CN108359868A - It is a kind of to be used to be implanted into magnesium alloy of bone and preparation method thereof - Google Patents

It is a kind of to be used to be implanted into magnesium alloy of bone and preparation method thereof Download PDF

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CN108359868A
CN108359868A CN201810197277.6A CN201810197277A CN108359868A CN 108359868 A CN108359868 A CN 108359868A CN 201810197277 A CN201810197277 A CN 201810197277A CN 108359868 A CN108359868 A CN 108359868A
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magnesium alloy
alloy
bone
implanted
layer
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周建武
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Wenzhou Win Innovation Material Technology Co Ltd
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Wenzhou Win Innovation Material Technology Co Ltd
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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
    • A61L27/02—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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • 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
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/086—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • 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
    • A61L31/148—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/08—Coatings comprising two or more layers
    • 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

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  • Life Sciences & Earth Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Vascular Medicine (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is Zn 1.5 3%, Mn 0.6 1.1%, Ca 0.3 0.8%, Si 0.3 0.45%, Sr 0.45 0.8%, Li 1 1.8%, Cr 2.5 3.5%, Cu 1 2%, Mo 1.3 1.4%, Sc+La+Ce by weight percentage：0.01 0.08%, Nb：0.1%~0.8%, surplus is Mg and inevitable impurity element.The magnesium alloy of the present invention, yield strength >=370MPa, tensile strength >=410MPa, elongation >=18.5%, sterilizing rate >=90%, hence it is evident that lack the product of alloying element higher than other, hence it is evident that higher than the similar product without carrying out surface coating processing.

Description

It is a kind of to be used to be implanted into magnesium alloy of bone and preparation method thereof
Technical field
The invention belongs to alloy fields, especially provide a kind of magnesium alloy for being implanted into bone.
Background technology
In medical Bone Defect Repari and bone implant material, stainless steel, titanium titanium alloy are because of its excellent mechanical property, biofacies Capacitive and corrosion resistance become widely used material.But the mechanical property of stainless steel and titanium alloy and bone tissue are not Match, especially elasticity modulus, such as：The elasticity modulus of stainless steel is about 200GPa, and the elasticity modulus of titanium alloy is about 100GPa, And the elasticity modulus of bone tissue is about 10-40GPa.Therefore, implant assumes responsibility for almost all load.So in use " stress shielding " can be caused, the bone tissue around implant is caused atrophy or loose phenomenon occur.Meanwhile stainless steel and titanium close The implants such as golden nail, bone plate need subsequent operation to take out it from human body, increase patient's after bone tissue recovery from illness Pain and financial burden.
Currently, the intravascular stent of clinical application prepares material with stainless steel and NiTi alloys to be main.These blood vessel branch Frame is other than the shortcomings that may causing toxic side effect there are Ni dissolutions, and there is also reangiostenosis and thrombus (about 20%), blood Pipe endometrial hyperplasia, chronic inflammation, Antiplatelet therapy time length (Long-term taking medicine is needed to treat), (blood vessel of implantation holder) nothing Method can not carry out surgical revascularization art (second operation), long-term endothelium machine when adapting to the natural growth of blood vessel, occurring unexpected It can disorderly, subsequent monitoring difficulty.
Research and development is high tough and can become the important development side in the field with the medical material of degradation in vivo To.Degradable high polymer material can be with degradation in vivo, but its mechanical property is relatively low, such as its elasticity modulus is about 3- 5GPa can not be applied to bearing position when being applied to bone implant；Applied to intravascular stent, there are serious rebound, Wu Fada To the effect of support blood vessels, and acid accumulation is generated after macromolecule degradation, causes injected organism tissue inflammation.
