CN106521272B - A kind of anti-corrosion Biological magnesium alloy and preparation method thereof - Google Patents
A kind of anti-corrosion Biological magnesium alloy and preparation method thereof Download PDFInfo
- Publication number
- CN106521272B CN106521272B CN201610947204.5A CN201610947204A CN106521272B CN 106521272 B CN106521272 B CN 106521272B CN 201610947204 A CN201610947204 A CN 201610947204A CN 106521272 B CN106521272 B CN 106521272B
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- pure
- alloy
- magnesium
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 title claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 37
- 239000011701 zinc Substances 0.000 claims description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 25
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000007499 fusion processing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000012890 simulated body fluid Substances 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000007769 metal material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000005275 alloying Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 5
- 239000007943 implant Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 239000012567 medical material Substances 0.000 description 4
- 239000003519 biomedical and dental material Substances 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910018645 Mn—Sn Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- LQHZJYFIRFRDKF-UHFFFAOYSA-N gold magnesium Chemical compound [Mg].[Au] LQHZJYFIRFRDKF-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials 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
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- A61L31/00—Materials 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Landscapes
- 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)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials For Medical Uses (AREA)
Abstract
A kind of anti-corrosion medical wrought magnesium alloy, belongs to biomedical metallic material field.Its ingredient and mass percent are：Sn1 4%, Mn 0.01 1%, Zn 0.05 1%, remaining is Mg.The invention also discloses the preparation methods of the alloy：It weighs raw material according to alloying component and polishes and be placed in high purity graphite crucible, with SF6And N2Mixed gas be protective gas molten alloy in well formula resistance furnace, stirring melt, after standing casting obtain ingot casting, the extruded alloy bar being had excellent performance by extrusion-processing technology.The present invention prepares the anti-corrosion medical magnesium alloy without rare earth element by microalloying has preferable biocompatibility and mechanical property, and solves the problems, such as medical magnesium alloy degradation rate is too fast in application process.
Description
Technical field：
The invention belongs to biomedical metallic material fields, 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.With Chinese society aging of population accelerates, in, the increase of young wound, the injection of new and high technology, with
And people improves the attention rate of own health with economic development, bio-medical material industry is by high speed development.Currently, having applied
Include mainly 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, medical metal material is in clinic
A kind of surgical implantation material being most widely used.It is with higher intensity.Good toughness, counter-bending fatigue strength and
Excellent machine-shaping property, with the irreplaceable excellent performance of other types medical material.
Traditional medical metal material is mainly stainless steel, titanium alloy, cochrome etc., is all existed in use certain
Defect.Such as cause metal ion to fall off to cause inflammation due to corroding or wearing.Titanium alloy and cochrome elasticity modulus and day
The elasticity modulus difference of right bone is too big, and stress-shielding effect can be caused when as orthopaedics implant, is unfavorable for symphysis, is easy
Cause secondary fracture.Further, since these materials cannot need second operation to take out into degradation in vivo, increase medical treatment at
This has aggravated the pain of patient.Therefore, for the defect of existing biological implantation material, exploitation new medical metal implant material needs
There is good biocompatibility, excellent mechanical property, and can degrade and be absorbed by the body automatically.Magnesium alloy materials are precisely
Meet a kind of new medical metal material of these application requirements.
Magnesium alloy has the following advantages as medical metal material：(1) have good biocompatibility, it is nontoxic can be in people
Degradation in vivo, catabolite will not generate harm to human body.(2) elasticity modulus of magnesium alloy is 45GPa or so, with people's bone
Elasticity modulus is close, can effectively mitigate " stress-shielding effect " as orthopaedics implant.(3) have higher specific strength and
Specific stiffness, and processing performance is good, disclosure satisfy that the requirement of medical embedded material.(4) resourceful, it is cheap.Therefore, magnesium
Alloy has broad application prospects as degradable medical metal material.But magnesium alloy is limited there is also some defects
Its some application as medical material.The key factor that wherein limitation magnesium alloy uses is exactly poor corrosion resistance, especially
It is to contain Cl-In the medium of ion, corrosion rate can be accelerated.As implantation material, Corrosion Behaviors of Magnesium Alloys is too fast to be caused
Liberation of hydrogen rate is larger, vivo environment pH value quickly increases and is abnormal reaction, will also cause mechanical performance decline that cannot meet work
For the requirement of orthopaedics implant mechanical property.
