CN107435113B - A kind of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo and preparation method thereof - Google Patents

A kind of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo and preparation method thereof Download PDF

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CN107435113B
CN107435113B CN201710555400.2A CN201710555400A CN107435113B CN 107435113 B CN107435113 B CN 107435113B CN 201710555400 A CN201710555400 A CN 201710555400A CN 107435113 B CN107435113 B CN 107435113B
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alloy
melt
temperature
magnesium
magnesium alloy
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CN107435113A (en
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许春香
刘燕萍
张金山
卜颖宏
阎佩雯
杨文甫
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Taiyuan University of Technology
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    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
    • 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
    • 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
    • A61L27/58—Materials at least partially resorbable by the body
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C22B9/026—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves by acoustic waves, e.g. supersonic waves
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a kind of tough corrosion-resistant orthopaedics magnesium alloys of height degradable in vivo and preparation method thereof, belong to technical field of biological material.It is a kind of magnesium alloy being made of Mg, Sr, Zr, and chemical composition is by mass percentage are as follows: Sr0.5-4.0%, Zr0.4-0.7%, remaining is Mg.Ingot casting is manufactured using whole gas shield resistance furnace melting+rotating excitation field and ultrasonic wave outfield composite treatment technology, using Homogenization Treatments and hot extrusion deformation, obtain on magnesium matrix Dispersed precipitate extremely uniformly tiny Mg17Sr2Second phase, thus obtain can promote the healing of bone tissue, the generation of new bone, enhancing synosteosis ability, Gao Qiangren, corrosion-resistant, biological medical magnesium alloy that can be degradable.The present invention is mainly suitable for orthopaedics implantable medical fields.

Description

A kind of height degradable in vivo is tough corrosion-resistant orthopaedics magnesium alloy and its system Preparation Method
Technical field
The present invention relates to a kind of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo and preparation method thereof, Belong to magnesium alloy biomaterials field.
Background technique
Biological degradable in vivo absorbing material is the hot spot of biomaterial research.The biological degradable in vivo of clinical application is inhaled Receiving material is mainly polymer and certain ceramic materials, such as polylactic acid, calcium phosphate, but polymer material low strength, ceramics The plasticity and toughness of material are again poor.The advantage for metallic orthopaedic implant material such as stainless steel, titanium alloy and cochrome is it Good mechanical property and corrosion resistance can keep whole stable structure for a long time in vivo.However, these metal materials are planted It after entering, cannot degrade, permanently be retained as foreign matter in vivo, this can allow patient suffering can't bear in vivo.In most cases, also It needs to carry out second operation to take out implantation material.Therefore, can biodegradable orthopaedics metal material just become implantation material not The research and development direction come, and the magnesium alloy closest with skeleton density has unique advantage, magnesium alloy is easy It shapes, and there is excellent comprehensive mechanical property and unique biological degradation function.Magnesium is magnanimity necessary to human body again One of metallic element.The elasticity modulus of magnesium alloy is about 45GPa, close to skeleton (10~40GPa), can effectively be alleviated Even avoid " stress-shielding effect ".For magnesium alloy implantation material in degradation process, the magnesium ion released may additionally facilitate osteocyte Proliferation and differentiation, promote the growth and healing of bone.Its catabolite is mainly Mg (OH)2、(Ca,Mg)3(PO4)2And hydroxyl Base apatite (HA), HA can effectively improve the biocompatibility and synosteosis ability of alloy material.
In conclusion manufacturing orthopaedics implant according to magnesium alloy, after the state of an illness of patient is cured, implantation material is in vivo Slowly degradation and finally replaced newly-generated bone tissue, eliminates second operation bring and perplexs, alleviate the pain of patient Bitter and medical burden.It has broad application prospects in medical field.