The elasticity modulus of magnesium alloy is about 40GPa, very close with bone tissue, can effectively mitigate stainless steel or titanium Alloy is implanted into " stress shielding " phenomenon caused by material.Meanwhile magnesium alloy have higher tensile strength, can bear compared with Big load is applied to bone tissue and carries position, can also be applied to intravascular stent, play the role of support blood vessels.Magnesium is people Be only second to the intracellular cation of potassium in vivo, it participates in a series of metabolic processes in vivo, including osteocyte formation and add Fast knitting ability etc..It proves on evidence, the loss of magnesium can cause bone tissue to stop growing in turn, reduce osteoblast With osteoclast activity and lead to poor bone quality.Magnesium is also in close relations with nerve, muscle and cardiac function.The U.S. suggest at Year man is 420mg per the magnesium amount taken in day by day.Therefore, use magnesium and magnesium alloy as medical embedded material, corrosion dissolution Magnesium ion is to the micro release of human body or beneficial.In addition, the relatively low (- 2.36V of the standard electrode potential of magnesium and magnesium alloy SCE), not corrosion-resistant, degradation is especially easily corroded in the human body fluid containing Cl-1 ions.So magnesium and magnesium alloy at For the degradable implantation material of a new generation.
Magnesium and magnesium alloy originate in the 30-40 ages in last century as the research of bone implant material.Although clinical application is Verified, magnesium alloy has extraordinary biocompatibility, but since corrosion degradation is too in human body for magnesium and magnesium alloy Soon, hydrogen is will produce, application of the magnesium alloy as implantation material is limited.Although high-purity magnesium (such as 99.99% high purity magnesium) With good resistance to NaCl corrosive natures, but its mechanical property is less than 65MPa, also too late poly- not as good as the mechanical property of bone tissue Object is closed, load Bone Defect Repari and intravascular stent can not be applied to.Therefore, corrosion degradation speed of the magnesium alloy in body fluid is being reduced While, improving the strength and toughness of magnesium alloy becomes the key that magnesium alloy is applied to medical material.
It is well known that the corrosive nature of alloy depends on alloying component and corrosive environment.The purity of alloy is improved, is reduced Objectionable impurities elements in alloy can be effectively reduced the corrosion rate of magnesium alloy such as Ni, Cu, Fe.Magnesium alloy is closed Aurification processing is also to improve alloy strength and the improvement effective method of corrosion resistance.Aluminium element is added in the magnesium alloy to carry out Alloying can not only improve the mechanical property of alloy, while can also improve its corrosion resistance.Such as：Corrosion resistance Best AZ91E alloys have with the comparable corrosion resistance of A380 aluminium alloys, and be heat-treated after tensile strength reach 250MPa can meet the requirement of mechanical property.But the research to medical titanium alloy is it has been shown that aluminium element can be strong to human body Health generates harm.Therefore, the magnesium alloy containing aluminium is unsafe to human body.Thus, it is necessary to which developing both has good biological Compatibility, and the corrosion resistance having had, and the magnesium alloy of also sufficient intensity.
Invention content
The present invention develops a kind of magnesium alloy for being implanted into bone, the conjunction on the basis of traditional biological medical magnesium alloy Gold utensil has excellent mechanical property and corrosion resisting property, on the basis of ensuring biocompatibility, reduce the cost of alloy, have Important social and economic implications.
The present invention specifically provides a kind of magnesium alloy for being implanted into bone, it is characterised in that：Change by weight percentage It studies and is divided into：Zn 1.5-3%, Mn 0.6-1.1%, Ca 0.3-0.8%, Si 0.3-0.45%, Sr 0.45-0.8%, Li 1-1.8%, Cr 2.5-3.5%, Cu 1-2%, Mo 1.3-1.4%, Sc+La+Ce：0.01-0.08%, Nb：0.1%~ 0.8%, surplus is Mg and inevitable impurity element.
Preferably a kind of magnesium alloy for being implanted into bone, it is characterised in that：Zn2-2.5%, Mn 1-1.1%, Ca 0.5-0.55%, Si 0.35-0.4%, Sr 0.5-0.6%, Li 1.5-1.6%, Cr 2.8-3%, Cu 1.2-1.25%, Mo 1.3-1.35%, Sc+La+Ce：0.01-0.05%, Nb 0.6-0.65%, surplus are Mg and inevitable impurity member Element.
Preferably a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage： Zn 1.5%, Mn 0.6%, Ca 0.3%, Si 0.3%, Sr 0.45%, Li 1%, Cr 2.5%, Cu 1%, Mo 1.3%, Sc+La+Ce：0.01%, Nb：0.1%, surplus is Mg and inevitable impurity element.
