CN106702212A - Medical degradable Zn-Cu-X alloy material and preparation method thereof - Google Patents
Medical degradable Zn-Cu-X alloy material and preparation method thereof Download PDFInfo
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- CN106702212A CN106702212A CN201510785360.1A CN201510785360A CN106702212A CN 106702212 A CN106702212 A CN 106702212A CN 201510785360 A CN201510785360 A CN 201510785360A CN 106702212 A CN106702212 A CN 106702212A
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/02—Alloys based on zinc with copper as the next major constituent
Abstract
The invention discloses a medical degradable Zn-Cu-X alloy material and a preparation method thereof. The alloy material includes the following components in percentage by weight: 1-10% of Cu, 0-4% of X and the balance Zn, wherein the element X is one of Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho and Dy or is a mixture of more of Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho and Dy. The invention further relates to the preparation method of the alloy material. The alloy material provided by the invention is a multi-element degradable Zn-based alloy material composed of the human nutrient elements Zn, Cu and X, which completely have biosecurity, has favorable biocompatibility, excellent mechanical properties and an adjustable and controllable corrosion rate, and has a favorable application prospect in the field of medical degradable inner implantation material.
Description
Technical field
The present invention relates to a kind of Zn base alloy materials of the biomedical materials field that can be degraded completely in organism,
It particularly relates to be Zn-Cu-X alloy materials of a kind of medical degradable and preparation method thereof.
Background technology
At present, the medical material in operation implantation human body is generally adopted by nondegradable metal material, such as austenite
Stainless steel, cochrome, Medical tantalum, titanium and its alloy, niti-shaped memorial alloy, platinumiridio.These are permanent
The drawbacks of application for being implanted into material clinically has certain.Therefore, biological degradable in vivo absorbing material becomes biology
One important directions of Materials, the biological degradable in vivo absorbing material of current clinical practice be mainly polymer and certain
A little ceramic materials, such as PLA, calcium phosphate.But due to polymeric material low strength, ceramic material plasticity compared with
Differ from and limit its extensive use clinically.
In recent years, degradable metal base biomaterial for medical purpose receives the special attention of people, and this kind of new Metal Substrate can
The proposition of degraded biomaterial for medical purpose changes the traditional concept that people are implanted into material for Metal Substrate, i.e., using bioactivity
Material is used as metal implant material.At present, degradable metal base biomaterial mainly has three major types：Iron-based, magnesium-based and zinc
Based alloy, dexterously using these alloys, the easily characteristic corroded realizes metal implanting device in human body environment for they
Part is gradually degraded in vivo until the final clinical medicine purpose for disappearing.Simultaneously as they are metal_based material, relatively
For polymer and some ceramic materials, its intensity, plasticity, rigidity, processing characteristics are much better than and have started clinic
The degradable high polymer materials such as medical PLA, thus the clinic being more suitable in terms of orthopaedics and cardiovascular intervention support should
With.
In three foregoing metalloid base biomaterials, iron-based biomaterial degradation rate is slow；And magnesium-based biomaterial
Corrosion degradation speed is again relatively fast, therefore for magnesium-based biomaterial generally requires to carry out surface modification treatment to reduce it
Degradation speed；The degraded corrosion rate of zinc-base biomaterial is occupy between above-mentioned two classes biomaterial, and its corrosion rate is most held
The need for easily meeting clinic.In addition zinc is one of necessary trace element of human body, and the Zn content in adult body is 1.4~2.3g,
The allowance,dietary of the daily zinc of health adult is 15~40mg, therefore zinc has good biocompatibility.However, pure zinc
Mechanical property it is poor, intensity and plasticity can not all meet the requirement of implantation.
The content of the invention
For defect of the prior art, it is an object of the invention to provide a kind of degradable kirsite of medical bio and its system
Preparation Method.The alloying element for selecting harmless or toxic minimum carries out Alloying Treatment to pure zinc, then pairing
Kirsite after aurification is heat-treated and is plastically deformed processing, and the degradable kirsite that acquisition meets clinical needs is medical
Biomaterial.
