CN106544563B - A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application - Google Patents

A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application Download PDF

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CN106544563B
CN106544563B CN201610958729.9A CN201610958729A CN106544563B CN 106544563 B CN106544563 B CN 106544563B CN 201610958729 A CN201610958729 A CN 201610958729A CN 106544563 B CN106544563 B CN 106544563B
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biodegradable
magnesium alloy
magnesium
purity
preparation
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CN106544563A (en
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于彦东
孙兆妹
李磊
李剑
张海波
霍小春
李毅
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Harbin University of Science and 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
    • A61L27/58Materials at least partially resorbable by the body
    • 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
    • A61L31/148Materials at least partially resorbable by the body
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a kind of biodegradable Mg Ca Mn Sn magnesium alloy materials and preparation method and application, the biodegradable Mg Ca Mn Sn magnesium alloy materials are prepared from the following components according to mass percent:Ca 0.5~3%, Mn 0.1~2%, Sn 1~5%, remaining is Mg and the inevitable impurity element brought by raw material.Specific preparation method includes melting, cast molding, the homogenizing annealing processing of raw material, hot extrusion processing.The biodegradable Mg Ca Mn Sn magnesium alloys of the present invention are to human body without any toxicity, good mechanical properties, preparation method is simple and at low cost, plate, the club-shaped material of different sizes and section requirement can be prepared according to demand, can be used as the preparation of the medical materials such as the orthopaedics implants such as bone plate, nail and angiocarpy bracket.

