CN106282664A - Biodegradable medical zinc lithium binary alloy material and preparation method and application - Google Patents

Biodegradable medical zinc lithium binary alloy material and preparation method and application Download PDF

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CN106282664A
CN106282664A CN201610726974.7A CN201610726974A CN106282664A CN 106282664 A CN106282664 A CN 106282664A CN 201610726974 A CN201610726974 A CN 201610726974A CN 106282664 A CN106282664 A CN 106282664A
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alloy
lithium
zinc
biodegradable
medical
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袁广银
岳锐
黄华
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Shanghai Jiaotong University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/32Materials or treatment for tissue regeneration for nerve reconstruction

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Abstract

The invention discloses a kind of biodegradable medical zinc lithium binary alloy material and preparation method and application;Described alloy material is made up of the material of following percentage by weight: lithium 0.55~10wt.%, and remaining is Zn.The alloy of melting gained is the most also needed to carry out pyroplastic deformation processing, refining alloy tissue thus put forward heavy alloyed performance.The kirsite of the present invention has the advantages such as comprehensive mechanical property, good biocompatibility and the regulatable degradation rate of excellence, it can be applied to prepare endovascular stent, bone implants, decorative sursery and neurocranial surgery implantation instrument, operation suture thread, various operation sticking patch, anastomat, vascular clamp or nerve rehabilitating tube etc. as preparing the material of degradable medical implantation instrument.

Description

Biodegradable medical zinc lithium binary alloy material and preparation method and application
Technical field
The invention belongs to biomedical materials field, be specifically related to a kind of biodegradable medical zinc lithium binary alloy material And preparation method and application.
Background technology
At present, operation is implanted the medical material in human body and is generally adopted by nondegradable metal material, such as (1) Austria Family name's body rustless steel (316LSS);(2) cochrome;(3) Medical tantalum;(4) titanium and alloy thereof;(5) niti-shaped memorial alloy.This There is following drawback in the application of a little permanent implanted materials, such as due to it after (1) permanent metal intravascular stent implants human body Non-degradable, also exists easily formation thrombosis and causes the deficiency of in-stent restenosis, intimal fibrosis, and support forever retains Internal, it is impossible to again to take out, once there is blood vessel blockage again at same position, then implant an intravascular stent and become to be stranded very much Difficult;(2), after rustless steel, titanium alloy nail, hone lamella etc. implant human body, second operation is needed to be drawn off after osseous tissue is fully recovered, Add misery and the financial burden of patient.Therefore research and development has the body of good mechanical property and bio-compatible performance The medical material of interior degraded becomes the important development direction in this field.
At present, in degradable biomaterial, degradable high polymer material, bioceramic, magnesium base alloy, ferrous alloy are near More deep material is studied over Nian.But due to the plasticity of polymeric material low strength, ceramic material poor and limit its Extensive application clinically.Magnesium base alloy has good biocompatibility, but its corrosion resistance is poor, is quickly dropped in human body Solve, lose its mechanical support effect.The corrosion rate of ferrous alloy is too slow, and the degradable time may be up to the several years.
Zinc is one of the most basic necessary trace element of human body.All physiological metabolism processes are almost participated in human body, Zinc is except playing catalysis or structure effect in addition in various metals enzyme, transcription factor and other albumen, also with neurotransmitter or tune The form of matter sample plays its function.Zinc can promote the renewal of cell, can strengthen the immunocompetence of human body, maintain human body growth and Growing, zinc defect may cause all of physiological disorders of human body.Zn content in adult body is 1.4~2.3g, healthy one-tenth The allowance,dietary of people's zinc every day is 15~40mg, and it is anti-that adult's daily intake of about 300mg zinc is only possible to have certain toxicity Should.Therefore, kirsite has good biocompatibility.The standard electrode potential of pure zinc is-0.763V, between pure magnesium (- 2.37V) and between pure iron (-0.44V), the corrosion rate of zinc-containing alloy also is located between magnesium base alloy and ferrous alloy, its fall Solve the requirement that speed is the most satisfied clinical implants.
