CN108642359A - A kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity and preparation method thereof - Google Patents

A kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity and preparation method thereof Download PDF

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CN108642359A
CN108642359A CN201810879128.8A CN201810879128A CN108642359A CN 108642359 A CN108642359 A CN 108642359A CN 201810879128 A CN201810879128 A CN 201810879128A CN 108642359 A CN108642359 A CN 108642359A
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alloy
medical
high intensity
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ingot
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CN108642359B (en
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刘运腾
林涛
周吉学
唐守秋
刘洪涛
马百常
庄海华
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New Material Institute of Shandong Academy of Sciences
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • 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
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • 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
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a kind of high intensity degradable biological medical Mg Zn Zr Fe alloy materials and preparation method thereof.The mass percent of the magnesium alloy each component is:Zn5.0~6.0%, Zr0.5~1.0%, Fe0.01~0.09%, remaining is Mg and its inevitable impurity.Specific preparation method includes melting, casting Homogenization Treatments, hot extrusion and artificial aging processing, obtains meeting biological medical magnesium alloy plate, stick, wire rod under biological fluid environment is on active service.The present invention is added to harmless alloying element in the magnesium alloy, and to human body without any toxicity after alloy degradation in vivo, excellent in mechanical performance has good mechanical property and processing performance, has with corrosion rate appropriate.The high intensity degradable biological medical Mg Zn Zr Fe alloy materials of the present invention, tensile strength >=360MPa, yield strength >=320MPa, suitable for preparing the medical materials such as nail.