Description

A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method thereof with Using
Technical field
The invention belongs to medical implant material technical fields, are related to a kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials Material and preparation method and application.
Background technology
At present, the conventional medical metal material clinically generally used mainly has medical stainless steel, medical titanium alloy, medical Cobalt alloy etc., but these materials as medical implant often there are certain hidden danger, such as:Corrode in human body fluid environment The release of toxic element can be generated;The elasticity modulus of conventional medical metal material is higher than the elasticity modulus of skeleton;Need into Row second operation is drawn off.
Before magnesium alloy can trace back to more than 100 years as medical metal material, still, since the corrosion resistance of magnesium alloy is poor, The too fast performance requirement that can not meet as medical implant of degradation speed in human body, therefore magnesium alloy is limited as medicine The extensive use of implantation material.But the clinical practice of early stage has confirmed that feasibility of the magnesium alloy as medical material.
Development and maturation with different processing method and process for treating surface, the corrosion resistance and mechanics of magnesium alloy Performance is obtained for very big raising.Recent years, countries in the world have more researchers to proceed by magnesium alloy as biology The research of material.Many In vitroandin vivotrial results are also it was demonstrated that degradable magnesium alloy has much as medical implant material Outstanding performance.
Compared with conventional medical metal material, research of the biodegradable magnesium alloy as the medical metal material of a new generation Hot spot has unique degradability and bio-compatibility, therefore contains in the application aspect of degradable medical implant Huge potentiality.Magnesium be nutrient indispensable in human body, elasticity modulus and density closer to people's bone, can avoid producing Raw " stress-shielding effect ", and with good osteoinductive energy, the growth and healing of bone can be promoted.Moreover, high intensity Magnesium alloy has good mechanical performance, meets the performance requirement of preferable medical implant.After knitting, magnesium alloy implantation material Without taking out, second operation is avoided to the injury that patient brings and additional financial burden.
Invention content
The object of the present invention is to provide it is a kind of to human body without any toxicity, good mechanical properties, preparation method it is simple and into This relatively low biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials, are prepared from the following components according to mass percent: Ca 0.5~3%, Mn 0.1~2%, Sn 1~5%, remaining is Mg and the inevitable impurity element brought by raw material.
A kind of preparation method of above-mentioned biodegradable Mg-Ca-Mn-Sn magnesium alloy materials, includes the following steps:
(1)Using high-purity magnesium ingot, high-purity calcium grain, Mg-10%Mn intermediate alloys and high purity tin grain as raw material, by above-mentioned quality Percentage carries out the configuration of alloy raw material, using graphite crucible and is continually fed into high-purity argon gas as protective gas during melting;
(2)When graphite crucible is preheating to 450~550 DEG C, coverture is equably sprinkled in the bottom of crucible, adds in fritter High-purity magnesium ingot is warming up to 700~740 DEG C and keeps the temperature 10~30min, after high-purity magnesium ingot is completely melt, removes surface scum, melts Liquid is warming up to 760~780 DEG C and sequentially adds high-purity calcium grain, tin grain and Mg-Mn intermediate alloys, stirs 3~5 times, and standing 10~ 20min;
(3)After whole metal moltens, metallic solution is cooled to 735~745 DEG C, adds in refining agent and is stirred continuously, stirs After mixing 3~5min, metallic solution carries out the standing refining of 20~40min;
(4)When metallic solution is cooled to 690~710 DEG C, it is then poured into the metal that preheating temperature is 340~360 DEG C In mould, as cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots are obtained after ingot casting cooling.
Further, as cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots carry out 6 at 350~450 DEG C~for 24 hours Homogenizing annealing processing, obtain homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys.
Further, the mold of different sizes and shaped cross-section is selected, by homogenizing annealing treated Mg-Ca-Mn-Sn Magnesium alloy carries out conventional hot extrusion, and rodlike or lath-shaped extruded Magnesium Alloy, the extrusion temperature of different extrusion ratios are needed for acquisition 250~400 DEG C, extrusion speed is 0.5~8mm/s.
Compared with prior art, the present invention has the advantage that and has the beneficial effect that:
(1)Mg-Ca-Mn-Sn magnesium alloys in the present invention are using the addition design of nontoxic trace alloying element, to ensure that magnesium closes Gold will not generate toxic element after degrading in human body, while the addition of alloying element can improve magnesium alloy as medicine It is implanted into the mechanical property and corrosion resistance of material, it is ensured that the effect that magnesium alloy is played as implantation material.
(2)Biodegradable magnesium alloy in the present invention selects Mg, Ca, Sn and Mg-10%Mn intermediate alloy as former material Material, wherein Mg, Ca, Mn, Sn are the indispensable nutrients of human body, with automatic degradation of the magnesium alloy in human body, are released The non-toxic alloys element of releasing can be absorbed by the body, and avoid biosafety issues caused by alloying element.At the same time, Ca can To improve the creep-resistant property of magnesium alloy;Mn has the function of crystal grain thinning;Sn is conducive to the growth and development of body, can promote The healing of wound participates in influencing the function of hemoglobin, meanwhile, Sn, which is added in magnesium alloy, to be improved magnesium with crystal grain thinning and be closed The mechanical property and corrosion resistance of gold.
(3)The preparation method of the biodegradable Mg-Ca-Mn-Sn magnesium alloys of the present invention is simple and at low cost, can basis Demand prepares the plate of different sizes and section requirement, club-shaped material, can be used as the orthopaedics implants such as bone plate, nail and painstaking effort The preparation of the medical materials such as pipe holder.
Specific embodiment
Technical scheme of the present invention is further described with reference to embodiment, however, it is not limited to this, every right Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention, should all be contained It covers in protection scope of the present invention.
Embodiment 1:
Biodegradable Mg-Ca-Mn-Sn magnesium alloy materials in the present embodiment are according to mass percent by following components system It is standby to form:Ca 0.5%, Mn 1%, Sn 2%, remaining is Mg and the inevitable impurity element brought by raw material.Specifically Preparation process is as follows:
(1)Using high-purity magnesium ingot, high-purity calcium grain, Mg-10%Mn intermediate alloys and high purity tin grain as raw material, by above-mentioned quality Percentage carries out the configuration of alloy raw material, using graphite crucible and is continually fed into high-purity argon gas as protective gas during melting;
(2)When graphite crucible is preheating to 500 DEG C, suitable RJ-2 covertures are equably sprinkled in the bottom of crucible, are kept away Exempt to generate combustion phenomena.Then the high-purity magnesium ingot of fritter is added in, 720 ± 20 DEG C is warming up to and keeps the temperature 20min, treat that high-purity magnesium ingot is complete After fusing, surface scum is removed, melt is warming up to 780 DEG C and sequentially adds high-purity calcium grain, tin grain and Mg-Mn intermediate alloys, stirring 4 It is secondary, stand 15min;
(3)After whole metal moltens, metallic solution is cooled to 740 ± 5 DEG C, adds in suitable RJ-5 refining agents and continuous Stirring avoids generating combustion phenomena, and after stirring 5min, metallic solution carries out the standing refining of 30min;
(4)When metallic solution is cooled to 700 ± 10 DEG C, then it is poured into the metal pattern that preheating temperature is 350 DEG C, treats As cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots are obtained after ingot casting cooling.Casting cycle uniform speed slow, and it is molten in metal The argon gas of the continuous transport flow in liquid surface is protected.
Embodiment 2:
As different from Example 1, as cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots are at 400 DEG C for the present embodiment The lower homogenizing annealing processing for carrying out 12h, obtains homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys.
Embodiment 3:
The present embodiment as different from Example 2, selects the mold of different sizes and shaped cross-section, at homogenizing annealing Mg-Ca-Mn-Sn magnesium alloys after reason carry out conventional hot extrusion, the rodlike or lath-shaped As-extruded of different extrusion ratios needed for acquisition Magnesium alloy, extrusion temperature are 300 DEG C, extrusion speed 5mm/s.
Embodiment 4:
The present embodiment is unlike embodiment 1,2 or 3, and biodegradable Mg-Ca-Mn-Sn magnesium alloy materials are according to matter Amount percentage is prepared from the following components:Ca 1%, Mn 1.5%, Sn 3%, remaining for Mg and by raw material bring into can not The impurity element avoided.
Embodiment 5:
The present embodiment is unlike embodiment 1,2 or 3, and biodegradable Mg-Ca-Mn-Sn magnesium alloy materials are according to matter Amount percentage is prepared from the following components:Ca 1.25%, Mn 0.8%, Sn 1%, remaining is Mg and is brought by raw material Inevitable impurity element.
Embodiment 6:
The present embodiment is unlike embodiment 1,2 or 3, and biodegradable Mg-Ca-Mn-Sn magnesium alloy materials are according to matter Amount percentage is prepared from the following components:Ca 2%, Mn 0.5%, Sn 2%, remaining for Mg and by raw material bring into can not The impurity element avoided.