In conclusion solving the problems, such as the too fast pass that will be applied as implantation material as magnesium alloy of Corrosion Behaviors of Magnesium Alloys rate
Key.And research shows that：The alloying and deformation processing of magnesium can significantly improve the corrosion resistance of magnesium alloy.Therefore, it selects
The elements such as Zn, Mn, Sn with preferable biocompatibility are carried using microalloying and by extrusion process crystal grain thinning tissue
The corrosion resistance of high magnesium alloy, to meet requirement of the magnesium alloy as medical material to corrosive nature.This is closed to improving magnesium
Gold is of great significance in the application of bio-medical field.
Invention content
The purpose of the present invention is to provide a kind of anti-corrosion bio-medical wrought magnesium alloys and preparation method thereof.
The purpose of the present invention is what is be 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 mass percentage are：Sn
1-4%, Mn 0.01-1%, Zn 0.05-1%, remaining is Mg and inevitable impurity element.
Mass percentage shared by component Zn, Mn, Sn and inevitable impurity element is not more than in the magnesium alloy
5%.
Above-mentioned bio-medical wrought magnesium alloy constituent is mutually strip phase.
The preparation method of the medical magnesium alloy includes the following steps：
(1) raw material preparation：It is respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin to test raw material
(99.99wt.%) and Mg-Mn intermediate alloys (preferably 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, is passed through into 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 is risen to 680-760 DEG C, wait for that pure magnesium ingot is completely melt, according to the sequence of pure zinc, Mg-Mn intermediate alloys, pure tin
Add melting；A kind of raw material are often added, at the uniform velocity, after stirring 5-8min counterclockwise are stood after raw material are completely melt, finally
Melt temperature is down to 720 DEG C, stands heat preservation 30min.Entire fusion process is continually fed into N2+SF6Hybrid protection gas, prevent
The only oxidation or burning of magnesium alloy fused mass.
(3) it casts：It skims, melt is then at the uniform velocity poured into the metal die of preheating, demoulded after solidification and obtain magnesium alloy casting
Ingot, the preheating temperature of metal die are 200 DEG C, and to prevent to aoxidize or burn when casting, protection is first passed through in mold
Gas is protected toward continuous conveying protective gas at liquid stream in casting process.
(4) extrusion process：The magnesium alloy ingot that step (3) is obtained is preheated at 300-400 DEG C, then under preheating temperature
It squeezes, extrusion speed 0.5-2.5mm/s, extrusion ratio 10:1.
The addition of pure zinc need to additionally increase by 10% as scaling loss during preparation.
Magnesium alloy mechanical properties of the present invention are up to 180MPa-300MPa, and elongation percentage is up to 12%-20%.In Hank '
Corrosion rate in s simulated body fluids is 0.2mm/y-0.8mm/y.
It can be used as orthopaedics implant application：Such as nail, bone plate.Apply also for Blood vessel stent product.
The beneficial effects of the present invention are：
1. magnesium alloy of the present invention has preferable biocompatibility.Sn, Zn, Mn alloy element of addition are function of human body
Essential element, and alloy is prepared using the theory of milligram ammonia.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 corrosion resistance.The raw material of molten alloy are high purity material, entirely
Fusion process carries out under a shielding gas completely, and unnecessary impurity and oxide is avoided to enter melt, improves the pure of alloy
Degree, to be conducive to improve the corrosion resistance of alloy.The addition of micro Mn elements can remove other heavy metal elements and avoid
Harmful intergranular compound is generated to improve the corrosion resistance of alloy.Pass through extrusion-processing technology, refining alloy grain structure, hence it is evident that
Improve the corrosion resistance of magnesium alloy.
3. magnesium alloy of the present invention has good mechanical property.Zn and Mn has solution strengthening effect.In addition, Sn be easy and
Other alloying elements or metal impurities form compound, can further strengthen solid solution strengthening effect.Pass through extrusion-processing technology, energy
The crystal grain of enough notable refining alloys, improves the yield strength of alloy.
4. the present invention passes through rational design of alloy and extrusion-processing technology, obtained Mg-Sn-Zn-Mn systems magnesium
The degradation rate and mechanical property of alloy are adjustable, disclosure satisfy that magnesium alloy as medical embedded material to its corrosive nature and machinery
The requirement of performance.
5. a preparation method has many advantages, such as that raw material cost is low, preparation process is simple to operation.