Summary of the invention
The present invention is intended to provide a kind of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo and its preparation Method passes through the uniform tiny Mg of Dispersed precipitate on magnesium matrix17Sr2Second phase, so that being cured for bone tissue can be promoted by obtaining Close, the generation of new bone, enhancing synosteosis ability, Gao Qiangren, corrosion-resistant, biological medical magnesium alloy that can be degradable.This hair It is bright to be primarily adapted for use in orthopaedics implantable medical field.
Sr is a kind of intracorporal microelement of people, and the overwhelming majority is present in bone tissue, and Sr can promote the work of osteocyte The formation of property and new bone；When adding Sr in magnesium alloy, the Mg of formation17Sr2The mechanical property of alloy and resistance to can be improved in second phase Corrosion energy.
Zr element as heterogeneous forming core core can significant refining alloy crystal grain, purify melt.
The present invention provides a kind of tough corrosion-resistant orthopaedics magnesium alloys of height degradable in vivo, by following quality The element of percentage forms: Sr0.5-4.0%, Zr0.4-0.7%, remaining is Mg and inevitable impurity element.
The impurity element includes Fe, Ni, Al, Cu, and by mass percentage, every kind of content does not surpass impurity element 0.1% is crossed, total amount is no more than 0.4%.
The described tough corrosion-resistant orthopaedics magnesium alloy of the height degradable in vivo Dispersed precipitate on magnesium matrix Mg17Sr2Second phase.
The present invention provides a kind of preparation method of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo, Specific process step are as follows:
Step 1: melting
(1) according to mass ratio Mg: Sr: Mg-30wt.%Zr=500: 2.5~21.3∶6.6~12.3 ratio weighs raw material；
(2) non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will take off Slag spoon, stirring spoon, mold are preheating to 200~210℃；
(3) 400 are raised to furnace temperature~At 450 DEG C, MAG block is put into crucible relaying is continuous to be warming up to 710~720 DEG C, heat preservation 15~20 Min melts MAG block；
(4) when magnesium-based melt temperature gos up to 750~It skims at 760 DEG C, pure Sr and Mg-30wt.%Zr intermediate alloy is same When be added, with stirring spoon be lower than liquid level gentle agitation 2~3min, 750~20min is kept the temperature at a temperature of 760 DEG C makes Sr and Mg- The fusing of 30wt.%Zr intermediate alloy；
(5) magnesium-based melt temperature is risen to 780 again~800 DEG C, heat preservation 20~30 min, are then cooled to 730~750 DEG C, Continuous electrorefining 8~10 min are warming up to 750 after refining~760 DEG C stand 25~40 min；
(6) melt and crucible are placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；
(7) rotating excitation field processing, technological parameter are as follows: melt temperature 730 are carried out to alloy melt~740 DEG C, output frequency 10~20Hz, magnetic field strength 60~80T, action time 5~10 min；
(8) ultrasonic wave external field treatment, technological parameter are as follows: melt temperature 730 are carried out to alloy melt again~740 DEG C, output Frequency 18~19K Hz, current strength 3~5A applies the vibration time 8~10 min。
(9) after combined processing, melt is stood 5~Skimming after 6 min and pouring into preheating temperature is 200~210 DEG C of cast iron die In to get arrive Mg-Sr-Zr magnesium alloy ingot.
In above-mentioned whole process, it is passed through 99%CO2+1%SF6Protective gas carries out whole gas shield.
Step 2: Homogenization Treatments
Mg-Sr-Zr magnesium alloy ingot obtained by the first step is subjected to Homogenization Treatments, process conditions are as follows: heating temperature is 450~500 DEG C, soaking time 8~10h, the type of cooling 60~70 DEG C of water quenchings.
Step 3: hot extrusion deformation
Second step is handled into later ingot casting cleaning polishing, obtain surface it is smooth, without being mingled with, squeezed without lofty and recess Green compact material, extrusion equipment choose 300T vertical extruder, and squeezing temperature is 350~450 DEG C, extrusion ratio 16, movable press head speed It is 1~2mm/s, the bar exit type of cooling are bar air-cooled, that finally acquisition diameter is 10mm.