Preferably a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage： Zn 3%, Mn 1.1%, Ca 0.8%, Si 0.45%, Sr 0.8%, Li 1.8%, Cr 3.5%, Cu 2%, Mo 1.4%, Sc+La+Ce：0.08%, Nb：0.8%, surplus is Mg and inevitable impurity element.
The preferably described magnesium alloy for being implanted into bone, wherein Sc, La, Ce mass ratio are 6: 3: 1.
The present invention also provides a kind of magnesium alloy for being implanted into bone, the system of the magnesium alloy for being implanted into bone Preparation Method,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
It is preferred that step（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80 minutes, extrusion forming, squeezes at 400 DEG C Pressure ratio 25, extruding rate 20mm/min obtain the magnesium alloy semi-finished product of a diameter of 20mm.
It is preferred that step（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 100 minutes, is squeezed at 410 DEG C Type, extrusion ratio 30, extruding rate are 40 mm/min, obtain the magnesium alloy semi-finished product of a diameter of 40mm.
It is preferred that step（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 120 minutes, is squeezed at 420 DEG C Type, extrusion ratio 35, extruding rate are 60 mm/min, obtain the magnesium alloy semi-finished product of a diameter of 50mm.
Preferably it is magnesium alloy surface of semi-finished coating processing, by step（5）The magnesium alloy prepared through Overheating Treatment Finished product, which is put into deposit made of in hydrogeneous fluorine-containing acid solution, carries out first layer processing in liquid, the thickness range of first layer is 2.5 μm, the second layer that the alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again later is handled, the second layer After the completion of processing, the thickness range of natural drying or drying 24 hours in 30~50 DEG C of baking ovens, second layer coating is 2.5 μm, Obtain final products.
Magnesium alloy provided by the present invention, the effect of each element is as follows in magnesium alloy：
Zinc is human body one of element the most basic.Zinc can promote the update of cell, be the essential trace elements of the human body, can increase The immune function of strong man's body maintains the growth and development of body.Zinc is the ingredient of many protein, nucleic acid synthesizing enzyme, is up to a hundred The activated centre of kind enzyme.Zinc is again insulin component, is the key factor of normal activity of sustaining life.Zinc defect may cause All physiological disorders of human body.Maximum solid solution degree of the zinc in magnesium is 6.2%, and be the another kind in addition to aluminium has very much The alloy element of effect has solution strengthening and ageing strengthening double action.The room temperature that addition zinc can improve magnesium alloy is strong Degree.Meanwhile zinc can also mitigate the corrosiveness caused by iron, nickel exist, and improve the corrosion resisting property of magnesium alloy.In the present invention, By weight percentage, zinc (Zn) preferred content is ranging from：1.5-3%, more preferable content range are：2-2.5%.Manganese is human body One of essential 15 kinds of trace elements of physiological function, for human body per manganese amount about 3-9mg day by day, it is metabolic in human body A kind of not replaceable trace element.Manganese participates in the activity of a variety of enzymes in vivo, is the activator of enzyme, boosts metabolism.Manganese is also It can promote bone calcification, improve the metabolism of protein, promote savings of the vitamin B1 in liver.When human body manganese deficiency, can lead Endocrine disturbance is caused, shows malnutrition, the symptoms such as sexual disorder accelerate the aging of people.Addition manganese can in the magnesium alloy With during melting, element harmful with part forms intermetallic compound and separates, and eliminates iron, silicon and other are heavy Metallic element avoids generating harmful intergranular compound, improves the anti-NaCl corrosive powers of magnesium alloy.Manganese is added can be by a small margin The intensity of magnesium alloy is improved, but when manganese content excess, manganese can be caused to be segregated on intergranular, reduces the resistance to of magnesium alloy instead Corrosion.In the present invention, by weight percentage, manganese (Mn) preferred content is ranging from：0.6-1.1%, more preferable content range For：1-1.1%.Calcium can improve the formability and intensity of magnesium alloy energy with refining alloy crystal grain.Calcium can also reduce magnesium alloy Micro cell effect, improve the corrosion resistance of magnesium alloy.Calcium is the important component for constituting plant cell wall and animal skeleton, The 