But, the comprehensive mechanical property of pure zinc is poor, and corrosion rate is the slowest, is difficult to meet clinical medical demand, right It is to improve the main method of its mechanical property and corrosion rate that pure zinc carries out alloying, adds in zinc as having in prior art simultaneously Add Fe, Li and trace element Mg, Ca, Sr, Si, Mn and rare earth element, but the intensity of zinc alloy material prepared by this technology Relatively low with plasticity, also do not reach the performance requirement of preferable intravascular stent material.Contain more alloying element, a side simultaneously Face discharges more alloying element kind in degradation process and adds human body potential risks, and on the other hand work prepared by alloy Skill replicates, and adds the quality control difficulty of material, and respective alloy cost too increases.We find zinc lithium binary under study for action Alloy has higher intensity and plasticity and suitable degradation rate, simultaneously because material component is simple, biological safety is more Good, smelting preparation process is easy, applies more advantage as medical embedded material.
Summary of the invention
The deficiency existed for existing medical degradable material, it is an object of the invention to provide that a kind of intensity is high, plasticity is good, Degradation rate is controlled, biodegradable biodegradable medical zinc lithium binary alloy material and preparation method and application.
It is an object of the invention to be achieved through the following technical solutions:
First aspect, the present invention relates to a kind of biodegradable medical zinc lithium binary alloy material, described alloy material bag Include each component of following weight percent content: lithium 0.55~10%, zinc 90~99.45%.
Preferably, described alloy material includes each component of following weight percent content: lithium 1~3%, zinc 97~ 99%, or lithium 4.1~10%, zinc 90~95.9%.Most preferably lithium 1~3%, zinc 97~99%.
Second aspect, the invention still further relates to the preparation side of a kind of aforesaid biodegradable medical zinc lithium binary alloy material Method, said method comprising the steps of:
S1, weigh zinc raw material, lithium raw material according to described alloy proportion;
S2, zinc raw material, mixed flux, lithium raw material are added heat fusing, stir, form alloy melt;
S3, described alloy melt through refine, stand, pour into a mould after cool down, obtain biodegradable medical zinc lithium binary close Gold ingot material.
Preferably, described zinc raw material is pure zinc, and described lithium raw material is pure lithium;Step S2 particularly as follows: first by pure zinc (purity >= 99.995%) be heated to 420 DEG C~440 DEG C after it is completely melt, add mixed when melt temperature is risen to 580~620 DEG C Closing flux, flux to be mixed is completely covered on bath surface and melt temperature is down to 540~560 DEG C simultaneously, in the protection of Ar gas The pure lithium of lower addition (purity >=99.999%).
Preferably, in step S1, described zinc raw material is pure zinc, and described lithium raw material is pure lithium;Claim according to described alloy proportion Taking particularly as follows: pure lithium is calculated by recovery rate 80~85%, other alloys (Zn) element is calculated by recovery rate 100%.
Preferably, described mixed flux is LiCl and LiF mixed flux.In the most described LiCl and LiF mixed flux The mass ratio of LiCl and LiF is 1: 2~4.
Preferably, the consumption of described mixed flux is 5~10mm for making covering at bath surface thickness.
Preferably, in step S3, described refine uses hexachlorethane to carry out refine, and refining temperature is 540 ± 20 DEG C, chlordene The amount of ethane is the 0.2~0.3% of alloy melt gross weight.
Preferably, also include that the alloy cast ingot material obtaining step S3 carries out Homogenization Treatments, and hot extrusion or roll The process of deformation processing processed.
Preferably, described Homogenization Treatments temperature is 320~380 DEG C, processes the time 4~10h;Described hot extrusion processing Deformation temperature is 190~280 DEG C, and extrusion ratio is 6~50: 1;The deformation temperature of described rolling deformation processing is 190~280 DEG C, Every time amount of rolling is 10~30%;The medical zinc of biodegradable is obtained after water-cooled or air cooling after described hot extrusion or rolling deformation Lithium bianry alloy plastic deformation processing state material.
