CN114231811B - Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy and preparation method thereof - Google Patents

Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy and preparation method thereof Download PDF

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CN114231811B
CN114231811B CN202111552512.5A CN202111552512A CN114231811B CN 114231811 B CN114231811 B CN 114231811B CN 202111552512 A CN202111552512 A CN 202111552512A CN 114231811 B CN114231811 B CN 114231811B
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magnesium alloy
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CN114231811A (en
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李经纬
戴悦来
李雨蕾
左欣
朱宇瑾
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China Weapon Science Academy Ningbo Branch
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China Weapon Science Academy Ningbo Branch
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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
    • C22C23/06Alloys based on magnesium with a rare earth metal 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
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Abstract

The invention relates to a Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy and a preparation method thereof, and the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy is characterized by comprising the following components in percentage by weight: nd: 4-5%, Zr: 1 to 1.5%, Sr: 2-2.5%, Sc: 1.2-2%, Sm: 0.8-2.8%, the content of other inevitable impurities is less than or equal to 0.1%, and the balance is Mg. The mechanical property and the corrosion resistance of the magnesium alloy are improved, after the therapeutic effect is realized, the magnesium alloy can be naturally degraded in a human body and discharged out of the human body, and the secondary injury to the human body is avoided.

Description

Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical metal material preparation, and particularly relates to a Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy and a preparation method thereof.
Background
Biomedical materials are a class of materials used to diagnose, treat, repair, or replace damaged tissues, organs, or enhance their function in living beings without adverse effects on the human body. At present, biomedical organic and inorganic materials, biomedical composite materials, biomedical metal materials and the like are widely used in clinical medicine as biomedical materials. Compared with other medical materials, the biomedical metal material has excellent mechanical properties such as higher strength, good toughness, higher bending fatigue resistance, excellent processability, good biocompatibility, corrosion resistance and the like, and is mainly used as a bearing material in medical application, such as: orthopedic implants, cardiovascular stents, and the like.
The magnesium alloy has a low density of 1.74g/cm 3 And the bone density of the human body is 1.78-2.1 g/cm 3 ) And (4) the equivalent. And magnesium is the most similar to the normal bone tissue of a human body in the biomechanical property (41-45 GPa) of all the existing metal materials, and can effectively relieve stress shielding. Meanwhile, magnesium is the second most important cation in the human body, and can participate in the synthesis of protein, activate various enzymes in the body, and regulate the activities of neuromuscular and central nervous systems. Magnesium is degraded in vivo into soluble non-toxic oxides and is discharged out of the body by circulation. The magnesium alloy is a biomedical metal material with wide application prospect due to excellent mechanical property, degradability and biocompatibility.
As another example of the chinese patent application "a degradable corrosion-resistant magnesium alloy stent for medical use implanted in the heart and a method for preparing the same", the patent application No. CN201810408301.6 (application publication No. CN108677074A) discloses that a degradable corrosion-resistant magnesium alloy stent for medical use implanted in the heart is composed of the following elements by mass percent: 12.5 to 13 portions of Zn, 3.6 to 3.8 portions of Nd, 3.2 to 3.8 portions of Ca, 1.1 to 1.3 portions of Mn, 0.5 to 0.8 portion of Y, 0.2 to 0.4 portion of Zr, 0.5 to 0.7 portion of Sn, 0.4 to 0.5 portion of Gd, 0.2 to 0.3 portion of Sr, 4.55 to 7 portions of Nd/Y, 1.1 to 2.4 portions of Gd/Zr, and the balance of Mg and inevitable impurity elements, wherein the inevitable impurity elements comprise the following components in percentage by weight: 0.002-0.005% of Fe, 0.005-0.008% of Ni, 0.015-0.05% of Si and Mg in metallographic structure 3 The grain diameter of Nd precipitate is 0.10-0.15 mu m, and Mg 3 Y 2 Zn 3 The grain diameter of the precipitate is 0.15-0.20 μm, and Ca in the metallographic structure 2 Mg 6 Zn 3 The grain size of the precipitate is 0.3-0.5 μm, in the patent, the grain size of the magnesium alloy is 50-60 μm, the tensile strength is 300-. The alloy content in the above patent is high and is not economically cost-effective; meanwhile, the addition of part of elements is repeated, for example, Zn is used as a weak grain refiner, the tendency of forming micro shrinkage porosity is formed, the addition amount is up to 12.5-13%, and Zr is used as the most effective grain refiner, and the refining effect of Zr on tissue grains is stronger than that of Zn. The heavy rare earth element Y is easy to enrich in brain, and is harmful to health when being used as a medical implant to add the heavy rare earth element.