99% of calcium is present in bone and tooth in human body, remaining is distributed mainly in body fluid, anti-to participate in certain important enzymes It answers.It plays an important role maintaining heart normal contraction, neural muscle excitability, blood coagulation and holding cell membrane integrity etc.. The most important biological function of calcium is courier's effect, and intracellular signal transmits the concentration difference by intraor extracellular calcium ion.As carefully Born of the same parents' excitation time, flow of calcium ions make its concentration increase.When the transhipment of calcium ion adjusting is abnormal, it is anti-just to generate pathologic It answers.In the present invention, by weight percentage, calcium (Ca) preferred content is ranging from：0.3-0.8%, more preferable content range are： 0.5-0.55%.Silicon can significantly improve the mobility of magnesium alloy fused mass.It, may drop but if ferro element also exists simultaneously The corrosion resisting property of low magnesium alloy.Silicon has been considered to mineral element needed by human, it is in human body with metasilicic acid or inclined silicon The growth form of hydrochlorate exists.It can promote the generation and optimization of mucopolysaccharide and collagen in connective tissue.Silicon is that bone is soft Bon e formation initial stage necessary element is the catalyst of mineral deposit.The structure and quickening for contributing to human immune system are cured Conjunction process.Silicon can keep the elasticity of vascular wall, be the required ingredient of collagen tissue, lack silicon and arteries and veins hardening may be actuated.In the present invention, by weight Percentages are measured, silicon (Si) preferred content is ranging from：0.3-0.45%, more preferable content range are：0.35-0.4%.Sr is bone The important component of bone and tooth can promote the formation of skeleton development and osteoid, adjust calcium metabolism.In recent years research hair Existing, Sr is essential and not replaceable in many molluscan embryonic developments.Osteoporosis may be Ca, Sr metabolism Caused by disorder, stable Sr compounds have therapeutic effect to osteoporosis.Studies have shown that low dosage Sr salt can reduce bone information, Higher bon e formation rate is maintained, synthesis, the metabolism of bone are promoted.Sr is important one of alloying element for magnesium alloy, and Sr's adds Add can effective Refining Mg Alloy tissue, improve the casting properties of magnesium alloy, improve the mechanical property of room temperature and high temperature, change The croop property of magnesium alloy has been apt to it, Sr elements can also improve the corrosion resistance of magnesium alloy to a certain extent.Although Sr at This is relatively high, but Sr can improve the casting manufacturability of alloy, and large batch of die casting life can be met by adding a small amount of Sr Production, to make production cost reduce.In the present invention, by weight percentage, strontium (Sr) preferred content is ranging from：0.45- 0.8%, more preferable content range is：0.5-0.6%.Li is the alloying element of unique changeable Mg structures, in human body environment Have the function of improving 2 compactness of corrosion product Mg (OH) of magnesium.In particular, in Mg-Ca alloys Li elements addition, Li+ from Son forms LiCl with MgCl2.LiCl precipitates in the magnesium hydroxide hole of surface and becomes barrier layer, results in Mg (OH) 2 The compactness of film improves.In the present invention, by weight percentage, lithium (Li) preferred content is ranging from：1-1.8% more preferably contains Amount is ranging from：1.5-1.6%.Magnesium alloy provided by the present invention contains chromium, and in biomedicine, chromium is a kind of required 's.Chromium is needed by human, has important trophism, needs chromium to participate in when insulin plays a role.Only Cr VI pair The toxic effect of human body, being irritating to the skin property also have sensitization.Chromium, which is magnesium alloy, simultaneously has the most important alloy of corrosion resistance Element, in oxide isolation, chromium can make to be quickly generated chromium oxide passivation film on alloy surface, this layer of passivating film be very it is fine and close and Stable, it can restore rapidly being destroyed.Chromium can effectively improve the pitting resistance of magnesium alloy, when have in alloy molybdenum and When nitrogen exists simultaneously, this validity of chromium greatly reinforces.Since chromium is main anti-corrosion element, and improve nitrogen in alloy Solubility, therefore in magnesium alloy of the present invention chromium content control in 2.5-3.5%, more preferable content range