Description

A kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity and its Preparation method
Technical field
The invention belongs to biomedical complex magnesium alloy field, more particularly to a kind of organism absorbable Mg-Zn- Zr-Fe complex magnesium alloy materials.
Background technology
Currently, it includes mainly stainless steel, cochrome, titanium alloy that it is metal material embedded, which to be widely used in clinical biology,. The equal non-degradable of these metal materials, implantation material must be taken out after tissue functional rehabilitation by second operation.Cause This, degradable metal material future has preferable development prospect in biomedical materials field.What is be currently in development can Degradation metal material has:Magnesium alloy, ferroalloy and kirsite.Magnesium alloy is because with good biocompatibility, mechanical compatibility The advantages that, it is increasingly becoming the research hotspot of biomedical materials field in recent years.The advantages of magnesium, is embodied in:(1) it is people A kind of mineral matter element necessary to body, can also be discharged when excessive by urine, because without causing toxic reaction;(2) Young Modulus is close with people's bone, and stress-shielding effect can be effectively relieved in the application of correlation implantation material.
In recent years, researcher develops a series of degradable magnesium alloys, such as patent of invention《Organism absorbable Mg- Zn-Fe ternary magnesium alloy materials》(the patent No.:200510111793.5), patent of invention《Organism absorbable Mg-Zn- Ca-Fe complex magnesium alloy materials》(the patent No.:200510111792.0), patent of invention《Bio-medical Mg-Zn-Zr-Mn magnesium closes Gold and preparation method thereof》(application number:201510870718.0), patent of invention《Biological medical degradable Mg-Zn-Zr-Sc alloys And preparation method thereof》(application number:201410101431.7), patent of invention《Biomedical degradable corrosion-resistant Mg-Zn-Zr is closed Gold and preparation method》(application number:201310275808.6).Above-mentioned patent by Mg-Zn systems alloys add Mn, Sc, Fe, The elements such as Ca, Zr crystal grain thinning and the corrosion resistance for improving alloy.However, above-mentioned strength of alloy generally in 300MPa hereinafter, And it is only used for making the longer medical instrument of Implantation Time.It cannot be satisfied convalescence shorter injury gained in sports treatment and rehabilitation Demand, this requires material not only to meet good biocompatibility, while also to have faster degradation rate and higher Tensile strength and yield strength.
Industrially, due to higher intensity, ZK60 systems magnesium alloy (Mg- (5.5~6.0) Zn- (0.3~0.9) Zr, Wt% application) is relatively broad.But some researches show that excessively high Zn (more than 8%) content can cause dredging for Mg alloy surface film It loosens and falls, reduce the corrosion resistance of magnesium alloy;And the elongation percentage of magnesium alloy can also be reduced with the increase of Zn contents.Therefore, it moulds The ZK60 alloys that property is relatively low, corrosion resistance is poor, are restricted in the application of biomedical sector.
On the other hand, it is that corrosion rate is too fast that magnesium alloy biomaterials application, which is existing main problem, especially impurity Content is to influence one of the most important factor of corrosion stability of magnesium alloy, especially harmful element, such as the content of Fe, Ni, Cu and Co, is needed The content of these harmful elements (the molten limit of highest of 3 kinds of elements of Fe, Cu and Ni in Mg below tolerable limit in control alloy Amount is respectively 170 × 10-6, 1000 × 10-6, 5 × 10-6) to effectively improve the corrosion resisting property of alloy.
Invention content
Insufficient existing for existing biological medical magnesium alloy in order to overcome, the present invention provides one kind and can be applied to organism plant Enter the fast degradation Mg-Zn-Zr-Fe alloys and preparation method thereof of the high intensity of material.The strength of alloy and yield strength It is higher, and there is good biocompatibility and fast degradation performance, it can be used as injury gained in sports treatment and rehabilitation interposers Tool.
To achieve the goals above, the present invention adopts the following technical scheme that:
There is provided a kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity for an object of the present invention Material, is made of the element of following weight percent:Zn 5.0~6.0%, Zr 0.5~1.0%, Fe 0.01~0.09%, Al < 0.01%, Ni < 0.005%, Cu < 0.005%.Remaining is Mg and its inevitable impurity.
The application research is found:In Mg-Zn-Zr alloys, the Fe of 0.01-0.09% is added, since Fe and Mg will not shape At interphase, Fe and Zr plays the role of equiax crystal simultaneously in casting process, therefore, can refine crystallite dimension, change It has been apt to microstructure segregation, has improved the corrosion resistance of magnesium alloy.But since the increase of Fe contents can have an adverse effect to the corrosion of Mg, it is This, the application improves the content of zinc in magnesium alloy, finds:When Zn contents are 5.0~6.0%, it can both be effectively improved improvement The performance of skin covering of the surface, and the safe level of objectionable impurities Fe, Ni, Cu in the alloy can be improved, the influence that Fe corrodes Mg is reduced, To obtain with excellent tensile strength, yield strength and suitable degradation speed magnesium alloy.
In some embodiments, tensile strength >=360MPa of the alloy material, yield strength >=320MPa, elongation percentage >=14%;In 37 DEG C of Hank ' s simulated body fluids, corrosion rate≤0.28mgcm-2·day-1
In some embodiments, impurity element mass percent is:Al < 0.01%, Ni < 0.005%, Cu < 0.005%.
The present invention also provides a kind of preparation sides of the fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity Method, including:
Magnesium ingot, zinc ingot metal, iron, Mg-30%Zr intermediate alloys are subjected to melting, pour into ingot casting;
Above-mentioned ingot casting is subjected to Homogenization Treatments, and is squeezed into plate, stick or wire rod;
By plate, stick, the wire rod after extruding carry out artificial aging processing, it is air-cooled to get.
In some embodiments, described " melting pours into ingot casting " the specific steps are:By magnesium ingot, zinc ingot metal, iron, Mg- 30%Zr intermediate alloys keep the temperature 40~60min at 780~800 DEG C, and 5~10min is stirred after above-mentioned raw materials all melt, is then dropped Temperature is warming up to 750~780 DEG C of 30~40min of standing, is poured at 710-730 DEG C to 730~750 DEG C of 20~30min of refining after refining Form ingot casting.
In some embodiments, the condition of the Homogenization Treatments is that Homogenization Treatments are carried out at 400~420 DEG C, is protected Warm time 16-18h, then in 50~60 DEG C of water coolings.
Mg-30%Zr intermediate alloys in the application can refer to paper《Rare metal and hard alloy》,2006,34(1): Prepared by the method for 30-32 (Liu Jiaxiang, Yang Qingshan, Liu Shuping, Chen Weiping, He Bining), or use commercial product.