Preferably, after step S3, may also include, by casting technique, alloy cast ingot material is further prepared into three-dimensional connection Logical tissue engineering bracket, by extrusion rolling drawing group technology alloy deformation state materials processing filamentation material and support hair The step of tubule material.
The third aspect, the invention still further relates to a kind of aforesaid biodegradable medical zinc lithium binary alloy material can in preparation Degrade the purposes in medical embedded apparatus.
Preferably, described degradable medical implantation instrument is planted for implanting support, bone implants, decorative sursery and neurocranial surgery Enter apparatus, operation suture thread, various operation sticking patch, anastomat, vascular clamp or nerve rehabilitating tube;Described implantation support includes Intravascular stent, biliary tract prosthesis, trachea bracket, urethra rack, esophageal stents appear or intestinal stent;Described bone implants include hone lamella, Nail, internal fixation screw, intramedullary needle or bone tissue engineering scaffold.
Preferably, described sticking patch includes intestinal surgery operation sticking patch or Craniocerebral Surgery sticking patch;Described anastomat Including bowel anastomosis device, blood vessel anastomat.
The present invention is by adding a certain amount of Li element, while significantly improving the mechanical property of alloy in matrix Zn Kirsite corrosion degradation speed in biological environment can also be regulated.
Compared with prior art, the method have the advantages that
1, the zinc lithium bianry alloy of the present invention can in human body natural degradation, reach after medical effect within a certain period of time Can disappear from vivo degradation and excrete safely eventually through metabolism.
2, the kirsite of the present invention selects elemental lithium as main alloy element, can significantly improve zinc lithium binary and close The intensity of gold and plasticity, the highest tensile break strength has reached 501MPa, and stretch percentage elongation has reached 48%.And by controlling The content of Li element (0.55~10wt.%, more preferably 1%~3% and 4.1~10%, most preferably 1.0~3wt.%) permissible Realize the regulation of intensity and plasticity.
3, the kirsite of the present invention comprehensively possesses good mechanical property, decay resistance and biocompatibility.According to not With the purposes requirement to material property, suitably regulate the content of Li element, it is possible to obtain corresponding mechanical property, corrosion resistance Energy.As suitably reduced the content of Li element, it is possible to obtain the material of moderate strength high-plasticity corrosion-resistance, it is suitable as drawing filamentation Material and intravascular stent capillary tubes;Suitably increasing the content of Li element, corrosion rate increases accordingly, it is possible to obtain in high intensity Etc. the material of plasticity, it is suitable as bone implants material.
4 is similar with zinc element, and in the present invention, the elemental lithium in Zn-Li alloy itself is also the trace element of needed by human One of;Lithium is it will be apparent that lithium salts for improvement and stabilizing the emotions and prevents spirit point to the effect of human central nervous system It is effective for splitting disease, and it can also improve hallucination and the positive symptom of vain hope isotomy disease.Medically with lithium carbonate, lithium sulfate, paddy The lithium salts such as propylhomoserin lithium control and treat spirit manic disorder.Li+Ion pair incidence of atherosclerosis rate has preventive effect.Normally People is about 60~100 μ g/d to the dietary requirement amount of lithium, and the intake of lithium will have a negative impact less than 25 μ g/d.
5, the zinc lithium bianry alloy composition of the present invention is simple, and alloy preparation technology is easy, convenient control quality of materials.Simultaneously Corrosion degradation product ion kind is few, little to the potential hazard of human body, compared with prior art has more preferable biocompatibility.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in the technology of this area Personnel are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into the present invention Protection domain.
Embodiment 1
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 0.55%, and remaining is Zn.