The average grain size of the alloy after squeezing of magnesium alloy materials prepared by the present invention are as follows: 1~2 μm, tensile strength is 325~355MPa, yield strength 265~295MPa, elongation 25~30%；According to the immersion standard of ASTMG31-72, As-extruded Average corrosion rate of the alloy in 37 ± 0.5 DEG C of dynamic analog body fluid SBF is 0.10~0.15 mm/a。
The purity of the raw material is respectively as follows: purity > 99.99wt.% of Mg, purity > 99.99wt.% of Sr, Mg- Purity > 99.95wt.% of 30wt.%Zr.
In preparation method of the present invention, the compound field action of rotating excitation field and ultrasonic wave outfield of use, is to pass through rotation first Magnetic field causes strenuous exercise inside melt, leads to the forced flowing of metal bath, keeps melt internal temperature field and solute field uniform Change, accelerate the diffusion of solute atoms in melt, overcome the problem of Tissue distribution unevenness, reduce the thickness of diffusion layer, accelerates Solidification boundary layer soluterich area excessive transmission and diffusion, reduce the probability of component segregation, increase degree of supercooling, significantly Improve nucleation rate；Secondly, ultrasonic treatment accelerates the flowing of melt, make die break, reduce forming core activation energy, improves forming core Rate, for dendrite in growth process, violent acoustic streaming causes a large amount of dendrite to take off from type wall the souring of dendrite on mould wall It falls, and floats to inside melt, dendrite is made to refine and be evenly distributed, improve the isotropism of crystal grain and lower segregation, simultaneously also There are degasification, impurity elimination and purification melt.The effect of the above Composite Field comprehensive function is available pure, tiny, uniform As-cast structure, the average grain size under as cast condition reach 35-40 μm, have established for subsequent Homogenization Treatments and hot extrusion deformation good Good basis.Therefore, it during the hot extrusion deformation then carried out, is reduced to once be squeezed by original secondary extrusion Type, the crystallite dimension of alloy is 1 after extruding~2 μm, production cost is also reduced while meeting performance requirement, is improved Production efficiency.
Beneficial effects of the present invention: the magnesium-alloy material prepared by the method for the invention, the Dispersed precipitate on magnesium matrix Uniform tiny Mg17Sr2Second phase, to obtain the generation of the healing, new bone that can promote bone tissue, enhancing synosteosis energy Power, Gao Qiangren, corrosion-resistant, biological medical magnesium alloy that can be degradable.The present invention is mainly suitable for orthopaedics implantable medical necks Domain.
Detailed description of the invention
Fig. 1 is embodiment 3~The XRD spectrum of 6 resulting as cast condition Mg-xSr-0.5Zr alloys.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
In the present embodiment, raw material composition is as follows: Sr 0.5%, Zr 0.4%, remaining is Mg and contains a small amount of impurity element Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 200 DEG C；Then when furnace temperature is raised to 400 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 710 DEG C, 15 min of heat preservation melt MAG block；；Skim when magnesium-based melt temperature gos up to 750 DEG C, by the pure Sr of 2.5g and 6.6gMg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 2min with stirring spoon, protects at a temperature of 750 DEG C Warm 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 780 DEG C again, keeps the temperature 20 min, Then 730 DEG C, continuous 8 min of electrorefining are cooled to, 750 DEG C of 25 min of standing are warming up to after refining；By melt and crucible one Playing merging has in the experimental rig of rotating excitation field and ultrasonic wave outfield compound action；Alloy melt is carried out at rotating excitation field Reason, technological parameter are as follows: 730 DEG C of melt temperature, output frequency 10Hz, magnetic field strength 60T, 5 min of action time；Again to alloy Melt carries out ultrasonic wave external field treatment, technological parameter are as follows: and 730 DEG C of melt temperature, output frequency 18K Hz, current strength 3A, Apply vibration 8 min of time；After combined processing, the cast iron die that preheating temperature is 200 DEG C is poured by skimming after 5 min of melt standing In to get arrive Mg-Sr-Zr magnesium alloy ingot, be all to be passed through 99%CO in entire fusion process2+1%SF6Protective gas carries out Whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 450 DEG C, Soaking time is 8h, and the type of cooling is 60 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 350 DEG C, extrusion ratio 16, movable press head speed be 1mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Diameter is the bar of 10mm.