is：2.8-3%.Copper It is the essential trace element being present in organism, participates in all links of internal vital movement, has a variety of particularly important Physiology and biochemical action.Studies have shown that when occurring copper shortage in human body, since cupric enzymatic synthesis is reduced, angiocarpy meeting can not Maintain normal form and function；Atrial thrombus caused by copper lacks is formed most notable, and also seeing leads to coronary artery necrosis, hat The generation of the symptoms such as shape Arterial thrombosis, myocardial necrosis and ventricle calcification；Copper shortage can lead to migrating, moving for arterial smooth muscle Arteries and veins elastosis and fracture, the aortic smooth myodegeneration and formation of ventricle and coronary aneurysm.Therefore, by adding Cu The magnesium alloy of element persistently generates micro copper, and the Cu additions effect less than 1 (weight) % is not prominent enough, at heat Reason, due to not reaching the supersaturated content of copper in the magnesium alloy, the trace copper plasma diffusing W,Mo being unfavorable in practical application；Content When more than 2 (weight) %, even if may result in magnesium alloy can also retain a certain amount of copper-rich phase at high temperature, to serious shadow Ring processing performance, corrosion resisting property and the mechanical property to magnesium alloy itself.The content of Cu elements can be Cu：1.0- 2.0%, more preferable content range is：1.2-1.25%.Magnesium alloy provided by the present invention contains molybdenum element, is used as surgery first Implantation alloy, molybdenum is also a kind of important micro elements needed by human simultaneously in alloy.Secondly molybdenum is added magnesium alloy and mainly uses Corrosion resistance to improve alloy is especially the performances such as resistance to spot corrosion and crevice corrosion.Research Literature shows that the resistance to spot corrosion of molybdenum and gap are rotten The ability of erosion is 3 times or so of chromium, and many experiments are pointed out, molybdenum is mainly the anti-corrosion effect for strengthening chromium in steel.Therefore magnesium of the present invention Mo in alloy：1.3-1.4%, more preferable content range are：1.3-1.35%.Magnesium alloy provided by the present invention contains rare earth member Plain Sc, La, Ce, the addition of rare earth element can further reinforced magnesium alloy anti-microbial property, while improving oxidation film and matrix The bond strength of material is to enhance corrosion resisting property.Magnesium-rare earth has the potentiality as new bio medical material.Due to dilute The unique configuration of extra-nuclear electron of earth elements plays purification melt in casting process, crystal grain thinning, improves the works such as casting character With there is significant solid solution and ageing strengthening effect in the magnesium alloy, the comprehensive performance of magnesium alloy can be effectively improved.When adding When adding two or more rare earth elements, due to the interaction between rare earth element, the solid solubility in magnesium can be reduced each other, Additional reinforcing effect can also be generated.Rare earth is also the trace element in human body, and low dosage rare earth element is not only harmless, The growth and development that may additionally facilitate organism is conducive to improve body's immunity, has anti-oxidant and antimutagenesis.It examines simultaneously Considering reduces the density of magnesium alloy, and what is chosen as possible is the small rare earth element of atomic weight, and in addition this field has been generally acknowledged that a variety of dilute The effect of earth elements is more preferable than Rare Earth Elements Determination effect, so the present invention selects Sc+La+Ce：0.01-0.08%, more preferably Be Sc+La+Ce：0.01-0.05%, and Sc, La, Ce mass ratio are 6: 3: 1.It is other in magnesium alloy provided by the present invention Element such as Nb etc., Nb be nontoxic element or low cytotoxicity factor, good biocompatibility, can safety be used for alloy design. These elements are common addition element in biomedical alloy material, are primarily used to improve the intensity of product, in crystalline substance The carbide for the small and dispersed that boundary and interdendritic are precipitated, can prevent Grain Boundary Sliding, with obvious effects to the reinforcing of alloy, while also carry The abrasion resistance properties of high alloy, for ensureing the good mechanical property of the material, corrosion resistance and abrasion resistance properties.The present invention The Nb of selection：0.1%~0.8%, more preferable content range is：Nb：0.6%~0.65%.