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 implementation mode：
It is further illustrated the present invention as follows 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 alloys
1) raw material preparation：Experiment raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%) (by 10% burning
Damage calculates), 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, entire fusion process to be continually fed into N2+SF6Mixing protect
Protect gas, wherein N2And SF6Flow-rate ratio be 100:1；
A) crucible, Slag Tool, stirring rod and mold are dried in 200 DEG C of baking ovens for use；
B) crucible handled well is put into resistance furnace, set temperature is 300 DEG C, when furnace temperature reaches, is passed through protection 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 and at the uniform velocity, stirs 5min, furnace temperature counterclockwise after zinc is completely melt
740 DEG C are reduced to, Mg-7.4wt.%Mn intermediate alloys are added after keeping the temperature 15min, waits for that Mg-7.4wt.%Mn intermediate alloys are completely molten
After change at the uniform velocity, stir 5min counterclockwise, pure tin grain is added after 740 DEG C of heat preservation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise
Stir 5min；
E) furnace temperature is set as 720 DEG C, stands 30min, skims.
3) it casts：Crucible is taken out, is cast；To prevent to aoxidize or burn when casting, first it is passed through in casting mold
Protective gas is protected toward continuous conveying protective gas at liquid stream in casting process, after melt at the uniform velocity to be poured into 200 DEG C of preheatings
Metal die, after solidification demoulding obtain alloy cast ingot.
4) extrusion process：By alloy preparation process 3) obtained magnesium alloy ingot is processed intoExtrusion ingot, then
Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, then squeezed under preheating temperature, extrusion speed 0.5-
2.5mm/s, extrusion ratio 10:1.
5) alloy corrosion rate is 0.8mm/y in Hank ' s simulated body fluids.
Embodiment 2：
The preparation of as cast condition Mg-3.0wt%Sn-0.01wt%Mn-0.5wt%Zn magnesium alloys
1) raw material preparation：Experiment raw material are respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%) (by 10% burning
Damage calculates), 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, entire fusion process to be continually fed into N2+SF6Mixing protect
Protect gas, wherein N2And SF6Flow-rate ratio be 100:1；
A) crucible, Slag Tool, stirring rod and mold are dried in 200 DEG C of baking ovens for use；
B) crucible handled well is put into resistance furnace, set temperature is 300 DEG C, when furnace temperature reaches, is passed through protection 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 and at the uniform velocity, stirs 5min, furnace temperature counterclockwise after zinc is completely melt
740 DEG C are reduced to, Mg-7.4wt.%Mn intermediate alloys are added after keeping the temperature 15min, waits for that Mg-7.4wt.%Mn intermediate alloys are completely molten
After change at the uniform velocity, stir 5min counterclockwise, pure tin grain is added after 740 DEG C of heat preservation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise
Stir 5min；
E) furnace temperature is set as 720 DEG C, stands 30min, skims.
3) it casts：Crucible is taken out, is cast；To prevent to aoxidize or burn when casting, first it is passed through in casting mold
Protective gas is protected toward continuous conveying protective gas at liquid stream in casting process, after melt at the uniform velocity to be poured into 200 DEG C of preheatings
Metal die, after solidification demoulding obtain alloy cast ingot.
4) extrusion process：By alloy preparation process 3) obtained magnesium alloy ingot is processed intoExtrusion ingot, then
Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, then squeezed under preheating temperature, extrusion speed 0.5-
2.5mm/s, extrusion ratio 10:1.
5) alloy corrosion rate is 0.5mm/y in Hank ' s simulated body fluids.
Embodiment 3：
The preparation of as cast condition Mg-1.0wt%Sn-1wt%Mn-0.05wt%Zn magnesium alloys
1) raw material preparation：It is respectively pure magnesium (99.9wt.%) 820g, pure zinc (99.99wt.%) 10.9g to test raw material
(being calculated by 10% scaling loss), pure tin (99.99wt.%) 0.54g (being calculated by 30% scaling loss) and Mg-7.4wt.%Mn intermediate alloys
174.9g (is calculated) by 30% scaling loss, and raw material grinder buffing is removed oxide on surface.
2) melting：To prevent the oxidation or burning of magnesium alloy fused mass, entire fusion process to be continually fed into N2+SF6Mixing protect
Protect gas, wherein N2And SF6Flow-rate ratio be 100:1；
A) crucible, Slag Tool, stirring rod and mold are dried in 200 DEG C of baking ovens for use；
B) crucible handled well is put into resistance furnace, set temperature is 300 DEG C, when furnace temperature reaches, is passed through protection 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 and at the uniform velocity, stirs 5min, furnace temperature counterclockwise after zinc is completely melt
740 DEG C are reduced to, Mg-7.4wt.%Mn intermediate alloys are added after keeping the temperature 15min, waits for that Mg-7.4wt.%Mn intermediate alloys are completely molten
After change at the uniform velocity, stir 5min counterclockwise, pure tin grain is added after 740 DEG C of heat preservation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise
Stir 5min；
E) furnace temperature is set as 720 DEG C, stands 30min, skims.