The purpose of the present invention is to be achieved through the following technical solutions：
The invention provides a kind of medical degradable Zn-Cu-X alloy materials, the alloy material includes following weight percent
The each element of ratio：1≤Cu≤10%, 0 ＜ X≤4%, balance of zinc；The element X be Mg, Ca, Sr, Si, Fe,
One or more in Mn, Ag, Y, Nd, Gd, Er, Ho or Dy of mixing.
Preferably, the X is Mg, Fe, Ag, Nd, Gd.
In the Zn-Cu-X alloy materials, Cu too high levels can cause the comprehensive mechanical property of alloy material to decline, while
The corrosion degradation speed of alloy is increased considerably；Cu contents it is too low can when (Cu contents be less than 1% when) alloy elongation percentage
It is relatively low to cause alloy processing difficulties during medical implantation instrument is prepared into, and alloy content is too low so that alloy antibacterial
DeGrain.
Present invention also offers a kind of preparation method of medical degradable Zn-Cu-X alloy materials, comprise the following steps：
Step S1：Alloying element proportioning according to claim 1 weighs each raw material；
Step S2：Successively by pure zinc, raw material containing Cu, the heating fusing of raw material containing X, stir, form alloy melt；
Step S3：Alloy melt obtains medical degradable Zn-Cu-X alloy materials by cooling after refining, standing, casting.
Preferably, in step S2, the raw material containing Cu is pure Cu or Cu-Zn intermediate alloys；The raw material containing X is
One or more in pure X, Zn-X intermediate alloy or Cu-X intermediate alloys.
It is highly preferred that the raw material containing Cu is Cu-Zn intermediate alloys；The raw material containing X is Zn-X intermediate alloys.
Preferably, it is described to be successively specially pure zinc, raw material containing Cu, the heating fusing of raw material containing X in step S2：First
Pure zinc is added and is melted, add raw material containing Cu, Cu raw materials to be contained to melt completely when melt temperature rises to 530~550 DEG C
After change, raw material containing X is added.
It is highly preferred that it is described after raw material containing Cu is completely melt, raw material containing X is added at 480~510 DEG C.
Preferably, in the step S3, refined using carbon trichloride, refining temperature is 500 ± 20 DEG C.
Preferably, the amount of the carbon trichloride is the 0.2~0.3% of alloy melt gross weight.
Preferably, in step S3, the dwell temperature is 500 ± 20 DEG C, 10~15min of time of repose.
Preferably, also become including carrying out Homogenization Treatments and hot extrusion or rolling to the alloy material that step S3 is obtained
The treatment of shape.
Preferably, the Homogenization Treatments temperature is 350~380 DEG C, 6~10h of process time；The extrusion temperature
It it is 300~320 DEG C, extrusion ratio is 9~30:1.
The present invention significantly improves alloy by adding a certain amount of Cu elements with antibacterial effect in matrix Zn
Alloy can also be made while mechanical property has the biological effectiveness such as antibacterial under environment in vivo；Add simultaneously another
Constituent element X, has the biological effectiveness such as the reparation of promotion bio-tissue, anti-inflammatory or regulation and control alloy structure and regulates and controls using it
The effects such as alloy mechanical property, corrosion degradation performance, so as to further improve mechanical property, the corruption of Zn-Cu based alloys
Erosion degradation property and biology performance.
The present invention is a kind of by polynary being dropped by what the human nutrition element Zn of biological safety, Cu, X element were constituted completely
Solution Zn base alloy materials, with good biocompatibility, excellent mechanical property and regulatable corrosion rate,
Medical degradable inner implantation material field has important application potential, has a good application prospect.
Compared with prior art, the invention has the advantages that：
1st, from zinc-containing alloy as degradable medical metal material.It is well known that zinc is human body necessity the most basic
Trace element.Wherein, zinc can promote the renewal of cell, can strengthen the immunocompetence of human body, maintain growth and the hair of human body
Educate.Zinc is the composition of many protein, nucleic acid synthesizing enzyme, is the activated centre of hundreds of enzyme.Zinc is again insulin component,
It is the key factor of normal activity of sustaining life.Therefore, zinc-containing alloy has good biocompatibility.While kirsite
Corrosion degradation speed between ferrous alloy and magnesium base alloy, its corrosion rate is most suitable for clinical practice.