The magnesium alloy obtained using the above method, average grain size are 2 μm, tensile strength 325MPa, yield strength For 265MPa, elongation 25%.According to the immersion standard of ASTMG31-72, dynamic analog of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in body fluid (SBF) is 0.15 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Embodiment 2:
In the present embodiment, raw material composition is as follows: Sr 4.0%, Zr 0.7%, remaining is Mg and contains a small amount of impurity element Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 205 DEG C；Then when furnace temperature is raised to 420 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 720 DEG C, 20 min of heat preservation melt MAG block；Skim when magnesium-based melt temperature gos up to 760 DEG C, by the pure Sr of 21.3g and 12.3gMg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 3min with stirring spoon, protects at a temperature of 760 DEG C Warm 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 790 DEG C again, heat preservation 25 Then min is cooled to 740 DEG C, continuous 8 min of electrorefining, 760 DEG C of 30 min of standing are warming up to after refining；By melt and earthenware Crucible is placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；Rotating excitation field is carried out to alloy melt Processing, technological parameter are as follows: 735 DEG C of melt temperature, output frequency 15Hz, magnetic field strength 70T, 8 min of action time；Pairing again Golden melt carries out ultrasonic wave external field treatment, technological parameter are as follows: and 735 DEG C of melt temperature, output frequency 19K Hz, current strength 4A applies vibration 9 min of time；After combined processing, the pig mold that preheating temperature is 205 DEG C is poured by skimming after 6 min of melt standing It is all to be passed through 99%CO in entire fusion process to get Mg-Sr-Zr magnesium alloy ingot is arrived in tool2+1%SF6Protective gas into Go whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 460 DEG C, Soaking time is 9h, and the type of cooling is 65 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 360 DEG C, extrusion ratio 16, movable press head speed be 1.5mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Obtain the bar that diameter is 10mm.
The magnesium alloy obtained using the above method, average grain size are 1 μm, tensile strength 355MPa, yield strength For 295MPa, elongation 30%.According to the immersion standard of ASTMG31-72, dynamic analog of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in body fluid (SBF) is 0.10 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Embodiment 3:
In the present embodiment, raw material composition is as follows: Sr 0.5%, Zr0.5%, remaining is Mg and contains a small amount of impurity element Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 210 DEG C；Then when furnace temperature is raised to 430 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 715 DEG C, 18 min of heat preservation melt MAG block；Skim when magnesium-based melt temperature gos up to 755 DEG C, by the pure Sr of 2.6g and 8.35g Mg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 2.5min with stirring spoon, in 755 DEG C of temperature Lower heat preservation 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 800 DEG C again, heat preservation 30 Then min is cooled to 750 DEG C, continuous 10 min of electrorefining, 755 DEG C of 40 min of standing are warming up to after refining；By melt and Crucible is placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；Rotary magnetic is carried out to alloy melt Field processing, technological parameter are as follows: 740 DEG C of melt temperature, output frequency 20Hz, magnetic field strength 80T, 10 min of action time；Again Ultrasonic wave external field treatment, technological parameter are as follows: 740 DEG C of melt temperature, output frequency 18K Hz, electric current is strong are carried out to alloy melt 5A is spent, vibration 10 min of time is applied；After combined processing, the cast iron that preheating temperature is 210 DEG C is poured by skimming after 6 min of melt standing It is all to be passed through 99%CO in entire fusion process to get Mg-Sr-Zr magnesium alloy ingot is arrived in mold2+1%SF6Protective gas Carry out whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 470 DEG C, Soaking time is 10h, and the type of cooling is 70 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 370 DEG C, extrusion ratio 16, movable press head speed be 2mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Diameter is the bar of 10mm.
