CN116065073A - Degradable biological magnesium alloy and preparation method thereof - Google Patents
Degradable biological magnesium alloy and preparation method thereof Download PDFInfo
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- CN116065073A CN116065073A CN202310037413.6A CN202310037413A CN116065073A CN 116065073 A CN116065073 A CN 116065073A CN 202310037413 A CN202310037413 A CN 202310037413A CN 116065073 A CN116065073 A CN 116065073A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- 239000011701 zinc Substances 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000003723 Smelting Methods 0.000 claims description 40
- 230000006698 induction Effects 0.000 claims description 35
- 239000011159 matrix material Substances 0.000 claims description 33
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 238000000265 homogenisation Methods 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 21
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 15
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 244000137852 Petrea volubilis Species 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 12
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910009378 Zn Ca Inorganic materials 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000002513 implantation Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035772 mutation Effects 0.000 description 2
- 231100001081 no carcinogenicity Toxicity 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000012890 simulated body fluid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 equipment Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a degradable biological magnesium alloy and a preparation method thereof, wherein the degradable biological magnesium alloy comprises the following components in parts by weight, 0.4-0.6% of lithium, 2.5-3.5% of zinc, 0.4-0.6% of calcium, 0.6-0.8% of zirconium and the balance of magnesium. According to the invention, the Mg-Li-Zn-Ca alloy is modified by adopting the zirconium element with excellent grain refinement effect, and the plasticity of the biological magnesium alloy can be obviously improved by adding a trace of zirconium element, so that the performance of the biological magnesium alloy is improved; the design of low zinc element is adopted, so that on one hand, the degradation rate of the biological magnesium alloy in the body can be reduced, and on the other hand, the plastic deformation capability of the biological magnesium alloy can be obviously improved; the density of the biological magnesium alloy can be reduced by adding a small amount of lithium element, and the secondary hazard of rapid reduction of bearing caused by stronger local corrosion of the biological magnesium alloy after implantation in a body can be avoided.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a degradable biological magnesium alloy and a preparation method thereof.
Background
As the population increases, there is a great demand for biomedical materials, such as bone implant materials. As a novel degradable biomedical material, the biological magnesium alloy has become a leading edge research hot spot nowadays. However, compared with biological titanium alloy, the biological magnesium alloy has lower mechanical property and too high corrosion speed, and in the actual use process, the problem of failure in implantation of biological materials caused by insufficient bearing capacity and too high degradation speed is easy to occur, thus becoming the bottleneck for restricting the clinical application of biological magnesium alloy materials.
Disclosure of Invention
The invention solves the problem of providing a degradable biological magnesium alloy with higher mechanical property, stronger bearing capacity and proper corrosion speed.
In order to solve at least one aspect of the problems, the invention provides a degradable biological magnesium alloy which is characterized by comprising the following components, by weight, 0.4-0.6% of lithium, 2.5-3.5% of zinc, 0.4-0.6% of calcium and 0.6-0.8% of zirconium, and the balance of magnesium.
According to the invention, the Mg-Li-Zn-Ca alloy is modified by adopting the zirconium element with excellent grain refinement effect, the zirconium element has excellent in-vivo biocompatibility and degradability, no mutation and no carcinogenicity, and trace zirconium element is added to obviously refine the biological magnesium alloy tissue, so that the dendrite segregation in the alloy is reduced after homogenization treatment, the plasticity of the biological magnesium alloy is obviously improved, and the performance of the biological magnesium alloy is improved; in addition, the design of low zinc element is adopted, so that on one hand, the degradation rate of the biological magnesium alloy in the body can be reduced, and on the other hand, the plastic deformation capacity of the biological magnesium alloy can be obviously improved, and the requirement of later plastic deformation can be met; the density of the biological magnesium alloy can be reduced by adding a small amount of lithium elements, and the influence on corrosion resistance is small due to the fact that the adding amount of the lithium elements is small, the lithium elements are uniformly dissolved in the biological magnesium alloy matrix, so that the biological magnesium alloy can be uniformly corroded in the corrosion process, serious local corrosion is avoided, and secondary damage caused by rapid reduction of bearing caused by strong local corrosion after the biological magnesium alloy is implanted into a body is avoided.