In some embodiments, the actual conditions of the extruding are:250~300 DEG C of temperature of extruding, extrusion speed 0.1~ 5mm/s。
In some embodiments, the condition of the artificial aging processing is to keep the temperature 24~36h at 150~160 DEG C, empty It is cold.
The present invention also provides the fast degradation bio-medical Mg-Zn-Zr-Fe of high intensity prepared by any above-mentioned method Alloy material.
The present invention also provides any above-mentioned Mg-Zn-Zr-Fe alloy materials to prepare for injury gained in sports treatment and health Application in multiple tissue engineering bracket material.
Beneficial effects of the present invention
(1) Mg-Zn-Zr-Fe alloys of the present invention select Mg, Zn, Zr, Fe with good biocompatibility, close The degradation of gold will not generate harm to organism.
(2) Mg-Zn-Zr-Fe alloys of the present invention and preparation method thereof pass through the addition of appropriate Fe elements, refinement Tissue, improves component segregation, thus improves intensity so that material has excellent tensile strength, yield strength and drop Solve speed.This is particularly suitable for the preparation of the implantation instrument of convalescence shorter injury gained in sports treatment and rehabilitation;
On the other hand, the application is also additionally added the Zn of 5-6%, while improving the performance of skin covering of the surface, improves Fe and is closing Safe level in gold.
(3) preparation method of Mg-Zn-Zr-Fe alloys of the present invention big rule at low cost, simple for process, easy to implement Mold technique produces.
(4) crystallite dimension of the application squeeze wood is less than 10 μm, and crystallite dimension is small, and microstructure segregation is small, mechanics and corrosion resistance It can be excellent.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is Mg-Zn-Zr-Fe extruded bars alloy microscopic structures.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
The present invention relates to a kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloys of high intensity, the quality of alloying element Percentage is:Zn5.0~6.0%, Zr0.5~1.0%, Fe0.01~0.09%, remaining is Mg and its inevitable impurity.
In Mg-Zn-Zr-Fe alloys of the present invention, impurity element mass percent is:Al < 0.01%, Ni < 0.005%, Cu < 0.005%.
A kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy preparation methods of high intensity of the present invention, including it is following Step:
(1) weigh according to the ratio raw material, above-mentioned raw materials using high-purity magnesium ingot, high-purity zinc ingot metal, high purity iron, Mg-30%Zr among Alloy carries out melting to above-mentioned raw materials by vaccum sensitive stove under argon gas protective condition, at 780~800 DEG C keep the temperature 40~ 60min stirs 5~10min after above-mentioned raw materials all melt, and 730~750 DEG C of 20~30min of refining is then cooled to, after refining 750~780 DEG C of 30~40min of standing are warming up to, ingot casting is poured at 710-730 DEG C;
(2) above-mentioned ingot casting is subjected to Homogenization Treatments, soaking time 16-18h, 50~60 DEG C of water at 400~420 DEG C It is cold;
(3) by the alloy after Homogenization Treatments by extruder squeeze 250~300 DEG C of temperature, extrusion speed 0.1~ Plate, stick, wire rod are squeezed under conditions of 5mm/s;
(4) plate, stick, the wire rod after extruding are subjected to artificial aging processing at 150~160 DEG C, soaking time 24~ 36h, it is air-cooled.
The extrusion ratio of the extruder is selected according to the size of material requested.
Argon gas at least prepurging 2 times is used before melting.
Mg >=99.99% in high-purity magnesium ingot, remaining is impurity;Zn >=99.99% in high-purity zinc ingot metal, remaining is impurity;It is high Fe >=99.98% in straight iron powder, remaining is impurity;Zr mass percents are 29-31%, impurity in Mg-30%Zr intermediate alloys Mass percent < 0.005%, remaining is Mg.
Embodiment 1
The mass percent of Mg-Zn-Zr-Fe alloying elements is:Zn is 5.8%, Zr 0.65%, Fe 0.03%, Al For 0.005%, Ni 0.004%, Cu 0.004%, remaining is Mg.
Raw material is:The Mg ingots of purity 99.995%, the Zn ingots of purity 99.993%, purity 99.987% Fe ingots and The Mg-Zr intermediate alloys (impurity mass percent 0.004%) that the mass percent of Zr is 29.8%.
It weighs according to the ratio raw material, melting is carried out under argon gas protective condition to above-mentioned raw materials by vaccum sensitive stove, 800 DEG C heat preservation 60min, stir 5min after above-mentioned raw materials all melts, be then cooled to 730 DEG C refine 25min, be warming up to after refining 760 DEG C of standing 30min, ingot casting is poured at 710 DEG C;
Above-mentioned ingot casting is subjected to Homogenization Treatments, soaking time 16h, 60 DEG C of water coolings at 420 DEG C;
By the alloy after Homogenization Treatments by extruder under conditions of squeezing 250 DEG C of temperature, extrusion speed 0.1mm/s It is squeezed into stick, extrusion ratio 30;
Plate, stick, wire rod after extruding is subjected to artificial aging processing at 150 DEG C, soaking time is for 24 hours, air-cooled.
The bar microscopic structure of the alloy is as shown in Figure 1, its average grain size is about 7 μm;;The room temperature tensile of the alloy Intensity is 368MPa, yield strength 335MPa, elongation percentage 14%.;In 37 DEG C of Hank ' s simulated body fluids (ingredient is shown in Table 1) In, corrosion rate 0.26mgcm-2·day-1, forms of corrosion is homogeneous corrosion.
1 experiment Hank ' s simulated body fluids chemical compositions (g/L) of table
Embodiment 2
The mass percent of Mg-Zn-Zr-Fe alloying elements is:Zn is 5.6%, Zr 0.74%, Fe 0.05%, Al For 0.004%, Ni 0.003%, Cu 0.004%, remaining is Mg.
Raw material is:The Mg ingots of purity 99.995%, the Zn ingots of purity 99.993%, purity 99.987% Fe ingots and The Mg-Zr intermediate alloys (impurity mass percent 0.004%) that the mass percent of Zr is 30%.
It weighs according to the ratio raw material, melting is carried out under argon gas protective condition to above-mentioned raw materials by vaccum sensitive stove, 790 DEG C heat preservation 50min, stir 10min after above-mentioned raw materials all melts, be then cooled to 750 DEG C refine 30min, be warming up to after refining 780 DEG C of standing 40min, ingot casting is poured at 720 DEG C;
Above-mentioned ingot casting is subjected to Homogenization Treatments, soaking time 18h, 55 DEG C of water coolings at 410 DEG C;
By the alloy after Homogenization Treatments by extruder under conditions of squeezing 280 DEG C of temperature, extrusion speed 0.3mm/s It is squeezed into stick, extrusion ratio 20;
Plate, stick, wire rod after extruding is subjected to artificial aging processing at 155 DEG C, soaking time 30h is air-cooled.
The average grain size of the bar of the alloy is about 6 μm;The room temperature tensile intensity of the alloy is 372MPa, and surrender is strong Degree is 338MPa, elongation percentage 15%.;In 37 DEG C of Hank ' s simulated body fluids (ingredient is shown in Table 1), corrosion rate is 0.28mg·cm-2·day-1, forms of corrosion is homogeneous corrosion.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.