Beneficial effects of the present invention：
1) performances such as the density of this alloy, elasticity modulus and human body hard tissue are close, can effectively reduce stress-shielding effect；
2) the purer magnesium of the intensity and hardness of this alloy is high, and can adjust mechanical property by heat treatment, has preferable carrying Ability can be used for the load bearing position such as bone tissue, intravascular；
3) all catabolites of this alloy are harmless, and are easy to exclude by metabolism external；
4) this alloy may be used as the material of sclerous tissues' (such as bone tissue) replacement or interventional treatment, or as intravascular stent material Material, implants after a certain period of time, can be degradable；
5）The magnesium alloy of the present invention, yield strength >=370MPa, tensile strength >=410MPa, elongation >=18.5%, sterilizing rate >=90%, hence it is evident that lack the product of alloying element higher than other, hence it is evident that higher than the similar product without carrying out surface coating processing；
6）The second phase is formed in magnesium alloy：One or two of Mg2Si, Mg2Sr, Mg17Sr2, Mg2Ca, CaMgSi or more, Form the complex magnesium alloy with comprehensive performance；There is the material good biocompatibility and mechanical property, cytotoxicity to comment Grade is 0 grade.The degradable absorption in biological fluid or blood environment, which is applied to cardio-vascular interventional therapeutic or bone is implanted into Medical field is suitable as the implantation material used under human body environment.
Specific implementation mode
It elaborates to technical solution of the present invention below with reference to example embodiment.However, example embodiment can be with more Kind form is implemented, and is not understood as limited to embodiment set forth herein；On the contrary, thesing embodiments are provided so that this The design of example embodiment more comprehensively and completely, and is comprehensively communicated to those skilled in the art by invention.
Embodiment 1
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is Zn 1.5%, Mn by weight percentage 0.6%, Ca 0.3%, Si 0.3%, Sr 0.45%, Li 1%, Cr 2.5%, Cu 1%, Mo 1.3%, Sc+La+Ce： 0.01%, Nb：0.1%, surplus is Mg and inevitable impurity element, and wherein Sc, La, Ce mass ratio is 6: 3: 1.
The preparation method of the magnesium alloy for being implanted into bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Embodiment 2
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn2.5%, Mn 1.1%, Ca 0.55%, Si 0.4%, Sr 0.6%, Li 1.6%, Cr 3%, Cu 1.25%, Mo 1.35%, Sc+La+ Ce：0.05%, Nb 0.65%, surplus are Mg and inevitable impurity element.Wherein Sc, La, Ce mass ratio are 6: 3: 1. The preparation method of the magnesium alloy for being implanted into bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Embodiment 3
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn 3%, Mn 1.1%, Ca 0.8%, Si 0.45%, Sr 0.8%, Li 1.8%, Cr 3.5%, Cu 2%, Mo 1.4%, Sc+La+Ce： 0.08%, Nb：0.8%, surplus is Mg and inevitable impurity element.Wherein Sc, La, Ce mass ratio are 6: 3: 1.Described Preparation method for the magnesium alloy for being implanted into bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Comparative example 1
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is Zn 1.5%, Mn by weight percentage 0.6%, Ca 0.3%, Si 0.3%, Li 1%, Cr 2.5%, Cu 0.5%, Mo 1.3%, Sc+La+Ce：0.01%, it is remaining Amount is Mg and inevitable impurity element, and wherein Sc, La, Ce mass ratio is 6: 3: 1.