Claims (2)

1. a kind of preparation method of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials, it is characterised in that the method is in argon gas It carries out, includes the following steps as under conditions of protective gas:
(1) using high-purity magnesium ingot, high-purity calcium grain, Mg-10%Mn intermediate alloys and high purity tin grain as raw material, graphite is used during melting Crucible is simultaneously continually fed into high-purity argon gas as protective gas;
(2) when graphite crucible being preheating to 450~550 DEG C, coverture is equably sprinkled in the bottom of crucible, it is high-purity to add in fritter Magnesium ingot is warming up to 700~740 DEG C and keeps the temperature 10~30min, after high-purity magnesium ingot is completely melt, removes surface scum, melt liter Temperature sequentially adds high-purity calcium grain, tin grain and Mg-Mn intermediate alloys to 760~780 DEG C, stirs 3~5 times, stands 10~20min;
(3) after whole metal moltens, metallic solution is cooled to 735~745 DEG C, adds in refining agent and is stirred continuously, and stirring 3~ After 5min, metallic solution carries out the standing refining of 20~40min;
(4) it when metallic solution is cooled to 690~710 DEG C, is then poured into the metal pattern that preheating temperature is 340~360 DEG C, As cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots are obtained after ingot casting cooling;
(5) as cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots carry out to 6 at 350~450 DEG C~homogenization for 24 hours Annealing obtains homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys;
(6) homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys are subjected to conventional hot extrusion, different extrusion ratios needed for acquisition Rodlike or lath-shaped extruded Magnesium Alloy, extrusion temperature be 250~400 DEG C, extrusion speed be 0.5~8mm/s;
The biodegradable Mg-Ca-Mn-Sn magnesium alloy materials are prepared from the following components according to mass percent: Ca1.25%, Mn0.8%, Sn1%, remaining is Mg and the inevitable impurity element brought by raw material.
2. biodegradable Mg-Ca-Mn-Sn magnesium alloy materials described in claim 1 can be used as the preparation of medical implant material.
CN201610958729.9A 2016-11-04 2016-11-04 A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application Expired - Fee Related CN106544563B (en)

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Cited By (1)

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CN109972007A (en) * 2019-03-20 2019-07-05 北京科技大学 A kind of anastomosis staple material and preparation method thereof of biology degradable in vivo Mg-Zn-Ca-M

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EP3656884B1 (en) * 2017-07-18 2024-05-29 National Institute for Materials Science Magnesium-based alloy wrought product and method for producing same
CN108103335A (en) * 2017-09-12 2018-06-01 广东省材料与加工研究所 A kind of method for refining Mg-Zn systems alloy grain
CN108570585B (en) * 2018-06-13 2020-01-03 河南科技大学 Corrosion-resistant magnesium alloy and preparation method thereof
CN111218596A (en) * 2020-01-15 2020-06-02 太原科技大学 Short-term degradable magnesium alloy material for uterine cavity stent and preparation method thereof

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CN105401033A (en) * 2015-12-28 2016-03-16 太原理工大学 High strength and toughness anti-corrosion biomedical magnesium alloy

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CN102813966A (en) * 2012-08-29 2012-12-12 哈尔滨工程大学 Medical degradable magnesium alloy bone-fixing screw
CN105401033A (en) * 2015-12-28 2016-03-16 太原理工大学 High strength and toughness anti-corrosion biomedical magnesium alloy

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109972007A (en) * 2019-03-20 2019-07-05 北京科技大学 A kind of anastomosis staple material and preparation method thereof of biology degradable in vivo Mg-Zn-Ca-M

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