2nd, from copper alloy as main alloy element.Copper accounts for hundred a ten thousandths of body weight, everyone containing about
100~150mg.Adult must take in 3~5mg copper, the balance of ability maintenance metabolism daily.The physiological function of copper is main
Have following aspects：1) normal hematopoietic function is safeguarded, following two aspect is shown：1. absorption and the fortune of iron are promoted
It is defeated；2. CER can promote the synthesis of ferroheme and hemoglobin.2) the normal of bone, blood vessel and skin is safeguarded.
Cuprase lysyloxidase promotes the crosslinking of bone, blood vessel and skin collagen and elastin laminin.3) central nervous system is safeguarded
The health of system.4) body cell is protected from the murder by poisoning of superoxide ion.5) copper ion can inducing endothelial growth factor,
Promote the propagation of endothelial cell, accelerate revascularization process, but prevent the hyper-proliferative of smooth muscle cell；And blood can be suppressed
The effects such as bolt is formed, can effectively reduce the restenosis rate (bibliography triggered after the implantation such as intravascular stent：G.f.Hu.
Copper stimulates proliferation of human endothelial cells under culture[J].
Journal of Cellular Biochemistry.1998,69(3):326-335.).6) copper ion can be by promoting
Enter the deposition of ossein and promote the formation of bone tissue and grow, i.e., with promotion osteogenic action (bibliography：C.
G é rard, L.-J.Bordeleau, J.Barralet, C.J.Doillon.The stimulation of
angiogenesis and collagen deposition by copper[J].Biomaterials.
2010,31(5):824-831.).7) copper ion has bactericidal effect, and this has important value for implantation instrument, can
To avoid device from causing infection after being implanted into, so as to mitigate the pain and trouble of patient.8) other：Copper is to cholesterol generation
Thank, many physiology, biochemistry and the pathophysiological process such as cardiac muscle cell's oxidative metabolism, human body defensive enginery, hormone secretion
Have an impact.Therefore, selection copper for zinc-containing alloy main addition alloy element, on the one hand increase zinc intensity and
Plasticity plays a part of Toughened Materials, and during degraded, the release of micro copper ion is right to another aspect material
There is human body above-mentioned beneficial biological function to act on.
After 3rd, kirsite of the invention adds beneficial alloying constituent element X (X is Mg, Ca, Sr, Si, Fe, Mn,
One or more in Ag, Y, Nd, Gd, Er, Ho and Dy of mixing), can be by the regulation and control of its content come further
The tissue of optimized alloy, so as to improve the mechanical property and bio-compatible performance of alloy, it is possible to the corruption of appropriate regulation alloy
Erosion degradation rate.Obtainable tensile strength is 230~500MPa, and yield strength is 180MPa~430MPa, and elongation percentage is
3~55% sheet material, bar or wire rod etc., and corrosion degradation speed is in the range of 0.02~1.0mm/year.
4th, because this alloy belongs to deformation zinc alloy, plasticity is better than magnesium-based biomaterial, therefore is highly convenient for being processed into plant
Enter device, particularly can easily be processed into cardio-vascular interventional therapeutic support product.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to those skilled in the art
Member further understands the present invention, but the invention is not limited in any way.It should be pointed out that to the common skill of this area
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These are belonged to
Protection scope of the present invention.
Embodiment 1
The present embodiment designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 3%, Mg is 0.5%, and remaining is Zn.
The present embodiment further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, add H62 brass
(Cu-38wt.%Zn intermediate alloys), after H62 is completely melt, pure Mg (purity is more than 99.99%) is added at 500 DEG C,
Then alloy melt is slightly agitated for and is refined using carbon trichloride, and poured into a mould after 10~15min of standing.
