
宋雷鹏
陈晓阳
卢雅琳
丛孟启
李小平
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Jiangsu University of Technology
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    • 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
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    • 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
    • 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
    • A61L27/54Biologically active materials, e.g. therapeutic substances
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    • 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
    • C22F1/002Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • AHUMAN NECESSITIES
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    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention belongs to technical field of magnesium alloy material, and in particular to a kind of bio-medical Mg Sn Zn Sr magnesium alloys and preparation method thereof, the magnesium alloy includes following weight percent composition:The total amount of Sn 0.5 1.5%, Zn 0.3 0.7%, Sr 0.05 0.15%, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.Its technique is first to carry out mixed smelting to each ingredient, then carries out solution heat treatment, is finally plastically deformed.Magnesium alloy of the present invention selects a variety of the essential trace elements of the human bodys, while controlling alloying element total amount, and material non-toxic has good corrosion resistance and high-strength tenacity, can human body degradation.

Description

A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof
Technical field
The invention belongs to technical field of magnesium alloy material, and in particular to a kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and Preparation method.
Background technology
The metals such as traditional stainless steel, titanium alloy biological implantation material also exposes while obtaining extensive clinical application Go out some drawbacks:(1) stainless steel, titanium alloy etc materials and skeleton have a long way to go on elasticity modulus, generate and answer after implantation Power occlusion effect influences knitting process or leads to osteoporosis, or even causes secondary fracture;(2) although stainless steel, titanium alloy The chemical property of equal materials is stablized relatively, but may still release part harmful ion during being chronically implanted, and there is initiation Inflammation, the risk of allergy;(3) due to stainless steel, titanium alloy etc materials non-degradable in vivo, tissue functional rehabilitation it After need to take out by second operation, increase the pain, second operation risk and medical treatment cost of patient.With traditional stainless steel, The metal materials such as titanium alloy are compared, and magnesium alloy has a series of unique advantages as biological implantation material.In recent years, magnesium closes Golden material has become the research hotspot in biological implantation material field, and domestic and foreign scholars have carried out largely around Biological magnesium alloy material Research, but there are still a certain distance, major obstacle to be between clinical application at present:(1) alloy in the magnesium alloy of part There are genotoxic potentials for element;(2) in fluid environment, the degradation rate of magnesium alloy is too fast, is easy to happen serious local corrosion. Rational composition design and processing method selection, are exploitation new bio magnesium alloy materials, improve magnesium alloy in fluid environment Corrosion resistance, while improving the potential approach of its mechanical property.
In recent years, magnesium tin (Mg-Sn) is that alloy is used as a kind of potential Biological magnesium alloy material, gradually causes to learn both at home and abroad The attention of person.Sn belongs to the essential trace elements of the human body, and zoopery proves that Sn element toxicity is very low, meets biocompatibility It is required that.From the point of view of mechanical property angle, addition Sn elements can improve the intensity and plasticity of magnesium alloy.Zhen et al. is by Mg- 3Sn-0.5Mn (wt.%) alloys and the WE43 alloys of most study in current Biological magnesium alloy compare, and find the corrosion of the alloy Rate is less than WE43 alloys, and corrodes more uniformly (Zhen Z, Xi T, Zheng Y, et al.In vitro study on Mg-Sn-Mn alloy as biodegradable metals[J].Journal of Materials Science& Technology,2014,30(7):675-685.).J.Kub á sek et al. compared different-alloy constituent content Mg-Sn, Mg-Ga and Mg-In three classes cast bianry alloy, are examined from many-sided synthesis such as corrosion rate, cytotoxicity, mechanical property and cost Consider, it is believed that Mg-1Sn alloys are more suitable Biological magnesium alloy material (Kub á sek J, Vojt ě ch D, Lipov J, et al.Structure,mechaniSrl properties,corrosion behavior and cytotoxicity of Biodegradable Mg-X (X=Sn, Ga, In) alloys [J] .Materials Science and Engineering:C, 2013,33(4):2421-2432.)。
Invention content
Invention broadly provides a kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof, the alloy materials Nontoxicity has good corrosion resistance and high-strength tenacity, can human body degradation.Its technical solution is as follows:
A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys comprising following weight percent composition:Sn 0.5-1.5%, The total amount of Zn 0.3-0.7%, Sr 0.05-0.15%, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.