The invention also provides a preparation method of the degradable biological magnesium alloy, which is used for preparing the degradable biological magnesium alloy and comprises the following steps:
s1, carrying out vacuum smelting on magnesium, lithium, zinc and magnesium-calcium alloy to obtain a matrix alloy cast ingot;
s2, remelting the matrix alloy cast ingot, adding magnesium-zirconium alloy, melting to obtain biological magnesium alloy liquid, and casting the biological magnesium alloy liquid into a biological magnesium alloy ingot;
s3, processing the biological magnesium alloy ingot into a biological magnesium alloy plate;
s4, carrying out homogenization heat treatment on the biological magnesium alloy plate to obtain a homogenization heat treated biological magnesium alloy plate;
and S5, rolling the homogenized biological magnesium alloy plate to obtain the degradable biological magnesium alloy.
Preferably, in the step S1, the purity of the magnesium, the lithium and the zinc is greater than or equal to 99.9%, and the calcium content in the magnesium-calcium alloy is 20%.
Preferably, in the step S1, the magnesium, the lithium, the zinc and the magnesium-calcium alloy are placed into a graphite crucible, and placed into a vacuum induction melting furnace for vacuum melting, the melting power is set to be 10-15kW, when the magnesium, the lithium, the zinc and the magnesium-calcium alloy are all melted, a matrix alloy liquid is obtained, the temperature is kept for 10min, and then the matrix alloy liquid is cast into a mold, so as to obtain a matrix alloy ingot.
Preferably, the magnesium, the lithium, the zinc and the magnesium-calcium alloy are placed in a graphite crucible, placed in a vacuum induction furnace, the vacuum induction furnace is sealed, vacuumized to be below-98.75 KPa, then argon is introduced to the pressure in the vacuum induction furnace to reach 0KPa, vacuumized to be below-98.75 KPa for the second time, argon is introduced again to the pressure in the vacuum induction furnace to be below-30 KPa, the power of the vacuum induction furnace is adjusted to be 5kW, preheated for 10min, and then vacuum smelting is carried out.
Preferably, the mould is preheated to 180 ℃, and the matrix alloy liquid is cast into the preheated mould under the power condition of 10kW, so that the matrix alloy cast ingot is obtained.
Preferably, in the step S2, the base alloy ingot is cut and then placed in the vacuum induction melting furnace, the melting power is set to be 10-15kW under the protection of argon gas for melting, after the base alloy ingot is completely melted, the magnesium-zirconium alloy is added, the melting is performed again under the condition that the melting power is 10-15kW until the magnesium-zirconium alloy is completely melted, the standing and the heat preservation are performed for 10min, the biological magnesium alloy liquid is obtained, and the biological magnesium alloy liquid is cast into the biological magnesium alloy ingot.
Preferably, in the step S3, the biological magnesium alloy ingot is cut by wire, processed into a plate with the thickness of 10mm, polished by coarse sand paper, then ultrasonically cleaned by acetone and alcohol, and polished to 1200 meshes by sand paper, thereby obtaining the biological magnesium alloy plate.
Preferably, in the step S4, the biological magnesium alloy sheet is kept at 275-325 ℃ for 15min, and subjected to homogenization heat treatment, so as to obtain the homogenization heat treated biological magnesium alloy sheet.
Preferably, in the step S5, the homogenized biological magnesium alloy sheet is rolled at a temperature of 300 ℃ to obtain the degradable biological magnesium alloy, wherein the single-pass large deformation is 70%.
According to the invention, various elements in the biological magnesium alloy can be fully dispersed through vacuum melting, and after the melted biological magnesium alloy ingot is processed into the biological magnesium alloy plate, the structure of the dispersed biological magnesium alloy can be obviously refined after homogenization heat treatment and rolling, the preparation process is simple, and the prepared biological magnesium alloy has fine and uniform structure, good mechanical property and corrosion resistance, and has high value for application of the biological magnesium alloy in clinical medical treatment.
Drawings
FIG. 1 is a flow chart of a method for preparing a degradable magnesium alloy according to an embodiment of the invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that, without conflict, features in the embodiments of the present invention may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment, reagents are commercially available unless otherwise specified.
The embodiment of the invention provides a degradable biological magnesium alloy which is characterized by comprising the following components, by weight, 0.4-0.6% of lithium, 2.5-3.5% of zinc, 0.4-0.6% of calcium, 0.6-0.8% of zirconium and the balance of magnesium.