After temperature is reduced to below 200 DEG C, die sinking, taking-up sample is gone forward side by side, and water-filling is cold to obtain ingot casting blank.Blank is carried out 350 DEG C
After 8 hour Homogenization Treatments, turnery processing then carries out extrusion ratio 9 into the cylindrical ingot of diameter 60mm at 280 DEG C:1
Extruding and water-cooled, obtain Zn-Cu-Mg alloy bar materials.
Implementation result：Alloy yield strength is 425MPa, and fracture strength is 430MPa, elongation percentage about 3%, at 37 DEG C
Corrosion degradation speed in simulated body fluid hanks ' is 0.03mm/year.The alloy has intensity high and than relatively low
Elongation percentage, and Mg the and Cu elements for containing have the effect for promoting bone propagation, healing, suitable making can in the orthopaedics of part
Degraded implantation instrument.
Embodiment 2
The present embodiment designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 6%, Gd is 0.1%, and remaining is Zn.
The present embodiment further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, add H62 brass
(Cu-38wt.%Zn intermediate alloys), after H62 is completely melt, adds Zn-30%Gd intermediate alloys, treats in the middle of this
After alloy is completely melt, then alloy melt is slightly agitated for and is refined using carbon trichloride, and stood
Poured into a mould after 10~15min.After temperature is reduced to below 200 DEG C, die sinking, taking-up sample is gone forward side by side, and water-filling is cold to be cast
Ingot blank.After blank is carried out into 360 DEG C of 8 hour Homogenization Treatments, turnery processing into diameter 60mm cylindrical ingot,
Again extrusion ratio 20 is carried out at 300 DEG C:1 extruding and water-cooled, obtain Zn-Cu-Gd alloy bar materials.
Implementation result：Alloy yield strength is 290MPa, and fracture strength is 320MPa, elongation percentage about 45%, at 37 DEG C
Simulated body fluid hanks ' in corrosion degradation speed be 0.3mm/year, the alloy is due to excellent plasticity and ratio
Preferable intensity, is conveniently processed into the degradable implantation instrument of different size and shape need.
Embodiment 3
The present embodiment designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 2%, Mg is that 0.6%, Gd is 0.03%, and remaining is Zn.
The present embodiment further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, sequentially add H62
Brass (Cu-38wt.%Zn intermediate alloys) and Zn-30%Gd intermediate alloys, treat that both foregoing intermediate alloys are all complete
After fusing, pure Mg (purity is more than 99.99%) is added at 500 DEG C, then alloy melt is slightly agitated for and is used
Carbon trichloride is refined, and is poured into a mould after 10~15min of standing.After temperature is reduced to below 200 DEG C, die sinking,
Taking-up sample is gone forward side by side, and water-filling is cold to obtain ingot casting blank.After blank is carried out into 370 DEG C of 8 hour Homogenization Treatments, turning adds
Work then carries out extrusion ratio 9 into the cylindrical ingot of diameter 60mm at 300 DEG C:1 extruding and water-cooled, obtain Zn-Cu-Mg-Gd
Alloy bar material.
Implementation result：Alloy yield strength is 390MPa, and fracture strength is 410MPa, elongation percentage about 23%, at 37 DEG C
Simulated body fluid hanks ' in corrosion degradation speed there is medium plasticity and relatively good for the 0.08mm/year. alloys
Intensity level, it is adaptable to prepare some for plasticity and intensity all have necessarily required medical implantation instrument product.
Embodiment 4
The present embodiment designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 2%, Ag is 0.1%, and remaining is Zn.
The present embodiment further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, sequentially add H62
Brass (Cu-38wt.%Zn intermediate alloys), after the intermediate alloy is all completely melt, then adds Zn-40 at 500 DEG C
Wt.%Ag (impurity content is less than 0.01%), is slightly agitated for, and use chlordene after it is completely melt to alloy melt
Ethane is poured into a mould after standing 10~15min after being refined.After temperature is reduced to below 200 DEG C, examination is taken out in die sinking
Sample is gone forward side by side, and water-filling is cold to obtain ingot casting blank.After blank is carried out into 370 DEG C of 8 hour Homogenization Treatments, turnery processing Cheng Zhi
The cylindrical ingot of footpath 60mm, then carry out extrusion ratio 9 at 310 DEG C:1 extruding and water-cooled, obtain Zn-Cu-Ag alloy bars
Material.