The preparation method of the magnesium alloy for being implanted into bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 48-49: 1 to select Mg-Si intermediate alloys, wherein Mg: Si mass ratio, other are low Melting element is added in the form of the metal simple-substance that purity is 99.99% and/or in the form of low melting point intermediate alloy；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Comparative example 2
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn2.5%, Mn 1.1%, Ca 0.55%, Si 0.4%, Sr 0.6%, Li 0.8%, Cr 3%, Cu 1.25%, Mo 1.35%, Sc+La+ Ce：0.05%, surplus is Mg and inevitable impurity element.Wherein Sc, La, Ce mass ratio are 6: 3: 1.Described is used for It is implanted into the preparation method of the magnesium alloy of bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Comparative example 3
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn 3%, Mn 1.1%, Si 0.45%, Li 1.8%, Cr 3.5%, Cu 0.5%, Mo 0.4%, Sc+La+Ce：0.08%, Nb： 0.8%, surplus is Mg and inevitable impurity element.Wherein Sc, La, Ce mass ratio are 6: 3: 1.Described is used to be implanted into bone The preparation method of the magnesium alloy of bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 48-49: 1 to select Mg-Si intermediate alloys, wherein Mg: Si mass ratio, other are low Melting element is added in the form of the metal simple-substance that purity is 99.99% and/or in the form of low melting point intermediate alloy；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
Comparative example 4
A kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn 3%, Mn 1.1%, Si 0.45%, Li 1.8%, Cr 3.5%, Cu 0.5%, Mo 0.4%, Sc+La+Ce：0.08%, Nb： 0.8%, surplus is Mg and inevitable impurity element.Wherein Sc, La, Ce mass ratio are 6: 3: 1.Described is used to be implanted into bone The preparation method of the magnesium alloy of bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 48-49: 1 to select Mg-Si intermediate alloys, wherein Mg: Si mass ratio, other are low Melting element is added in the form of the metal simple-substance that purity is 99.99% and/or in the form of low melting point intermediate alloy；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy finished product of a diameter of 20-50mm；
Performance detection is carried out in the following manner to embodiment 1-3, comparative example 1-4 products obtained therefroms：
1, Mechanics Performance Testing
Mechanical property (yield strength and elongation after fracture) in testing example and comparative example, correlated results is shown in Table 1；
2, anti-microbial property detects
According to " JIS Z 2801-2000《Antibacterial fabricated product-antibiotic property test method and antibacterial effect》、 GB/T 2591- 2003《Antibiotic plastic anti-microbial property experimental method and antibacterial effect》" etc. correlation standards, quantitative test embodiment 1-3, The sterilizing rate of comparative example 1-4 products obtained therefroms.Anti-microbial property testing result is shown in Table 1, and the calculation formula of wherein sterilizing rate is：Sterilizing rate (%)=[(control sample viable count-antibacterial magnesium alloy viable count)/control sample viable count] × 100, control sample viable count It is that the viable count after Bacteria Culture is carried out in comparative example, antibacterial magnesium alloy viable count refers to being carried out carefully on antibacterial magnesium alloy Viable count after bacterium culture；
3. corrosion rate is tested
It is 37 DEG C in temperature, corrosion rate is measured in simulated body fluid commonly used in the art, test result is shown in Table 1.
Table 1
Although above the present invention is described in detail with a general description of the specific embodiments, in this hair On the basis of bright, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore, exist Without departing from these modifications or improvements on the basis of spirit of that invention, the scope of protection of present invention is belonged to.

Claims (10)

1. a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is Zn 1.5-3% by weight percentage, Mn 0.6-1.1%, Ca 0.3-0.8%, Si 0.3-0.45%, Sr 0.45-0.8%, Li 1-1.8%, Cr 2.5- 3.5%, Cu 1-2%, Mo 1.3-1.4%, Sc+La+Ce：0.01-0.08%, Nb：0.1%~0.8%, surplus is for Mg and not Evitable impurity element.
2. a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn2-2.5%, Mn 1-1.1%, Ca 0.5-0.55%, Si 0.35-0.4%, Sr 0.5-0.6%, Li 1.5-1.6%, Cr 2.8-3%, Cu 1.2-1.25%, Mo 1.3-1.35%, Sc+La+Ce：0.01-0.05%, Nb 0.6-0.65%, surplus are Mg and can not The impurity element avoided.
3. a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn 1.5%, Mn 0.6%, Ca 0.3%, Si 0.3%, Sr 0.45%, Li 1%, Cr 2.5%, Cu 1%, Mo 1.3%, Sc+La+ Ce：0.01%, Nb：0.1%, surplus is Mg and inevitable impurity element.
4. a kind of magnesium alloy for being implanted into bone, it is characterised in that：Chemical composition is by weight percentage：Zn 3%, Mn 1.1%, Ca 0.8%, Si 0.45%, Sr 0.8%, Li 1.8%, Cr 3.5%, Cu 2%, Mo 1.4%, Sc+La+Ce： 0.08%, Nb：0.8%, surplus is Mg and inevitable impurity element.