3) it casts：Crucible is taken out, is cast；To prevent to aoxidize or burn when casting, first it is passed through in casting mold
Protective gas is protected toward continuous conveying protective gas at liquid stream in casting process, after melt at the uniform velocity to be poured into 200 DEG C of preheatings
Metal die, after solidification demoulding obtain alloy cast ingot.
4) extrusion process：By alloy preparation process 3) obtained magnesium alloy ingot is processed intoExtrusion ingot, then
Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, then squeezed under preheating temperature, extrusion speed 0.5-
2.5mm/s, extrusion ratio 10:1.
5) alloy corrosion rate is 0.40mm/y in Hank ' s simulated body fluids.
Embodiment 4：
The preparation of as cast condition Mg-2.0wt%Sn-0.5wt%Mn-1wt%Zn magnesium alloys
1) raw material preparation：It is respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin to test raw material
(99.99wt.%) and Mg-7.4wt.%Mn intermediate alloys, and raw material grinder buffing is removed into oxide on surface.
2) melting：To prevent the oxidation or burning of magnesium alloy fused mass, entire fusion process to be continually fed into N2+SF6Mixing protect
Protect gas, wherein N2And SF6Flow-rate ratio be 100:1；
A) crucible, Slag Tool, stirring rod and mold are dried in 200 DEG C of baking ovens for use；
B) crucible handled well is put into resistance furnace, set temperature is 300 DEG C, when furnace temperature reaches, is passed through protection 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 and at the uniform velocity, stirs 5min, furnace temperature counterclockwise after zinc is completely melt
740 DEG C are reduced to, Mg-7.4wt.%Mn intermediate alloys are added after keeping the temperature 15min, waits for that Mg-7.4wt.%Mn intermediate alloys are completely molten
After change at the uniform velocity, stir 5min counterclockwise, pure tin grain is added after 740 DEG C of heat preservation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise
Stir 5min；
E) furnace temperature is set as 720 DEG C, stands 30min, skims.
3) it casts：Crucible is taken out, is cast；To prevent to aoxidize or burn when casting, first it is passed through in casting mold
Protective gas is protected toward continuous conveying protective gas at liquid stream in casting process, after melt at the uniform velocity to be poured into 200 DEG C of preheatings
Metal die, after solidification demoulding obtain alloy cast ingot.
4) extrusion process：By alloy preparation process 3) obtained magnesium alloy ingot is processed intoExtrusion ingot, then
Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, then squeezed under preheating temperature, extrusion speed 0.5-
2.5mm/s, extrusion ratio 10:1.
5) alloy corrosion rate is 0.35mm/y in Hank ' s simulated body fluids.
Embodiment 5
The preparation of as cast condition Mg-1.0wt%Sn-0.2wt%Mn-1wt%Zn magnesium alloys
3) raw material preparation：It is respectively pure magnesium (99.9wt.%), pure zinc (99.99wt.%), pure tin to test raw material
(99.99wt.%) and Mg-7.4wt.%Mn intermediate alloys, and raw material grinder buffing is removed into oxide on surface.
4) melting：To prevent the oxidation or burning of magnesium alloy fused mass, entire fusion process to be continually fed into N2+SF6Mixing protect
Protect gas, wherein N2And SF6Flow-rate ratio be 100:1；
F) crucible, Slag Tool, stirring rod and mold are dried in 200 DEG C of baking ovens for use；
G) crucible handled well is put into resistance furnace, set temperature is 300 DEG C, when furnace temperature reaches, is passed through protection 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 and at the uniform velocity, stirs 5min, furnace temperature counterclockwise after zinc is completely melt
740 DEG C are reduced to, Mg-7.4wt.%Mn intermediate alloys are added after keeping the temperature 15min, waits for that Mg-7.4wt.%Mn intermediate alloys are completely molten
After change at the uniform velocity, stir 5min counterclockwise, pure tin grain is added after 740 DEG C of heat preservation 15min, after the fusing of pure tin grain, at the uniform velocity, counterclockwise
Stir 5min；
J) furnace temperature is set as 720 DEG C, stands 30min, skims.