Implementation result：Alloy yield strength is 360MPa, and fracture strength is 395MPa, elongation percentage about 17%, at 37 DEG C
Simulated body fluid hanks ' in corrosion degradation speed be 0.6mm/year.The alloy is with intensity higher and preferably
Elongation percentage, and because Ag the and Cu elements for containing have good antibacterial effect, be adapted to make partial agonistic bacterium performance requirement
Compare the special degradable implantation instrument of some high.
Comparative example 1
This comparative example designs a kind of Zn-X alloy materials, and the alloy material includes the alloy compositions of following weight percentage：
Mg is 1%, and remaining is Zn.
This comparative example further relates to the preparation method of foregoing degradable medical Zn-X alloy materials, and preparation method includes following step
Suddenly：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle that pure Zn (purity is more than 99.994%) heating fusing is added into pure Mg (purity is more than 99.99%) at 500 DEG C, with
Alloy melt is slightly agitated for and is refined afterwards and using carbon trichloride, and poured into a mould after 10~15min of standing.
After temperature is reduced to below 200 DEG C, die sinking, taking-up sample is gone forward side by side, and water-filling is cold to obtain ingot casting blank.Blank is carried out 350 DEG C
After 8 hour Homogenization Treatments, turnery processing then carries out extrusion ratio 9 into the cylindrical ingot of diameter 60mm at 280 DEG C:1
Extruding and water-cooled, obtain Zn-Mg alloy bar materials.
Implementation result：Alloy yield strength is 387MPa, and fracture strength is 402MPa, elongation percentage about 2%, at 37 DEG C
Corrosion degradation speed in simulated body fluid hanks ' is 0.13mm/year.The alloy has intensity high and low-down
Elongation percentage causes alloy material to be not easy to plastic working into required product, and does not contain Cu elements so that material antibacterial is imitated
Fruit is not obvious.Zn-1%Mg alloys synthesis performance is poorer than Zn-4%Cu-1%Mg, particularly the plasticity and its antibacterial of material
Performance causes implementation result undesirable.
Comparative example 2
This comparative example designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 4%, Mg is 5%, and remaining is Zn.
This comparative example further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, add H62 brass
(Cu-38wt.%Zn intermediate alloys), after H62 is completely melt, then adds pure Mg (purity is more than 99.99%) at 500 DEG C,
Then alloy melt is slightly agitated for and is refined using carbon trichloride, and poured into a mould after 10~15min of standing.
After temperature is reduced to below 200 DEG C, die sinking, taking-up sample is gone forward side by side, and water-filling is cold to obtain ingot casting blank.Blank is carried out 350 DEG C
After 8 hour Homogenization Treatments, turnery processing then carries out extrusion ratio 9 into the cylindrical ingot of diameter 60mm at 280 DEG C:1
Extruding and water-cooled, obtain Zn-Cu-Mg alloy bar materials.
Implementation result：Alloy yield strength is 460MPa, and fracture strength is 480MPa, elongation percentage about 1%, at 37 DEG C
Corrosion degradation speed in simulated body fluid hanks ' is 0.73mm/year.The alloy has intensity very high and very low
Elongation percentage, it is difficult to the medicine equipment implantation needed for being processed into and easily produces brittle fracture at product, and implementation result is undesirable.
Comparative example 3
This comparative example designs a kind of degradable medical Zn-Cu-X alloy materials, and the alloy material contains including following weight percent
The alloy compositions of amount：Cu is that 15%, Gd is 0.1%, and remaining is Zn.