A kind of preparation method of above-mentioned bio-medical Mg-Sn-Zn-Sr magnesium alloys, includes the following steps:
(1) it is carried out under gas shield using pure magnesium ingot, pure tin ingot, pure zinc ingot and Mg-Sr intermediate alloys according to formula ratio Melting obtains Mg-Sn-Zn-Sr systems magnesium alloy ingot;
(2) solution heat treatment being carried out to Mg-Sn-Zn-Sr systems magnesium alloy ingot, solid solution temperature is 350-450 DEG C, when Between be 12-24h, water quenching is to room temperature after solid solution;
(3) the Mg-Sn-Zn-Sr systems magnesium alloy after solution heat treatment is plastically deformed, using mixing yoghurt skill Art, stirring-head rotating speed are 400-1600r/min, feed speed 40-200mm/min.
Preferably, protective gas is SF in step (1)6With CO2Mixed gas.
Preferably, method of smelting is in step (1):First pure magnesium is melted, pure tin is added when temperature rises to 720-740 DEG C With pure zinc, 8-12min is stirred after its fusing;Mg-10Sr intermediate alloys are then added, continuing stirring 8-12min keeps alloy first Element is evenly distributed, and is cooled to 710-720 DEG C of heat preservation 10min, removes surface scum, be poured into and be preheated to 180-220 DEG C of metal In pattern tool.
Each alloys producing is as follows in magnesium alloy:
Sn is one of the essential trace elements of the human body, and toxicity is minimum, and the adult of weight 70kg need to take in about 7.0mg daily Sn.Sn can improve the temperature-room type plasticity and intensity of magnesium alloy.
Zn is one of the essential trace elements of the human body, and participation forms follicle-stimulating hormone (FSH) and leuteinization hormone (LH), simultaneously The synthesis for participating in being formed DNA component zinc finger proteins, participates in the formation of a variety of enzymes.Zn can also promote the tensile strength of magnesium alloy And yield strength.
Sr also contributes to improve bone strength and bone mineral density, can be used for treating sclerotin shrinkage porosite disease.In addition, Sr also by It proves that osteoclast activity can be reduced and promotes the breeding of osteoblast, the suction of sclerotin is reduced while stimulating New bone formation It receives.Sr has strong Grain Refinement Effect in magnesium alloy crowd.
Plastic deformation can induce the recrystallization of magnesium alloy, and crystal grain thinning realizes refined crystalline strengthening, and crystal grain refinement is to improving magnesium The corrosion resistance of alloy also has very great help.
Using the above scheme, the present invention has the following advantages:
(1) a kind of degradable biological medical Mg- having both nontoxicity, good corrosion resistance and high-strength tenacity of the present invention Sn-Zn-Sr systems magnesium alloy and preparation method thereof, using nontoxic composition design, involved Sn, Zn and Sr element is all human body Required trace element;
(2) Mg-Sn-Zn-Sr systems of the present invention magnesium alloy, is designed using multicomponent microalloying, can be better The effect of each alloying element in the alloy is played, the corrosion resistance of alloy is improved, and improves its mechanical property;
(3) Mg-Sn-Zn-Sr systems of the present invention magnesium alloy controls alloying element total amount, cast, solid solution and plasticity Single-phase magnesium alloy is obtained after deformation, substantially eliminates the second phase, significantly inhibits the generation of galvanic corrosion, improves the corrosion resistant of alloy Corrosion energy, while ensuring can be degradable after the implantation organism of alloy is interior;
(4) Mg-Sn-Zn-Sr systems of the present invention magnesium alloy, after plastic deformation, crystal grain is refined, alloy it is resistance to Corrosive nature and mechanical property are improved.
Specific implementation mode
Experimental method in following embodiment is conventional method unless otherwise required, involved experiment reagent and material Material is conventional biochemical reagent and material unless otherwise required.
Embodiment 1
Magnesium alloy described in the present embodiment is made of Mg, Sn, Zn and Sr element, and each component mass percentage is:0.5% The total amount of Sn, 0.3%Zn, 0.15%Sr, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.