6) it casts：Crucible is taken out, is cast；To prevent to aoxidize or burn when casting, first it is passed through in casting mold
Protective gas is protected toward continuous conveying protective gas at liquid stream in casting process, after melt at the uniform velocity to be poured into 200 DEG C of preheatings
Metal die, after solidification demoulding obtain alloy cast ingot.
7) extrusion process：By alloy preparation process 3) obtained magnesium alloy ingot is processed intoExtrusion ingot, then
Extrusion ingot and extrusion die are preheated at 300-350 DEG C together, then squeezed under preheating temperature, extrusion speed 0.5-
2.5mm/s, extrusion ratio 10:1.
8) alloy corrosion rate is 0.2mm/y in Hank ' s simulated body fluids.
Embodiment 2-5 has optics metallograph similar to Example 1, stress-strain diagram, polarization curve, magnesium alloy
Mechanical properties are up to 180MPa-300MPa, and elongation percentage is up to 12%-20%.
Although listing in detail here and illustrating that case is preferably implemented, skilled person will appreciate that, it can not take off
Carried out in the case of from marrow of the present invention it is various improve, addition, the modes such as replace, these contents, which are all identified as belonging to right, to be wanted
Within the scope of the present invention defined by asking.
Claims (7)
1. a kind of preparation method of bio-medical wrought magnesium alloy, the magnesium alloy each component and its mass percentage are：Sn 1-
4%, Mn 0.01-1%, Zn 0.05-1%, remaining is Mg and inevitable impurity element；It is characterized in that,
(1) raw material preparation：It is respectively pure magnesium, pure zinc, pure tin and Mg-Mn intermediate alloys to test raw material；Raw material surface is used
Grinder buffing is cleared up, and oxide on surface is removed, 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 into stove2With
SF6Mixed gas；Wherein, N2And SF6Flow volume ratio be 100:1；Pure magnesium ingot is put into earthenware after logical protective gas 5-10min
Furnace temperature is risen to 680-760 DEG C by crucible, waits for that pure magnesium ingot is completely melt, is added according to the sequence of pure zinc, Mg-Mn intermediate alloys, pure tin
Melting；A kind of raw material are often added, at the uniform velocity, after stirring 5-8min counterclockwise stands after raw material are completely melt, will finally melt
Temperature is down to 720 DEG C, stands heat preservation 30min；Entire fusion process is continually fed into N2+SF6Hybrid protection gas, prevent magnesium
The oxidation or burning of alloy melt；
(3) it casts：It skims, melt is then at the uniform velocity poured into the metal die of preheating, demoulded after solidification and obtain magnesium alloy ingot, gold
The preheating temperature for belonging to mold is 200 DEG C, and to prevent to aoxidize or burn when casting, protective gas is first passed through in mold,
It is protected toward continuous conveying protective gas at liquid stream in casting process；
(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 0.5-2.5mm/s, extrusion ratio 10:1.
2. according to the method for claim 1, which is characterized in that Mg-Mn intermediate alloys are to be closed among Mg-7.4wt.%Mn
Gold, the purity 99.9wt.% of pure magnesium, the purity 99.99wt.% of pure zinc, the purity 99.99wt.% of pure tin.
3. according to the method for claim 1, which is characterized in that the addition of pure zinc need to additionally increase during preparation
10% is used as scaling loss.
4. according to the method for claim 1, which is characterized in that gained magnesium alloy mechanical properties reach 180MPa-
300MPa, elongation percentage reach 12%-20%.
5. according to the method for claim 1, which is characterized in that corrosion speed of the gained magnesium alloy in Hank ' s simulated body fluids
Rate is 0.2mm/y-0.8mm/y.
6. according to the method for claim 1, which is characterized in that in the magnesium alloy component Zn, Mn, Sn and inevitably
Mass percentage shared by impurity element is not more than 5%.