The preparation process of this alloy material is as follows:
S1, weigh each raw material according to above-mentioned alloy proportion;
S2, in inwall scribbles the iron crucible of protective coating, put into pure zinc (purity >=99.995%), be warming up to 420 DEG C and treat After pure zinc is completely melt, zinc melt is warming up to 580 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), treat After above-mentioned mixed solvent is completely covered zinc bath surface, then zinc melt temperature is down to 540 DEG C, now adds under the protection of Ar gas Enter pure lithium (purity >=99.999%), after pure lithium melts, stir, form alloy melt;
S3, to described alloy melt use hexachlorethane carry out refine, refining temperature is 540 ± 5 DEG C, the amount of hexachlorethane For alloy melt gross weight 0.25%;Refine stands 12min at 540 ± 5 DEG C after completing, and cools down after cast, and obtaining biology can Degrade medical zinc lithium bianry alloy ingot material;
S4, to obtain alloy cast ingot material carry out Homogenization Treatments and hot extrusion or rolling deformation processing process, State material is processed to biodegradable medical zinc lithium bianry alloy plastic deformation;Wherein, Homogenization Treatments temperature is 350 DEG C, place Reason time 8h;Hot extrusion or rolling processing deformation temperature are 250 DEG C, and extrusion ratio is 28: 1 or every time amount of rolling 20%, extruding Or water-cooled after rolling deformation.
Embodiment 2
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 10%, and remaining is Zn.
The preparation method of this alloy material is with embodiment 1, institute's difference:
S2, put into pure zinc after be warming up to 430 DEG C after pure zinc is completely melt, zinc melt is warming up to 600 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), after above-mentioned mixed solvent is completely covered zinc bath surface, then by zinc melt Temperature is down to 550 DEG C, now adds pure lithium under the protection of Ar gas;
S3, refining temperature are 540 ± 10 DEG C, and the amount of hexachlorethane is the 0.2% of alloy melt gross weight;After refine completes 10min is stood at 540 ± 10 DEG C;
S4, Homogenization Treatments temperature are 320 DEG C, process time 10h;Hot extrusion or rolling processing deformation temperature are 190 DEG C, Extrusion ratio is 50: 1 or every time amount of rolling 30%.
Embodiment 3
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 4.1%, and remaining is Zn.
The preparation method of this alloy material is with embodiment 1, institute's difference:
S2, put into pure zinc after be warming up to 440 DEG C after pure zinc is completely melt, zinc melt is warming up to 590 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), after above-mentioned mixed solvent is completely covered zinc bath surface, then by zinc melt Temperature is down to 560 DEG C, now adds pure lithium under the protection of Ar gas;
S3, refining temperature are 540 ± 10 DEG C, and the amount of hexachlorethane is the 0.3% of alloy melt gross weight;After refine completes 15min is stood at 540 ± 10 DEG C;
S4, Homogenization Treatments temperature are 380 DEG C, process time 6h;Hot extrusion or rolling processing deformation temperature are 250 DEG C, Extrusion ratio is 6: 1 or every time amount of rolling 10%.
Embodiment 4
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 1.0%, and remaining is Zn.
The preparation method of this alloy material is with embodiment 1, institute's difference:
S2, put into pure zinc after be warming up to 440 DEG C after pure zinc is completely melt, zinc melt is warming up to 620 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), after above-mentioned mixed solvent is completely covered zinc bath surface, then by zinc melt Temperature is down to 560 DEG C, now adds pure lithium under the protection of Ar gas;
S3, refining temperature are 550 ± 10 DEG C, and the amount of hexachlorethane is the 0.3% of alloy melt gross weight;After refine completes 15min is stood at 550 ± 10 DEG C;
S4, Homogenization Treatments temperature are 380 DEG C, process time 6h;Hot extrusion or rolling processing deformation temperature are 280 DEG C, Extrusion ratio is 6: 1 or every time amount of rolling 10%.
Embodiment 5
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 2.0%, and remaining is Zn.
The preparation method of this alloy material is with embodiment 1, institute's difference:
S2, put into pure zinc after be warming up to 435 DEG C after pure zinc is completely melt, zinc melt is warming up to 600 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), after above-mentioned mixed solvent is completely covered zinc bath surface, then by zinc melt Temperature is down to 560 DEG C, now adds pure lithium under the protection of Ar gas;
S3, refining temperature are 550 ± 10 DEG C, and the amount of hexachlorethane is the 0.3% of alloy melt gross weight;After refine completes 15min is stood at 550 ± 10 DEG C;
S4, Homogenization Treatments temperature are 380 DEG C, process time 6h;Hot extrusion or rolling processing deformation temperature are 280 DEG C, Extrusion ratio is 6: 1 or every time amount of rolling 10%.