The magnesium alloy obtained using the above method, average grain size are 2 μm, tensile strength 330MPa, yield strength For 270MPa, elongation 25%.According to the immersion standard of ASTMG31-72, dynamic analog of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in body fluid (SBF) is 0.14 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Embodiment 4:
In the present embodiment, raw material composition is as follows: Sr 1.0%, Zr0.5%, remaining is Mg and contains a small amount of impurity element Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 210 DEG C；Then when furnace temperature is raised to 450 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 720 DEG C, 20 min of heat preservation melt MAG block；Skim when magnesium-based melt temperature gos up to 760 DEG C, by the pure Sr of 5.14g and 8.58g Mg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 3min with stirring spoon, at a temperature of 760 DEG C Heat preservation 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 800 DEG C again, heat preservation 30 Then min is cooled to 740 DEG C, continuous 10 min of electrorefining, 760 DEG C of 35 min of standing are warming up to after refining；By melt and earthenware Crucible is placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；Rotating excitation field is carried out to alloy melt Processing, technological parameter are as follows: 735 DEG C of melt temperature, output frequency 20Hz, magnetic field strength 70T, 8 min of action time；Pairing again Golden melt carries out ultrasonic wave external field treatment, technological parameter are as follows: and 735 DEG C of melt temperature, output frequency 19K Hz, current strength 4A applies vibration 9 min of time；After combined processing, the pig mold that preheating temperature is 210 DEG C is poured by skimming after 6 min of melt standing It is all to be passed through 99%CO in entire fusion process to get Mg-Sr-Zr magnesium alloy ingot is arrived in tool2+1%SF6Protective gas into Go whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 480 DEG C, Soaking time is 9h, and the type of cooling is 60 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 400 DEG C, extrusion ratio 16, movable press head speed be 2mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Diameter is the bar of 10mm.
The magnesium alloy obtained using the above method, average grain size are 1.5 μm, tensile strength 340MPa, and surrender is strong Degree is 280MPa, elongation 28%.According to the immersion standard of ASTMG31-72, dynamic analog of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in quasi- body fluid (SBF) is 0.12 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Embodiment 5:
In the present embodiment, raw material composition is as follows: Sr 2.0%, Zr0.5%, remaining is Mg and contains a small amount of impurity element Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 200 DEG C；Then when furnace temperature is raised to 400 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 710 DEG C, 15 min of heat preservation melt MAG block；Skim when magnesium-based melt temperature gos up to 750 DEG C, by the pure Sr of 10.38g and 8.67g Mg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 2min with stirring spoon, at a temperature of 750 DEG C Heat preservation 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 780 DEG C again, heat preservation 20 Then min is cooled to 730 DEG C, continuous 8 min of electrorefining, 750 DEG C of 25 min of standing are warming up to after refining；By melt and earthenware Crucible is placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；Rotating excitation field is carried out to alloy melt Processing, technological parameter are as follows: 730 DEG C of melt temperature, output frequency 10Hz, magnetic field strength 60T, 5 min of action time；Pairing again Golden melt carries out ultrasonic wave external field treatment, technological parameter are as follows: and 730 DEG C of melt temperature, output frequency 18K Hz, current strength 3A applies vibration 8 min of time；After combined processing, the pig mold that preheating temperature is 200 DEG C is poured by skimming after 5 min of melt standing It is all to be passed through 99%CO in entire fusion process to get Mg-Sr-Zr magnesium alloy ingot is arrived in tool2+1%SF6Protective gas into Go whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 500 DEG C, Soaking time is 8h, and the type of cooling is 70 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 420 DEG C, extrusion ratio 16, movable press head speed be 1.5mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Obtain the bar that diameter is 10mm.