7. a kind of bio-medical wrought magnesium alloy being prepared according to the method for claim 1, which is characterized in that biology
Medical wrought magnesium alloy constituent is mutually strip phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947204.5A CN106521272B (en) | 2016-10-26 | 2016-10-26 | A kind of anti-corrosion Biological magnesium alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947204.5A CN106521272B (en) | 2016-10-26 | 2016-10-26 | A kind of anti-corrosion Biological magnesium alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106521272A CN106521272A (en) | 2017-03-22 |
| CN106521272B true CN106521272B (en) | 2018-07-31 |
Family
ID=58293362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610947204.5A Expired - Fee Related CN106521272B (en) | 2016-10-26 | 2016-10-26 | A kind of anti-corrosion Biological magnesium alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106521272B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3656884B1 (en) | 2017-07-18 | 2024-05-29 | National Institute for Materials Science | Magnesium-based alloy wrought product and method for producing same |
| 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 |
| CN109112377B (en) * | 2018-11-09 | 2020-06-02 | 吉林大学 | Corrosion-resistant biomedical magnesium alloy and preparation method and application thereof |
| CN109295366B (en) * | 2018-12-03 | 2020-03-27 | 北京工业大学 | Room-temperature high-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 |
| CN114075629B (en) * | 2021-10-25 | 2022-06-10 | 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433477A (en) * | 2011-12-22 | 2012-05-02 | 哈尔滨工程大学 | Biomedical Mg-Sn-Zn-Mn magnesium alloy and preparation method thereof |
| CN102813966A (en) * | 2012-08-29 | 2012-12-12 | 哈尔滨工程大学 | Medical degradable magnesium alloy bone-fixing screw |
| CN105568103A (en) * | 2016-01-04 | 2016-05-11 | 青岛工学院 | Degradable biomedical magnesium alloy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006015457A1 (en) * | 2006-03-31 | 2007-10-04 | Biotronik Vi Patent Ag | Magnesium alloy and related manufacturing process |
-
2016
- 2016-10-26 CN CN201610947204.5A patent/CN106521272B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433477A (en) * | 2011-12-22 | 2012-05-02 | 哈尔滨工程大学 | Biomedical Mg-Sn-Zn-Mn magnesium alloy and preparation method thereof |
| CN102813966A (en) * | 2012-08-29 | 2012-12-12 | 哈尔滨工程大学 | Medical degradable magnesium alloy bone-fixing screw |
| CN105568103A (en) * | 2016-01-04 | 2016-05-11 | 青岛工学院 | Degradable biomedical magnesium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106521272A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106521272B (en) | A kind of anti-corrosion Biological magnesium alloy and preparation method thereof | |
| Wei et al. | Influence of oxygen content on microstructure and mechanical properties of Ti–Nb–Ta–Zr alloy | |
| Gunde et al. | High-strength magnesium alloys for degradable implant applications | |
| CA2455426C (en) | Casting alloy | |
| CN101550510B (en) | High intensity degradable biological medical magnesium alloy and preparation method thereof | |
| Freese et al. | Metallurgy and technological properties of titanium and titanium alloys | |
| CA2510545A1 (en) | Aluminium diecasting alloy | |
| CN104674103A (en) | CrFeCoNiNbx high-entropy alloy and preparation method thereof | |
| CN109112377B (en) | Corrosion-resistant biomedical magnesium alloy and preparation method and application thereof | |
| CN104862566A (en) | High-strength high-plasticity medical magnesium alloy, and preparation method and applications thereof | |
| CN107557632A (en) | A kind of degradable biological medical Mg Zn Zr Nd alloy materials and preparation method thereof | |
| CN107460370A (en) | A kind of low-cost high-strength high-ductility metastable β Titanium-alloy and preparation method thereof | |
| CN104674093B (en) | Medical high-toughness corrosion-resistant magnesium based composite material and preparation method thereof | |
| CN105401033B (en) | High strength and toughness anti-corrosion biomedical magnesium alloy | |
| CN105568082A (en) | Heat treatment method for Al-Si-Cu-Mg casting alloy | |
| CN110117743A (en) | A kind of corrosion-proof and high-strength tough magnesium alloy tubing and preparation process | |
| CN109136719A (en) | A kind of ageing strengthening type Ni-Cr base high-temperature corrosion-resistant alloy and heat treatment method | |
| CN108277407A (en) | A kind of intravascular stent degradable corrosion-resistant magnesium alloy and preparation method thereof | |
| CN108411158B (en) | A kind of biodegradable Zn-Mg-Zr alloy material, preparation method and application | |
| CN113444919A (en) | Zinc alloy material for degradable cardiovascular stent and preparation method thereof | |
| CN108070763A (en) | A kind of magnesium alloy with LPSO and/or SFs structures and preparation method thereof | |
| CN110923486B (en) | Heat treatment process for degradable magnesium alloy | |
| CN103184380A (en) | Biodegradable Mg-Gd-Zn-Ag-Zr series magnesium alloy and preparation method thereof | |
| CN114107712A (en) | Medical magnesium-based composite material bar and preparation method thereof | |
| Mohammadi et al. | Microstructure characterization and effect of extrusion temperature on biodegradation behavior of Mg-5Zn-1Y-xCa alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180731 |