Embodiment 6
A kind of degradable medical Zn-Li alloy material that the present embodiment relates to, this alloy material includes following weight percent The alloy compositions of content: Li is 3%, and remaining is Zn.
The preparation method of this alloy material is with embodiment 1, institute's difference:
S2, put into pure zinc after be warming up to 420 DEG C after pure zinc is completely melt, zinc melt is warming up to 610 DEG C, now adds LiCl and LiF mixed flux (mass ratio is 1: 3), after above-mentioned mixed solvent is completely covered zinc bath surface, then by zinc melt Temperature is down to 550 DEG C, now adds pure lithium under the protection of Ar gas;
S3, refining temperature are 540 ± 10 DEG C, and the amount of hexachlorethane is the 0.2% of alloy melt gross weight;After refine completes 13min is stood at 540 ± 10 DEG C;
S4, Homogenization Treatments temperature are 340 DEG C, process time 7h;Hot extrusion or rolling processing deformation temperature are 220 DEG C, Extrusion ratio is 15: 1 or every time amount of rolling 15%.
Embodiment 7
With the Zn-Li alloy of the crimp state that embodiment 1~6 prepares, it is simulated body fluid (Hank ' s solution) and soaks Experiment, records the corrosion rate such as table 1 of Zn-Li binary kirsite:
Table 1
Sequence number Experiment material Corrosion rate (mm/y)
1 Embodiment 1 0.12
2 Embodiment 2 0.29
3 Embodiment 3 0.21
4 Embodiment 4 0.14
5 Embodiment 5 0.16
6 Embodiment 6 0.17
The external degradation speed of Zn-Li binary kirsite is entered by the present embodiment according to ASTM-G31-72 standard method of test Having gone research, found in the simulated body fluid environment of 37 DEG C, the degradation rate of Zn-Li binary kirsite is slow, and can lead to The content overregulating Li element regulates and controls.
Embodiment 8
With the Zn-Li alloy of the compressional deformation state that embodiment 1~6 prepares, carry out tensile strength test result such as table 2 institute Show.
Table 2
Zn-Li binary kirsite embodiment 1~6, according to GB/T228.1-2010 testing standard, is drawn by the present embodiment Stretching Mechanics Performance Testing, result is as shown in table 2.Research finds, the yield strength of Zn-Li bianry alloy is up to 501MPa, disconnected Split elongation percentage and be up to 50%;Far above Zn-Fe-Li system kirsite (Zn 99.975%, Fe under equal test condition 0.01%, Li 0.015%) yield strength 290MPa, fracture elongation 36%.By rationally adding the content of Li element (0.55~10wt.%, most preferably 1.0~3wt.%), it is possible to obtain varying strength and the kirsite of plasticity, meets different medical The degradation material performance requirement to kirsite.
Embodiment 7
The Zn-Li alloy prepared with embodiment 1~6, carries out vitro cytotoxicity test.
The present embodiment has carried out cell in vitro (L-929 fibroblast) according to GB/T 16886.5-2003 to kirsite Toxotest, obtains above-mentioned kirsite catabolite and has not significant impact cytoactive, and cytotoxicity is 1 grade, demonstrates excellent Good cell compatibility.
Embodiment 8
For the Zn-Li alloy material described in above-described embodiment 1-6, conventional casting can be passed through further Zn-Li Ingot material is prepared as three-dimensional UNICOM tissue engineering bracket;By extrusion rolling drawing group technology Zn-Li deformation state material Processing filamentation material and support capillary tubes.Thus the medical embedded apparatus of degradable in vivo can be further prepared into.Described Degradable medical implantation instrument for implant support, bone implants, decorative sursery and neurocranial surgery implantation instrument, operation suture thread, Various operation sticking patch, anastomat, vascular clamp or nerve rehabilitating tube etc..Wherein implant support and include that intravascular stent, bile duct prop up Frame, trachea bracket, urethra rack, esophageal stents appear or intestinal stent;Bone implants apparatus include hone lamella, nail, internal fixation screw, Intramedullary needle or bone tissue engineering scaffold etc.;Sticking patch includes intestinal surgery operation sticking patch and Craniocerebral Surgery sticking patch;Kiss Clutch includes bowel anastomosis device, blood vessel anastomat etc..