The magnesium alloy obtained using the above method, average grain size 1m, tensile strength 350MPa, yield strength are 290MPa, elongation 28%.According to the immersion standard of ASTMG31-72, dynamic analog body of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in liquid (SBF) is 0.11 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Embodiment 6:
In the present embodiment, raw material composition it is as follows: Sr3.0%, Zr0.5%, remaining be Mg and containing a small amount of Impurity Fe, Ni, Al, Cu, by mass percentage, every kind of content is no more than 0.1% to impurity element, and total amount is no more than 0.4%.
In the present embodiment magnesium alloy the preparation method is as follows:
Non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will be skimmed Spoon, stirring spoon, mold are preheating to 210 DEG C；Then when furnace temperature is raised to 420 DEG C, 500g MAG block is put into crucible and relays temperature of continuing rising To 720 DEG C, 15 min of heat preservation melt MAG block；Skim when magnesium-based melt temperature gos up to 750 DEG C, by the pure Sr of 15.7g and 8.76g Mg-30wt.%Zr intermediate alloy is added simultaneously, is lower than liquid level gentle agitation 3min with stirring spoon, at a temperature of 750 DEG C Heat preservation 20min melts Sr and Mg-30wt.%Zr intermediate alloy；Magnesium-based melt temperature is risen to 790 DEG C again, keeps the temperature 25 min, Then 740 DEG C, continuous 10 min of electrorefining are cooled to, 760 DEG C of 30 min of standing are warming up to after refining；By melt and crucible one Playing merging has in the experimental rig of rotating excitation field and ultrasonic wave outfield combined processing；Rotating excitation field is carried out to alloy melt Processing, technological parameter are as follows: 740 DEG C of melt temperature, output frequency 20Hz, magnetic field strength 60T, 6 min of action time；Pairing again Golden melt carries out ultrasonic wave external field treatment, technological parameter are as follows: and 740 DEG C of melt temperature, output frequency 19K Hz, current strength 3A applies vibration 9 min of time；After combined processing, the pig mold that preheating temperature is 210 DEG C is poured by skimming after 5 min of melt standing It is all to be passed through 99%CO in entire fusion process to get Mg-Sr-Zr magnesium alloy ingot is arrived in tool2+1%SF6Protective gas into Go whole gas shield.
Gained magnesium alloy ingot is subjected to Homogenization Treatments, Homogenization Treatments process conditions are as follows: heating temperature is 490 DEG C, Soaking time is 10h, and the type of cooling is 60 DEG C of water quenchings.
Finally the ingot casting after Homogenization Treatments is polished smooth, 300T vertical extrusion machine equipment is chosen and is squeezed, squeezed Temperature be 450 DEG C, extrusion ratio 16, movable press head speed be 2mm/s, the bar exit type of cooling be it is air-cooled, finally obtain Diameter is the bar of 10mm.
The magnesium alloy obtained using the above method, average grain size are 1 μm, tensile strength 365MPa, yield strength For 295MPa, elongation 20%.According to the immersion standard of ASTMG31-72, dynamic analog of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in body fluid (SBF) is 0.10 mm/a.Meet the performance requirement that ideal medical bone is implanted into.
Attached drawing 1 is the XRD spectrum of as cast condition Mg-xSr-0.5Zr alloy, the corresponding relationship of curve in figure: (1) x=0.5；(2)x = 1.0；(3)x= 2.0；(4)x= 3.0；This four groups the case where being embodiment 3, embodiment 4, embodiment 5, embodiment 6 respectively.