According to the embodiment of the invention, the Mg-Li-Zn-Ca alloy is modified by adopting the zirconium element with excellent grain refinement effect, the zirconium element has excellent in-vivo biocompatibility and degradability, no mutation and no carcinogenicity, and the biological magnesium alloy structure can be obviously refined by adding a trace of zirconium element, so that the dendrite segregation in the alloy is reduced, the plasticity of the biological magnesium alloy is obviously improved, and the performance of the biological magnesium alloy is improved; in addition, the design of low zinc element is adopted, so that on one hand, the degradation rate of the biological magnesium alloy in the body can be reduced, and on the other hand, the plastic deformation capacity of the biological magnesium alloy can be obviously improved, and the requirement of later plastic deformation can be met; the density of the biological magnesium alloy can be reduced by adding a small amount of lithium elements, and the influence on corrosion resistance is small due to the fact that the adding amount of the lithium elements is small, the lithium elements are uniformly dissolved in the biological magnesium alloy matrix, so that the biological magnesium alloy can be uniformly corroded in the corrosion process, serious local corrosion is avoided, and secondary damage caused by rapid reduction of bearing caused by strong local corrosion after the biological magnesium alloy is implanted into a body is avoided.
Another embodiment of the present invention provides a method for preparing a degradable magnesium alloy, for preparing a degradable magnesium alloy as described above, as shown in fig. 1, comprising the steps of:
s1, carrying out vacuum smelting on magnesium, lithium, zinc and magnesium-calcium alloy to obtain a matrix alloy cast ingot;
s2, remelting the matrix alloy cast ingot, adding magnesium-zirconium alloy, melting to obtain biological magnesium alloy liquid, and casting the biological magnesium alloy liquid into a biological magnesium alloy ingot;
s3, processing the biological magnesium alloy ingot into a biological magnesium alloy plate;
s4, carrying out homogenization heat treatment on the biological magnesium alloy plate to obtain a homogenization heat treated biological magnesium alloy plate;
and S5, rolling the homogenized biological magnesium alloy plate to obtain the degradable biological magnesium alloy.
In the step S1, the purities of the magnesium, the lithium and the zinc are greater than or equal to 99.9%, and the calcium content in the magnesium-calcium alloy is 20%. The high-purity magnesium, lithium and zinc are used as raw materials, so that the influence of impurities can be reduced, the magnesium-calcium alloy adopts commercial intermediate alloy Mg-20Ca, and the calcium content is 20%.
Specifically, cutting the magnesium, the lithium, the zinc and the magnesium-calcium alloy into blocks, placing the blocks into a graphite crucible, placing the graphite crucible into a vacuum induction smelting furnace for vacuum smelting, setting the smelting power to be 10-15kW, ensuring that the materials are melted for about 20min to obtain a matrix alloy liquid, then preserving heat for 10min, improving the uniformity of the matrix alloy liquid, casting the matrix alloy liquid into a die, and cooling to obtain a matrix alloy cast ingot.
In one embodiment, the magnesium, the lithium, the zinc and the magnesium-calcium alloy are placed in a graphite crucible, placed in a vacuum induction furnace, the vacuum induction furnace is sealed, vacuumized to below-98.75 KPa, then argon is introduced into the vacuum induction furnace until the pressure in the vacuum induction furnace reaches 0KPa, vacuumized to below-98.75 KPa for the second time, argon is introduced again until the pressure in the vacuum induction furnace is below-30 KPa, the power of the vacuum induction furnace is adjusted to 5kW, preheated for 10min, and then vacuum smelting is carried out.
After the first vacuumizing, argon is introduced to vacuumize again, so that air in the vacuum induction melting furnace can be exhausted as much as possible, and the vacuum induction melting furnace is kept under proper pressure conditions by introducing the argon, so that melting can be performed under the vacuum condition of an argon protective atmosphere, and the melting effect is ensured.
In another embodiment, the mold is preheated to 180 ℃, and the base alloy liquid is cast into the preheated mold under 10kW of power to obtain the base alloy ingot. By preheating the die, the phenomenon that the temperature difference between the base alloy liquid and the die is too large in casting, so that the base alloy liquid is too fast in cooling, cold insulation is generated, the fluidity of the alloy is increased, the casting stress is reduced, and the surface hot crack tendency is reduced can be avoided.