Claims (10)

1. a kind of fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity, which is characterized in that by following weight hundred Divide the element composition of ratio:Zn 5.0~6.0%, Zr 0.5~1.0%, Fe 0.01~0.09%, Al < 0.01%, Ni < 0.005%, Cu < 0.005%.Remaining is Mg and its inevitable impurity.
2. alloy material as described in claim 1, which is characterized in that tensile strength >=360MPa of the alloy material is bent Take intensity >=320MPa, elongation percentage >=14%;In 37 DEG C of Hank ' s simulated body fluids, corrosion rate≤0.28mgcm-2· day-1
3. alloy material as described in claim 1, which is characterized in that impurity element mass percent is:Al < 0.01%, Ni < 0.005%, Cu < 0.005%.
4. a kind of preparation method of the fast degradation bio-medical Mg-Zn-Zr-Fe alloy materials of high intensity, which is characterized in that packet It includes:
Magnesium ingot, zinc ingot metal, iron, Mg-30%Zr intermediate alloys are subjected to melting, pour into ingot casting;
Above-mentioned ingot casting is subjected to Homogenization Treatments, and is squeezed into plate, stick or wire rod;
By plate, stick, the wire rod after extruding carry out artificial aging processing, it is air-cooled to get.
5. method as claimed in claim 4, which is characterized in that " melting pours into ingot casting " the specific steps are:By magnesium Ingot, zinc ingot metal, iron, Mg-30%Zr intermediate alloys keep the temperature 40~60min at 780~800 DEG C, and 5 are stirred after above-mentioned raw materials all melt ~10min, be then cooled to 730~750 DEG C refining 20~30min, be warming up to after refining 750~780 DEG C stand 30~ 40min pours into ingot casting at 710-730 DEG C.
6. method as claimed in claim 4, which is characterized in that the condition of the Homogenization Treatments be at 400~420 DEG C into Row Homogenization Treatments, soaking time 16-18h, then in 50~60 DEG C of water coolings.
7. method as claimed in claim 4, which is characterized in that the actual conditions of the extruding are:Squeeze temperature 250~300 DEG C, 0.1~5mm/s of extrusion speed.
8. method as claimed in claim 4, which is characterized in that the condition of the artificial aging processing is at 150~160 DEG C Under, 24~36h is kept the temperature, it is air-cooled.
9. the fast degradation bio-medical Mg-Zn-Zr-Fe of high intensity prepared by claim 4-8 any one of them methods is closed Golden material.
10. claim 1-3,9 any one of them Mg-Zn-Zr-Fe alloy materials are being prepared for injury gained in sports treatment and health Application in multiple tissue engineering bracket material.
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CN114921700B (en) * 2022-05-25 2023-09-26 中南大学 Biodegradable Mg-Zn-Ca-Re alloy

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