Claims (4)

1. a kind of tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo, it is characterised in that: by following quality hundred Divide the element composition of ratio: Sr0.5-4.0%, Zr0.4-0.7%, remaining is Mg and inevitable impurity element；The magnesium closes Golden product on magnesium matrix Dispersed precipitate Mg17Sr2Second phase；
The preparation method of the tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo, processing step are as follows:
Step 1: melting
(1) according to mass ratio Mg: Sr: Mg-30wt.%Zr=500: 2.5~21.3∶6.6~12.3 ratio weighs raw material；
(2) non-magnetic stainless steel crucible inner wall will be made by oneself with ZnO and talcum powder coating first uniformly to brush to white, and will skim Spoon, stirring spoon, mold are preheating to 200~210℃；
(3) 400 are raised to furnace temperature~At 450 DEG C, MAG block is put into crucible relaying is continuous to be warming up to 710~720 DEG C, heat preservation 15~20 min Melt MAG block；
(4) when magnesium-based melt temperature gos up to 750~It skims at 760 DEG C, pure Sr and Mg-30wt.%Zr intermediate alloy is added simultaneously Enter, is lower than liquid level gentle agitation 2 with stirring spoon~3min, 750~20min is kept the temperature at a temperature of 760 DEG C makes Sr and Mg-30wt.%Zr Intermediate alloy fusing；
(5) magnesium-based melt temperature is risen to 780 again~800 DEG C, heat preservation 20~30 min, are then cooled to 730~750 DEG C, constantly Electrorefining 8~10 min are warming up to 750 after refining~760 DEG C stand 25~40 min；
(6) melt and crucible are placed in together in the experimental rig with rotating excitation field and ultrasonic wave outfield compound action；
(7) rotating excitation field processing, technological parameter are as follows: melt temperature 730 are carried out to alloy melt~740 DEG C, output frequency 10~ 20Hz, magnetic field strength 60~80T, action time 5~10 min；
(8) ultrasonic wave external field treatment, technological parameter are as follows: melt temperature 730 are carried out to alloy melt again~740 DEG C, output frequency 18~19K Hz, current strength 3~5A applies the vibration time 8~10 min；
(9) after combined processing, melt is stood 5~Skimming after 6 min and pouring into preheating temperature is 200~In 210 DEG C of cast iron die, Obtain Mg-Sr-Zr magnesium alloy ingot；
In above-mentioned whole process, it is passed through 99%CO2+1%SF6Protective gas carries out whole gas shield；
Step 2: Homogenization Treatments
Mg-Sr-Zr magnesium alloy ingot obtained by the first step is subjected to Homogenization Treatments, process conditions are as follows: heating temperature 450~500 DEG C, soaking time 8~10h, the type of cooling 60~70 DEG C of water quenchings；
Step 3: hot extrusion deformation
Second step is handled into later ingot casting cleaning polishing, obtain surface it is smooth, without be mingled with, without lofty and recess extruded stock Material, is once squeezed to obtain required alloy material；
During hot extrusion deformation, extrusion equipment chooses 300T vertical extruder, and squeezing temperature is 350~450 DEG C, extrusion ratio is 16, movable press head speed is 1~2mm/s, the bar exit type of cooling are bar air-cooled, that finally acquisition diameter is 10mm.
2. the tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo according to claim 1, feature exist In: the impurity element includes Fe, Ni, Al, Cu, and by mass percentage, every kind of content is no more than 0.1%, and total amount is no more than 0.4%。
3. the tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo according to claim 1, feature exist In: the average grain size of magnesium alloy alloy after squeezing are as follows: 1~2 μm, tensile strength 325~355MPa, yield strength are 265~295MPa, elongation 25~30%；According to the immersion standard of ASTMG31-72, dynamic of the As-extruded alloy at 37 ± 0.5 DEG C Average corrosion rate in simulated body fluid SBF is 0.10~0.15 mm/a。
4. the tough corrosion-resistant orthopaedics magnesium alloy of height degradable in vivo according to claim 1, feature exist In: the purity of the raw material is respectively as follows: purity > 99.99wt.% of Mg, and purity > 99.99wt.% of Sr, Mg-30wt.%Zr's is pure Degree > 99.95wt.%.
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