In the step S2, cutting the matrix alloy cast ingot, placing the cut matrix alloy cast ingot into a vacuum induction melting furnace, setting the smelting power to be 10-15kW under the protection of argon gas for smelting, adding the magnesium-zirconium alloy after the matrix alloy cast ingot is completely melted, smelting again under the condition that the smelting power is 10-15kW until the magnesium-zirconium alloy is completely melted, standing and preserving heat for 10min, obtaining the biological magnesium alloy liquid, and casting the biological magnesium alloy liquid into the biological magnesium alloy ingot.
The smelting power is set to be 10-15kW, so that the smelting rate can be ensured, the matrix alloy and the magnesium-zirconium alloy can be completely melted within 20min, the uniformity of biological magnesium alloy liquid can be ensured after heat preservation for 10min, and various metal elements are uniformly dispersed.
Wherein the magnesium-zirconium alloy is commercial intermediate alloy Mg-30Zr, namely the zirconium content in the magnesium-zirconium alloy is 30 percent.
In the step S3, the biological magnesium alloy ingot is cut by a wire, processed into a plate with the thickness of 10mm, polished by coarse sand paper, then ultrasonically cleaned by acetone and alcohol, and polished to 1200 meshes by sand paper, thereby obtaining the biological magnesium alloy plate.
Oil stains and impurities on the surface of the biological magnesium alloy ingot can be removed by ultrasonic cleaning, and the defect on the surface of the biological magnesium alloy plate is eliminated by polishing to 1200 meshes by sand paper, so that the rolling quality is improved.
In the step S4, the biological magnesium alloy plate is subjected to heat preservation for 15min at 275-325 ℃ and is subjected to homogenization heat treatment, so that the homogenization heat treatment biological magnesium alloy plate is obtained.
Before rolling, the biological magnesium alloy sheet material is subjected to homogenization heat treatment, so that the structure defects and residual stress in the biological magnesium alloy sheet material can be eliminated, grains are refined, the structure is improved, and the rolling quality is improved.
In the step S5, rolling the homogenized biological magnesium alloy plate at the temperature of 300 ℃, wherein the single-pass large deformation is 70%, and the degradable biological magnesium alloy is obtained.
The single-pass rolling process with the large deformation of 70% is adopted to process, so that a better tissue improvement effect can be realized, and the performance of the biological magnesium alloy is obviously improved.
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The biological magnesium alloy in the embodiment comprises the following components in parts by weight: 0.4wt% of lithium, 2.5wt% of zinc, 0.4wt% of calcium, 0.6wt% of zirconium and the balance of magnesium. The preparation method comprises the following steps:
1.1, calculating the required quantity of each raw material according to the set components and considering the burning loss rate of alloy elements, cutting magnesium, zinc, lithium and Mg-20Ca intermediate alloy into blocks according to the calculation result, placing the blocks in a graphite crucible, placing the graphite crucible into a vacuum induction smelting furnace, and sealing the smelting furnace; then vacuumizing to below-98.75 KPa, introducing argon gas until the pressure in the furnace is about 0KPa, vacuumizing again to below-98.75 KPa, and introducing argon gas until the pressure in the furnace is-30 KPa; setting the power of a vacuum induction melting furnace to be 5kW, preheating for 10min, then raising the power to 10kW until the raw materials are completely melted, standing for 10min, and casting into a steel mold preheated to 180 ℃ under the condition of 10kW of melting power to obtain a matrix alloy ingot; wherein the purities of magnesium, zinc and lithium are all more than or equal to 99.9 percent;
1.2, cutting a matrix alloy ingot into blocks, putting the blocks into a steel crucible, putting the steel crucible into a vacuum induction smelting furnace, setting smelting power to be 10-15kW, carrying out vacuum smelting in an argon protective atmosphere, wrapping commercial intermediate alloy of Mg-30Zr with aluminum foil after the matrix alloy ingot is completely melted, putting the commercial intermediate alloy into the steel crucible, setting the smelting power to be 10kW, standing for 10min, and casting the commercial intermediate alloy into a preheated die under the smelting power condition of 10kW to obtain a biological magnesium alloy ingot;
1.3, performing wire cutting on the biological magnesium alloy ingot, processing the biological magnesium alloy ingot into a plate with the thickness of 10mm, then adopting coarse sand paper to polish off oil stains on the surface, adopting acetone and alcohol to perform ultrasonic cleaning for 3min, and then using fine sand paper to polish to 1200 meshes to obtain the biological magnesium alloy plate;
1.4, preserving the temperature of the biological magnesium alloy plate for 15min at the temperature of 300 ℃ and carrying out homogenization heat treatment to obtain a homogenization heat treatment biological magnesium alloy plate;
and 1.5, placing the homogenized biological magnesium alloy plate into a rolling mill for rolling, wherein the temperature is set to 300 ℃ in the rolling process, and the single-pass large deformation is 70% in the rolling process, so that the degradable biological magnesium alloy is obtained.