5. the magnesium alloy according to any one of claims 1-4 for being implanted into bone, wherein Sc, La, Ce mass ratio are 6: 3: 1。
6. the preparation method as described in any one in claim 1-5 for being implanted into the magnesium alloy of bone,
(1) dispensing：For the composition design needed for magnesium alloy, dispensing is first carried out, Mg-Zn intermediate alloys is selected, is closed among Mg-Zn Mg: Zn mass ratio is 0.8-0.82: 1 in gold；It is 0.42-0.44: 1 to select Mg-Sr intermediate alloys, Mg: Sr mass ratio；It selects Mg-Si intermediate alloys, wherein Mg: Si mass ratio are 48-49: 1, the metal list that other low melting point elements are 99.99% with purity Matter form and/or the form of low melting point intermediate alloy are added；
(2) alloy melting：Alloy cast ingot/powder is preheated in 100-150 DEG C of container, is moved it into vacuum arc furnace ignition later, It is evacuated down to 10-3-10-4Pa, early period, power with 100KW/min progressively increased to 800KW, keeps 400-450 DEG C of temperature, keeps 1-3min, later stage power progressively increase to 1800KW with 200KW/min, and smelting temperature is 650 DEG C~720 DEG C, at this temperature Smelting time is 8-10min, makes the complete melting of alloy material；
（3）By step（2）Obtained alloy melt casting becomes long 120-140cm, width 50-60cm, and thickness is the casting of 10-20cm Ingot；Above-mentioned ingot casting is preheated 30 minutes at 200-300 DEG C, is forged under inert gas protection, the amount of forging is 10-20%；
（4）It is cooling in 70-80 DEG C of hot water after forging, it then preheats 80-120 minutes, extrusion forming, squeezes at 400-420 DEG C Than 25-35, extruding rate is 20-60 mm/min, obtains the magnesium alloy semi-finished product of a diameter of 20-50mm；
（5）Magnesium alloy surface of semi-finished coating processing, by step（4）The magnesium alloy finished product prepared through Overheating Treatment is put by hydrogeneous First layer processing is carried out in fluorine-containing acid solution in manufactured deposition liquid, the thickness range of first layer is 1 μm~5 μm, later The second layer that alloy after coating first layer is carried out to atomizing spraying fluoridated hydroxyapatite again is handled, and second layer processing is completed Afterwards, the thickness range of natural drying or drying 4~48 hours in 30~50 DEG C of baking ovens, second layer coating is 1 μm~5 μm, is obtained To final products.
7. the preparation method of the magnesium alloy for being implanted into bone as described in claim 1, it is characterised in that step（4）After forging, It is cooling in 70-80 DEG C of hot water, it is then preheated 80 minutes at 400 DEG C, extrusion forming, extrusion ratio 25, extruding rate 20mm/ Min obtains the magnesium alloy semi-finished product of a diameter of 20mm.
8. the preparation method of the magnesium alloy for being implanted into bone as described in claim 1, it is characterised in that step（4）After forging, It is cooling in 70-80 DEG C of hot water, it is then preheated 100 minutes at 410 DEG C, extrusion forming, extrusion ratio 30, extruding rate is 40 mm/ Min obtains the magnesium alloy semi-finished product of a diameter of 40mm.
9. being used to be implanted into the preparation method of the magnesium alloy of bone such as claim 1, it is characterised in that step（4）After forging, in 70- It is cooling in 80 DEG C of hot water, it is then preheated 120 minutes at 420 DEG C, extrusion forming, extrusion ratio 35, extruding rate is 60 mm/min, Obtain the magnesium alloy semi-finished product of a diameter of 50mm.
10. being used to be implanted into the preparation method of the magnesium alloy of bone such as claim 1, it is characterised in that magnesium alloy surface of semi-finished applies Processing is covered, by step（5）The magnesium alloy finished product prepared through Overheating Treatment is put into sink made of in hydrogeneous fluorine-containing acid solution First layer processing is carried out in hydrops, the thickness range of first layer is 2.5 μm, and the alloy after coating first layer is carried out mist again later The second layer processing for changing spraying fluoridated hydroxyapatite spontaneously dries or after the completion of second layer processing in 30~50 DEG C of baking ovens 24 hours dry, the thickness range of second layer coating is 2.5 μm, obtains final products.
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CN109330674A (en) * 2018-09-07 2019-02-15 西安卓恰医疗器械有限公司 A kind of internal fixation system and its usage mode
CN111321332A (en) * 2018-12-17 2020-06-23 佳能株式会社 Magnesium-lithium alloy member, method for manufacturing same, optical device, and imaging device
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