This comparative example further relates to the preparation method of foregoing degradable medical Zn-Cu-X alloy materials, and preparation method includes as follows
Step：
The scaling loss for disregarding alloying element in fusion process carries out alloy raw material proportioning, by the way of resistance melting, in crucible
It is middle to melt pure Zn (purity is more than 99.994%) heating, when melt temperature rises to 550 DEG C, add H62 brass
(Cu-38wt.%Zn intermediate alloys), after H62 is completely melt, adds Zn-30%Gd intermediate alloys, treats in the middle of this
After alloy is completely melt, then alloy melt is slightly agitated for and is refined using carbon trichloride, and stood
Poured into a mould after 10~15min.After temperature is reduced to below 200 DEG C, die sinking, taking-up sample is gone forward side by side, and water-filling is cold to be cast
Ingot blank.After blank is carried out into 360 DEG C of 8 hour Homogenization Treatments, turnery processing into diameter 60mm cylindrical ingot,
Again extrusion ratio 20 is carried out at 300 DEG C:1 extruding and water-cooled, obtain Zn-Cu-Gd alloy bar materials.
Implementation result：Alloy yield strength is 260MPa, and fracture strength is 310MPa, elongation percentage about 28%, at 37 DEG C
Simulated body fluid hanks ' in corrosion degradation speed be 0.27mm/year, although the alloy still have excellent modeling
Property and relatively good intensity, but the alloy is for Zn-6Cu-0.1Gd (wt.%) alloy in embodiment 2,
The mechanical property of material has declined, simultaneously because the substantial amounts of addition of Cu, its cost of alloy also increases, compares
Under, implementation result shows as that cost is higher but the performance of material that obtain has declined.Therefore, major alloy unit
The content of plain Cu should preferably last 1≤Cu≤10%.
Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in upper
Particular implementation is stated, those skilled in the art can within the scope of the claims make various deformations or amendments,
This has no effect on substance of the invention.
Claims (9)
1. a kind of medical degradable Zn-Cu-X alloy materials, it is characterised in that the alloy material includes following weight
The each element of percentage：1≤Cu≤10%, 0 ＜ X≤4%, balance of zinc；The element X be Mg, Ca, Sr, Si,
One or more in Fe, Mn, Ag, Y, Nd, Gd, Er, Ho or Dy of mixing.
2. a kind of preparation method of medical degradable Zn-Cu-X alloy materials according to claim 1, its feature
It is to comprise the following steps：
Step S1：Alloy proportion according to claim 1 weighs each raw material；
Step S2：Successively by pure zinc, raw material containing Cu, the heating fusing of raw material containing X, stir, form alloy melt；
Step S3：Alloy melt obtains medical degradable Zn-Cu-X alloy materials by cooling after refining, standing, casting.
3. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 2, it is characterised in that
In step S2, the raw material containing Cu is pure Cu or Cu-Zn intermediate alloys；The raw material containing X is in pure X, Zn-X
Between one or more in alloy or Cu-X intermediate alloys.
4. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 2, it is characterised in that
It is described to be successively specially pure zinc, raw material containing Cu, the heating fusing of raw material containing X in step S2：It is first that the heating of pure zinc is molten
Change, raw material containing Cu is added when melt temperature rises to 530~550 DEG C, after raw material containing Cu is completely melt, add
Raw material containing X.
5. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 2, it is characterised in that
In the step S3, refined using carbon trichloride, refining temperature is 500 ± 20 DEG C.
6. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 5, it is characterised in that
The amount of the carbon trichloride is the 0.2~0.3% of alloy melt gross weight.
7. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 2, it is characterised in that
In step S3, the dwell temperature is 500 ± 20 DEG C, 10~15min of time of repose.
8. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 2, it is characterised in that
Also include that the alloy material obtained to step S3 carries out Homogenization Treatments and hot extrusion or the treatment of rolling deformation.
9. the preparation method of medical degradable Zn-Cu-X alloy materials according to claim 8, it is characterised in that
The Homogenization Treatments temperature is 350~380 DEG C, 6~10h of process time；The extrusion temperature is 250~350 DEG C,
Extrusion ratio is 6~50:1.
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| PCT/CN2016/089733 WO2017084363A1 (en) | 2015-11-16 | 2016-07-12 | Medical degradable zn-cu-x alloy material and preparation method thereof |
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| CN115927913B (en) * | 2022-12-16 | 2024-04-26 | 中国矿业大学 | Containing Mg2Zn11Zn-Mg-Cu alloy with Zn trilobal eutectic structure |
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