Example 2
The biological magnesium alloy in the embodiment comprises the following components in parts by weight: 0.6wt% of lithium, 3.5wt% of zinc, 0.6wt% of calcium, 0.8wt% of zirconium and the balance of magnesium. The preparation method comprises the following steps:
2.1, calculating the required quantity of each raw material according to the set components and considering the burning loss rate of alloy elements, cutting magnesium, zinc, lithium and Mg-20Ca intermediate alloy into blocks according to the calculation result, placing the blocks in a graphite crucible, placing the graphite crucible in a vacuum induction smelting furnace, and sealing the smelting furnace; then vacuumizing to below-98.75 KPa, introducing argon gas until the pressure in the furnace is about 0KPa, vacuumizing again to below-98.75 KPa, and introducing argon gas until the pressure in the furnace is-30 KPa; setting the power of a vacuum induction melting furnace to be 5kW, preheating for 10min, then raising the power to 15kW until the raw materials are completely melted, standing for 10min, and casting into a steel mold preheated to 180 ℃ under the condition of 10kW of melting power to obtain a matrix alloy ingot; wherein the purities of magnesium, zinc and lithium are all more than or equal to 99.9 percent;
2.2, cutting a matrix alloy ingot into blocks, putting the blocks into a steel crucible, putting the steel crucible into a vacuum induction smelting furnace, setting the smelting power to be 15kW, carrying out vacuum smelting in an argon protective atmosphere, wrapping the commercial Mg-30Zr intermediate alloy with aluminum foil after the matrix alloy ingot is completely melted, putting the commercial Mg-30Zr intermediate alloy into the steel crucible, setting the smelting power to be 15kW, standing for 10min, and casting the commercial Mg-30Zr intermediate alloy into a preheated die under the smelting power condition of 10kW to obtain a biological magnesium alloy ingot;
2.3, performing wire cutting on the biological magnesium alloy ingot, processing the biological magnesium alloy ingot into a plate with the thickness of 10mm, then adopting coarse sand paper to polish off oil stains on the surface, adopting acetone and alcohol to perform ultrasonic cleaning for 3min, and then using fine sand paper to polish to 1200 meshes to obtain the biological magnesium alloy plate;
2.4, preserving the temperature of the biological magnesium alloy plate for 15min at the temperature of 275 ℃ and carrying out homogenization heat treatment to obtain a homogenization heat treated biological magnesium alloy plate;
and 2.5, placing the homogenized biological magnesium alloy plate into a rolling mill for rolling, wherein the temperature is set to 300 ℃ in the rolling process, and the single-pass large deformation is 70% in the rolling process, so that the degradable biological magnesium alloy is obtained.