The preparation method of the alloy includes three melting, solution heat treatment and plastic deformation technique processes.
Wherein, preceding smelting technology process is in SF6And CO2It is carried out under the conditions of mixed gas protected, steps are as follows:It will be pure Magnesium melts in crucible electrical resistance furnace, and pure tin and pure zinc are added when temperature rises to 730 DEG C, and 10min is stirred after its fusing;Then Mg-10Sr intermediate alloys are added, continuing stirring 10min keeps alloying elements distribution uniform.720 DEG C of heat preservation 10min are cooled to, fishing is gone Surface scum is poured into and is preheated in 200 DEG C of metal type dies.
Subsequent solution heat treatment process is:The alloy cast ingot that melting is obtained is kept the temperature for 24 hours at 350 DEG C, subsequent water It quenches to room temperature.
Subsequent plastic deformation process process is:Mg-Sn-Zn-Sr alloys after solution treatment are plastically deformed, are adopted With mixing yoghurt technology, stirring-head rotating speed is 400r/min, feed speed 200mm/min.
The room temperature tensile intensity of acquired alloy is 257MPa, elongation percentage 21%.
Embodiment 2
Magnesium alloy described in the present embodiment is made of Mg, Sn, Zn and Sr element, and each component mass percentage is:1.0% The total amount of Sn, 0.5%Zn, 0.1%Sr, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.
The preparation method of the alloy includes three melting, solution heat treatment and plastic deformation technique processes.
Wherein, preceding smelting technology process is in SF6And CO2It is carried out under the conditions of mixed gas protected, steps are as follows:It will be pure Magnesium melts in crucible electrical resistance furnace, and pure tin and pure zinc are added when temperature rises to 730 DEG C, and 10min is stirred after its fusing;Then Mg-10Sr intermediate alloys are added, continuing stirring 10min keeps alloying elements distribution uniform.720 DEG C of heat preservation 10min are cooled to, fishing is gone Surface scum is poured into and is preheated in 200 DEG C of metal type dies.
Subsequent solution heat treatment process is:The alloy cast ingot that melting is obtained keeps the temperature 16h, subsequent water at 400 DEG C It quenches to room temperature.
Subsequent plastic deformation process process is:Mg-Sn-Zn-Sr alloys after solution treatment are plastically deformed, are adopted With mixing yoghurt technology, stirring-head rotating speed is 1000r/min, feed speed 120mm/min.
The room temperature tensile intensity of acquired alloy is 289MPa, elongation percentage 19%.
Embodiment 3
Magnesium alloy described in the present embodiment is made of Mg, Sn, Zn and Sr element, and each component mass percentage is:1.5% The total amount of Sn, 0.7%Zn, 0.05%Sr, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.
The preparation method of the alloy includes three melting, solution heat treatment and plastic deformation technique processes.
Wherein, preceding smelting technology process is in SF6And CO2It is carried out under the conditions of mixed gas protected, steps are as follows:It will be pure Magnesium melts in crucible electrical resistance furnace, and pure tin and pure zinc are added when temperature rises to 730 DEG C, and 10min is stirred after its fusing;Then Pure calcium is added, continuing stirring 10min keeps alloying elements distribution uniform.720 DEG C of heat preservation 10min are cooled to, fishing is removed surface scum, poured It notes and is preheated in 200 DEG C of metal type dies.
Subsequent solution heat treatment process is:The alloy cast ingot that melting is obtained keeps the temperature 12h, subsequent water at 450 DEG C It quenches to room temperature.
Subsequent plastic deformation process process is:Mg-Sn-Zn-Sr alloys after solution treatment are plastically deformed, are adopted With mixing yoghurt technology, stirring-head rotating speed is 1600r/min, feed speed 40mm/min.
The room temperature tensile intensity of acquired alloy is 299MPa, elongation percentage 22%.
It will be apparent to those skilled in the art that technical solution that can be as described above and design, make various other Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention Within.

Claims (4)

1. a kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys comprising following weight percent composition:Sn 0.5-1.5%, Zn The total amount of 0.3-0.7%, Sr 0.05-0.15%, impurity element S i, Fe, Cu and Ni are less than 0.02%, surplus Mg.