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformation or amendment without departing from the inventive concept of the premise, This has no effect on the flesh and blood of the present invention, all should be considered as belonging to protection scope of the present invention.

Claims (10)

1. a biodegradable medical zinc lithium binary alloy material, it is characterised in that described alloy material includes following weight Each component of degree: lithium 0.55~10%, zinc 90~99.45%.
2. a preparation method for biodegradable as claimed in claim 1 medical zinc lithium binary alloy material, its feature exists In, said method comprising the steps of:
S1, weigh zinc raw material, lithium raw material according to described alloy proportion;
S2, zinc raw material, mixed flux, lithium raw material are added heat fusing, stir, form alloy melt;
S3, described alloy melt through refine, stand, pour into a mould after cool down, obtain biodegradable medical zinc lithium bianry alloy casting Ingot material.
The preparation method of biodegradable the most according to claim 2 medical zinc lithium binary alloy material, it is characterised in that After step S2 particularly as follows: be heated to 420 DEG C~440 DEG C insulation fusings by pure zinc, when melt temperature rises to 580~620 DEG C Adding mixed flux, flux to be mixed is completely covered on bath surface and melt temperature is down to 540~560 DEG C simultaneously, at Ar gas Protection under add pure lithium.
The preparation method of biodegradable the most according to claim 3 medical zinc lithium binary alloy material, it is characterised in that Described mixed flux is the mixed flux of LiCl and LiF.
The preparation method of biodegradable the most according to claim 3 medical zinc lithium binary alloy material, it is characterised in that In step s3, described refine uses hexachlorethane to carry out refine, and refining temperature is 540 ± 20 DEG C, and the amount of hexachlorethane is alloy The 0.2~0.3% of total melt weight.
The preparation method of biodegradable the most according to claim 3 medical zinc lithium binary alloy material, it is characterised in that Also include that the alloy cast ingot material obtaining step S3 carries out Homogenization Treatments, and the place that hot extrusion or rolling deformation are processed Reason.
The preparation method of biodegradable the most according to claim 6 medical zinc lithium binary alloy material, it is characterised in that Described Homogenization Treatments temperature is 320~380 DEG C, processes the time 4~10h;Described hot extrusion processing deformation temperature be 190~ 280 DEG C, extrusion ratio is 6~50: 1;The deformation temperature of described rolling deformation processing is 190~280 DEG C, and every time amount of rolling is 10 ~30%;Biodegradable medical zinc lithium bianry alloy plasticity shape is obtained after water-cooled or air cooling after described hot extrusion or rolling deformation Become processing state material.
8. according to the preparation method of the biodegradable medical zinc lithium binary alloy material according to any one of claim 2~7, It is characterized in that, after step S3, may also include, by casting technique, alloy cast ingot material is further prepared into three-dimensional UNICOM group Weaver's engineering support, by extrusion rolling drawing group technology alloy deformation state materials processing filamentation material and support capillary tube The step of material.
9. a biodegradable as claimed in claim 1 medical zinc lithium binary alloy material is preparing degradable medical implantation Purposes in apparatus.