Example 3
The biological magnesium alloy in the embodiment comprises the following components in parts by weight: 0.5wt% of lithium, 3.0wt% of zinc, 0.5wt% of calcium, 0.7wt% of zirconium and the balance of magnesium. The preparation method comprises the following steps:
3.1, calculating the required quantity of each raw material according to the set components and considering the burning loss rate of alloy elements, cutting magnesium, zinc, lithium and Mg-20Ca intermediate alloy into blocks according to the calculation result, placing the blocks in a graphite crucible, placing the graphite crucible in a vacuum induction smelting furnace, and sealing the smelting furnace; then vacuumizing to below-98.75 KPa, introducing argon gas until the pressure in the furnace is about 0KPa, vacuumizing again to below-98.75 KPa, and introducing argon gas until the pressure in the furnace is-30 KPa; setting the power of a vacuum induction melting furnace to be 5kW, preheating for 10min, then raising the power to 12kW until the raw materials are completely melted, standing for 10min, and casting into a steel mold preheated to 180 ℃ under the condition of 10kW of melting power to obtain a matrix alloy ingot; wherein the purities of magnesium, zinc and lithium are all more than or equal to 99.9 percent;
3.2, cutting a matrix alloy ingot into blocks, putting the blocks into a steel crucible, putting the steel crucible into a vacuum induction smelting furnace, setting smelting power to be 12kW, carrying out vacuum smelting in an argon protective atmosphere, packaging the commercial Mg-30Zr intermediate alloy with aluminum foil after the matrix alloy ingot is completely melted, putting the commercial Mg-30Zr intermediate alloy into the steel crucible, setting the smelting power to be 12kW, standing for 10min, and casting the commercial Mg-30Zr intermediate alloy into a preheated die under the smelting power condition of 10kW to obtain a biological magnesium alloy ingot;
3.3, performing wire cutting on the biological magnesium alloy ingot, processing the biological magnesium alloy ingot into a plate with the thickness of 10mm, then adopting coarse sand paper to polish off oil stains on the surface, adopting acetone and alcohol to perform ultrasonic cleaning for 3min, and then using fine sand paper to polish to 1200 meshes to obtain the biological magnesium alloy plate;
3.4, preserving the temperature of the biological magnesium alloy plate for 15min at 325 ℃ and carrying out homogenization heat treatment to obtain a homogenization heat treatment biological magnesium alloy plate;
and 3.5, placing the homogenized biological magnesium alloy plate into a rolling mill for rolling, wherein the temperature is set to 300 ℃ in the rolling process, and the single-pass large deformation is 70% in the rolling process, so that the degradable biological magnesium alloy is obtained.
Comparative example 1
The comparative example differs from example 1 in that the biological magnesium alloy consists of the following components in parts by weight: 0.6wt% of lithium, 3.5wt% of zinc, 0.6wt% of calcium and the balance of magnesium.
The remaining conditions were the same as in example 1.
Comparative example 2
The comparative example differs from example 1 in that the biological magnesium alloy consists of the following components in parts by weight: 3.0wt% of lithium, 3.0wt% of zinc, 0.5wt% of calcium, 0.7wt% of zirconium and the balance of magnesium.
The remaining conditions were the same as in example 1.
Experimental example 1
The tensile strength of the degradable magnesium alloy obtained in examples 1-3 and comparative examples 1-2 was tested according to GB/T228-2020 Metal Material tensile test.
Wherein the tensile strength of the degradable biological magnesium alloy in example 1, example 2, example 3, comparative example 1 and comparative example 2 is 330MPa, 355MPa, 337MPa, 289MPa and 310MPa, respectively. It can be seen that the degradable biological magnesium alloys obtained in comparative examples 1 and 2 are significantly lower in tensile strength than the degradable biological magnesium alloys obtained in examples 1 to 3, indicating that the composition of the components provided by the examples of the present invention contributes to the improvement of mechanical properties of the degradable biological magnesium alloys.
Experimental example 2
The degradable biological magnesium alloys obtained in examples 1-3 and comparative examples 1-2 were tested for corrosion performance according to the method of astm g31-1972 (2004) Standard Practice for Lab Immersion Corrosion Testing of Metals, using simulated body fluids as the corrosion medium, maintaining the temperature at 36.5±0.5 ℃ and replacing the simulated body fluids every 12 hours.
Test results show that the degradable biological magnesium alloy in the examples 1-3 has slower corrosion rate, can realize slow degradation in clinical application, and ensures the strength requirement in the healing process. The degradable magnesium alloys of comparative examples 1 and 2 have poor corrosion resistance, which is significantly lower than the examples of the present invention.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. The degradable biological magnesium alloy is characterized by comprising the following components, by weight, 0.4-0.6% of lithium, 2.5-3.5% of zinc, 0.4-0.6% of calcium, 0.6-0.8% of zirconium and the balance of magnesium.
2. A method for preparing the degradable biological magnesium alloy, which is used for preparing the degradable biological magnesium alloy according to claim 1, and is characterized by comprising the following steps:
s1, carrying out vacuum smelting on magnesium, lithium, zinc and magnesium-calcium alloy to obtain a matrix alloy cast ingot;
s2, remelting the matrix alloy cast ingot, adding magnesium-zirconium alloy, melting to obtain biological magnesium alloy liquid, and casting the biological magnesium alloy liquid into a biological magnesium alloy ingot;
s3, processing the biological magnesium alloy ingot into a biological magnesium alloy plate;
s4, carrying out homogenization heat treatment on the biological magnesium alloy plate to obtain a homogenization heat treated biological magnesium alloy plate;
and S5, rolling the homogenized biological magnesium alloy plate to obtain the degradable biological magnesium alloy.