2. a kind of preparation method of bio-medical Mg-Sn-Zn-Sr magnesium alloys described in claim 1, it is characterised in that:Including Following steps:
(1) melting is carried out under gas shield using pure magnesium ingot, pure tin ingot, pure zinc ingot and Mg-Sr intermediate alloys according to formula ratio, Obtain Mg-Sn-Zn-Sr systems magnesium alloy ingot;
(2) solution heat treatment is carried out to Mg-Sn-Zn-Sr systems magnesium alloy ingots, solid solution temperature is 350-450 DEG C, and the time is 12-24h, water quenching is to room temperature after solid solution;
(3) the Mg-Sn-Zn-Sr systems magnesium alloy after solution heat treatment is plastically deformed, using mixing yoghurt technology, Stirring-head rotating speed is 400-1600r/min, feed speed 40-200mm/min.
3. the heat treatment method of bio-medical Mg-Sn-Zn-Sr magnesium alloys according to claim 2, it is characterised in that:Step Suddenly protective gas is SF in (1)6With CO2Mixed gas.
4. the heat treatment method of bio-medical Mg-Sn-Zn-Sr magnesium alloys according to claim 2, it is characterised in that:Step Suddenly method of smelting is in (1):First pure magnesium is melted, pure tin and pure zinc are added when temperature rises to 720-740 DEG C, after its fusing Stir 8-12min;Mg-10Sr intermediate alloys are then added, continuing stirring 8-12min keeps alloying elements distribution uniform, is cooled to 710-720 DEG C of heat preservation 10min, removes surface scum, is poured into the metal type dies for being preheated to 180-220 DEG C.
CN201810272939.1A 2018-03-29 2018-03-29 A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof Pending CN108411173A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110042289A (en) * 2019-04-18 2019-07-23 北京大学 A kind of magnesium alloy containing Sr
CN111676390A (en) * 2020-08-03 2020-09-18 北京科技大学 Zn-Ga alloy, preparation method and application thereof
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
CN116024471A (en) * 2022-12-01 2023-04-28 中南大学 High-strength plastic multi-water-soluble channel magnesium alloy and preparation method thereof

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CN101831580A (en) * 2010-04-19 2010-09-15 哈尔滨工程大学 Biomedical Mg-Sn-Mn series magnesium alloy and plate rolling process thereof
CN101869726A (en) * 2010-06-08 2010-10-27 东北大学 Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating and preparation method thereof
CN102552973A (en) * 2012-02-17 2012-07-11 浙江海圣医疗器械有限公司 Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof
CN102978495A (en) * 2012-12-13 2013-03-20 北京大学 Mg-Sr-Zn alloy and preparation method thereof
CN104328318A (en) * 2014-10-20 2015-02-04 东北大学 Preparation method of high-corrosion-resistance biodegradable magnesium alloy
CN105671391A (en) * 2016-01-19 2016-06-15 周倩 Full-degradable magnesium alloy and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831580A (en) * 2010-04-19 2010-09-15 哈尔滨工程大学 Biomedical Mg-Sn-Mn series magnesium alloy and plate rolling process thereof
CN101869726A (en) * 2010-06-08 2010-10-27 东北大学 Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating and preparation method thereof
CN102552973A (en) * 2012-02-17 2012-07-11 浙江海圣医疗器械有限公司 Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof
CN102978495A (en) * 2012-12-13 2013-03-20 北京大学 Mg-Sr-Zn alloy and preparation method thereof
CN104328318A (en) * 2014-10-20 2015-02-04 东北大学 Preparation method of high-corrosion-resistance biodegradable magnesium alloy
CN105671391A (en) * 2016-01-19 2016-06-15 周倩 Full-degradable magnesium alloy and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110042289A (en) * 2019-04-18 2019-07-23 北京大学 A kind of magnesium alloy containing Sr
CN111676390A (en) * 2020-08-03 2020-09-18 北京科技大学 Zn-Ga alloy, preparation method and application thereof
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
CN116024471A (en) * 2022-12-01 2023-04-28 中南大学 High-strength plastic multi-water-soluble channel magnesium alloy and preparation method thereof

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