Purposes the most according to claim 9, it is characterised in that: described degradable medical implantation instrument is for implanting support, bone Implants, decorative sursery and neurocranial surgery implantation instrument, operation suture thread, various operation sticking patch, anastomat, vascular clamp or god Repaired conduit;Described implantation support includes intravascular stent, biliary tract prosthesis, trachea bracket, urethra rack, esophageal stents appear or intestinal Support;Described bone implants includes hone lamella, nail, internal fixation screw, intramedullary needle or bone tissue engineering scaffold.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108396176A (en) * 2018-01-24 2018-08-14 烟台南山学院 A kind of medical degradable zinc alloy flakes of Guided Bone Regeneration and preparation method thereof
CN110512117A (en) * 2019-09-27 2019-11-29 石家庄新日锌业有限公司 Medical zinc alloy material and preparation method thereof
CN110585475A (en) * 2019-09-18 2019-12-20 西南大学 Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof
CN110878395A (en) * 2019-12-11 2020-03-13 浙江工贸职业技术学院 High-plasticity biodegradable Zn-2Li alloy under high-pressure action of GPa grade and preparation method thereof
CN113005330A (en) * 2021-03-17 2021-06-22 昆明理工大学 Biodegradable superfine crystal Zn-Li alloy material and preparation method and application thereof
CN113637861A (en) * 2021-08-13 2021-11-12 湘潭大学 Zn-Se alloy and preparation method and application thereof
CN113633831A (en) * 2021-08-25 2021-11-12 天津理工大学 Porous zinc alloy bone tissue engineering scaffold coated with bioactive coating and preparation method thereof
CN114075634A (en) * 2020-08-18 2022-02-22 上海交通大学 Medical degradable Zn-Cu-Li ternary alloy and preparation and application thereof
CN116036076A (en) * 2022-12-13 2023-05-02 安域生物科技(杭州)有限公司 Application of lithium amino acid in preparation of medicine for treating manic mental diseases

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101748313A (en) * 2008-12-19 2010-06-23 北京有色金属与稀土应用研究所 Zinc-lithium alloy material and preparation method thereof
CN104195368A (en) * 2014-08-21 2014-12-10 北京大学 Zn-Sr series zinc alloy as well as preparation method and application of Zn-Sr series zinc alloy
CN107460371A (en) * 2016-06-02 2017-12-12 北京大学 A kind of Zn-Li systems kirsite and preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101748313A (en) * 2008-12-19 2010-06-23 北京有色金属与稀土应用研究所 Zinc-lithium alloy material and preparation method thereof
CN104195368A (en) * 2014-08-21 2014-12-10 北京大学 Zn-Sr series zinc alloy as well as preparation method and application of Zn-Sr series zinc alloy
CN107460371A (en) * 2016-06-02 2017-12-12 北京大学 A kind of Zn-Li systems kirsite and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARCELA TRYBULA等: "Bulk and Surface Properties of Liquid Al-Li and Li-Zn Alloys", 《METALLURGICAL AND MATERIALS TRANSACTIONS A》 *

Cited By (11)

* Cited by examiner, † Cited by third party
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CN108396176A (en) * 2018-01-24 2018-08-14 烟台南山学院 A kind of medical degradable zinc alloy flakes of Guided Bone Regeneration and preparation method thereof
CN110585475A (en) * 2019-09-18 2019-12-20 西南大学 Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof
CN110512117A (en) * 2019-09-27 2019-11-29 石家庄新日锌业有限公司 Medical zinc alloy material and preparation method thereof
CN110512117B (en) * 2019-09-27 2022-05-13 石家庄新日锌业有限公司 Medical zinc alloy material and preparation method thereof
CN110878395A (en) * 2019-12-11 2020-03-13 浙江工贸职业技术学院 High-plasticity biodegradable Zn-2Li alloy under high-pressure action of GPa grade and preparation method thereof
CN114075634A (en) * 2020-08-18 2022-02-22 上海交通大学 Medical degradable Zn-Cu-Li ternary alloy and preparation and application thereof
CN114075634B (en) * 2020-08-18 2022-08-12 上海交通大学 Medical degradable Zn-Cu-Li ternary alloy and preparation and application thereof
CN113005330A (en) * 2021-03-17 2021-06-22 昆明理工大学 Biodegradable superfine crystal Zn-Li alloy material and preparation method and application thereof
CN113637861A (en) * 2021-08-13 2021-11-12 湘潭大学 Zn-Se alloy and preparation method and application thereof
CN113633831A (en) * 2021-08-25 2021-11-12 天津理工大学 Porous zinc alloy bone tissue engineering scaffold coated with bioactive coating and preparation method thereof
CN116036076A (en) * 2022-12-13 2023-05-02 安域生物科技(杭州)有限公司 Application of lithium amino acid in preparation of medicine for treating manic mental diseases

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