3. The method of producing a degradable magnesium alloy according to claim 2, wherein in the step S1, the purity of the magnesium, the lithium and the zinc is 99.9% or more, and the calcium content in the magnesium-calcium alloy is 20%.
4. The method for preparing the degradable biological magnesium alloy according to claim 2, wherein in the step S1, the magnesium, the lithium, the zinc and the magnesium-calcium alloy are placed into a graphite crucible, placed into a vacuum induction melting furnace for vacuum melting, the melting power is set to be 10-15kW, a matrix alloy liquid is obtained after the magnesium, the lithium, the zinc and the magnesium-calcium alloy are all melted, the temperature is kept for 10min, and then the matrix alloy liquid is cast into a mold to obtain a matrix alloy cast ingot.
5. The method for preparing the degradable biological magnesium alloy according to claim 4, wherein the magnesium, the lithium, the zinc and the magnesium-calcium alloy are placed in a graphite crucible, placed in a vacuum induction furnace, the vacuum induction furnace is sealed, vacuumized to be below-98.75 KPa, then argon is introduced into the vacuum induction furnace until the pressure in the vacuum induction furnace reaches 0KPa, vacuumized to be below-98.75 KPa for the second time, argon is introduced again until the pressure in the vacuum induction furnace is-30 KPa, the power of the vacuum induction furnace is adjusted to be 5kW, the vacuum induction furnace is preheated for 10min, and then vacuum smelting is carried out.
6. The method for producing a degradable magnesium alloy according to claim 4, wherein the mold is preheated to 180 ℃, and the base alloy liquid is cast into the preheated mold under a power condition of 10kW, to obtain the base alloy ingot.
7. The method for preparing the degradable biological magnesium alloy according to claim 2, wherein in the step S2, the substrate alloy cast ingot is cut and then placed in the vacuum induction melting furnace, the smelting power is set to be 10-15kW for smelting under the protection of argon, after the substrate alloy cast ingot is completely melted, the magnesium-zirconium alloy is added, smelting is performed again under the condition of the smelting power of 10-15kW until the magnesium-zirconium alloy is completely melted, standing and preserving heat for 10min, so as to obtain the biological magnesium alloy liquid, and the biological magnesium alloy liquid is cast into the biological magnesium alloy ingot.
8. The method for preparing the degradable magnesium alloy according to claim 2, wherein in the step S3, the magnesium alloy ingot is cut by wire, processed into a plate with the thickness of 10mm, polished by coarse sand paper, then ultrasonically cleaned by acetone and alcohol, and polished to 1200 meshes by sand paper, thereby obtaining the magnesium alloy plate.
9. The method for preparing the degradable biological magnesium alloy according to claim 2, wherein in the step S4, the biological magnesium alloy plate is subjected to homogenization heat treatment at 275-325 ℃ for 15min, and the homogenization heat treated biological magnesium alloy plate is obtained.
10. The method for preparing a degradable biological magnesium alloy according to claim 2, wherein in the step S5, the homogenized biological magnesium alloy sheet is rolled at a temperature of 300 ℃, and the single-pass large deformation is 70%, so as to obtain the degradable biological magnesium alloy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102392163A (en) * | 2011-11-07 | 2012-03-28 | 山东科技大学 | Degradable high-toughness corrosion-resistant medical Mg-Li-Ca alloy |
| CN107435116A (en) * | 2017-07-10 | 2017-12-05 | 太原理工大学 | A kind of magnesium alloy biological implantation material and preparation method thereof |
| CN112494725A (en) * | 2020-10-16 | 2021-03-16 | 珠海中科先进技术研究院有限公司 | Biodegradable composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392163A (en) * | 2011-11-07 | 2012-03-28 | 山东科技大学 | Degradable high-toughness corrosion-resistant medical Mg-Li-Ca alloy |
| CN107435116A (en) * | 2017-07-10 | 2017-12-05 | 太原理工大学 | A kind of magnesium alloy biological implantation material and preparation method thereof |
| CN112494725A (en) * | 2020-10-16 | 2021-03-16 | 珠海中科先进技术研究院有限公司 | Biodegradable composite material and preparation method and application thereof |
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