If the applicant previously applied for a Chinese invention patent, namely a Mg-Y-Nd- (La + Ce) -Zr biodegradable magnesium alloy, the patent number is ZL201910743108.2 (the publication number is CN110468319B), the Mg-Y-Nd- (La + Ce) -Zr biodegradable magnesium alloy comprises the following components in percentage by mass: y: 3.0-4.5%, Nd: 2.0-3.5%, Zr: 0.3-1.0%, lanthanum cerium composite rare earth: 0.05-0.5 percent of magnesium and inevitable impurities in balance, and the impurity content is less than or equal to 0.1 percent, wherein the content of lanthanum and cerium in the lanthanum and cerium composite rare earth is respectively 50 percent. Although better corrosion resistance is obtained, the tensile strength is lower than 225MPa, and the requirements cannot be met. Ce is cytotoxic and harmful to health. In addition, literature studies indicate that heavy rare earth elements are readily enriched in the brain. Considering that the medical implant is harmless to human body, the addition of heavy rare earth element Y or a small amount of Y is avoided as much as possible.
As another example of the invention patent "a novel biodegradable zinc-based metal material and ureteral stent obtained by using the same" in china, the patent application No. CN201610310818.2 discloses a novel biodegradable zinc-based metal material, which is composed of zinc and/or zinc alloy, wherein the zinc alloy is an alloy of Zn and one or more of the following elements: mg, Al, Ti, Cu, Ag, Si, Ca, Sr, Y, Zr, Sc, Gd, Nd, Dy, Er, Li, Mn, La, Ce, Pr, Sm, Tb, Ho, Tm, Yb, Lu. Controllable mechanical property and corrosion property are realized, the range of tensile strength is 110-400MPa, the range of room temperature elongation is 0.3-50%, the degradation rate in simulated urine is 0.1-1.5 mm/year, and the degradation time is controlled to be 3 weeks-1.5 years. The light rare earth element Ce has cytotoxicity, the heavy rare earth element comprises Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, Lu and the like which are easy to enrich in the brain, meanwhile, Al is harmful to osteoblasts and neurons, can kill nerve cells, and has adverse effects of hypomnesis, slow movement and the like. Considering that the medical implant should be harmless to the human body, the addition of the above elements or a very small amount should be avoided.
Therefore, further improvements to the existing biodegradable magnesium alloys are needed.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a biodegradable magnesium alloy of Mg-Nd-Zr-Sr-Sc-Sm with high tensile strength, hardness and good corrosion resistance.
The invention aims to solve the second technical problem of providing a preparation method of the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy is characterized by comprising the following components in percentage by weight: nd: 4-5%, Zr: 1 to 1.5%, Sr: 2-2.5%, Sc: 1.2-2%, Sm: 0.8-2.8%, the content of other inevitable impurities is less than or equal to 0.1%, and the balance is Mg.
Among the light rare earth elements, the solid solubility of Sm in magnesium is the largest and is as high as 5.8 percent; the maximum solid solubility of Nd in magnesium is also 3.6%, and two elements have excellent strengthening effect in magnesium alloy, and the mass ratio of Sm: 0.8-2.8% and Nd: the tensile strength is improved by 4-5%. Precipitated phase Mg formed by Sm, Nd and Mg 24 Sm 5 、Mg 12 Nd is completely dissolved back into the matrix in the process of solution treatment to form a supersaturated solid solution, and the hardness is greatly improved after aging. Meanwhile, Nd and Mg form a strengthening phase Mg 2 Nd increases the tensile strength of the magnesium alloy. With the increase of the temperature, the strengthening effect is more obvious, the strength is improved, and the plasticity is also improved. Meanwhile, Nd can improve the corrosion resistance of the magnesium alloy.
Sc is added into magnesium to refine grains and improve the strength and plasticity of the magnesium alloy. Sc has larger solid solubility in magnesium, and a solid solution formed by Sc and Mg and Zr can play a role in precipitation strengthening, so that the strength of the magnesium alloy is improved. Meanwhile, the finer the crystal grain, the more uniform the galvanic corrosion, and the better the corrosion resistance of the magnesium alloy. Sc is not easy to form a second phase with magnesium, and the single-phase magnesium alloy has better corrosion resistance. And Sc formed by oxidation 2 O 3 Can react with Mg (OH) 2 Together forming a denser passivation layer to protect the substrate. The Mg-Sc alloy is a magnesium-based alloy with shape memory, and provides a new way for the research of medical implantsA new development direction.
The alloying element Zr is usually added to the magnesium alloy together with the rare earth elements and is the most effective grain refiner. By the mutual matching action of Zr and rare earth elements Sm, Nd and Sc, the crystal grains of the magnesium alloy can be refined in the solidification process. Compared with pure magnesium, the tensile strength and the elongation of the Mg-Zr alloy are improved, and the corrosion rate is reduced. Meanwhile, Zr can remove Fe, Al, Si and other elements in the melt, and the tensile property at room temperature is improved.
Sr is one of essential trace elements of human body, and the adult human body probably contains 140mgSr which is almost completely contained in bone, so that the bone tissue can be promoted to heal, and the bone tissue strength can be improved; and has good biocompatibility. Sr can be enriched at the front edge of solid-liquid during magnesium alloy solidification, the actual supercooling degree of the front edge of a solid-liquid interface is increased, the magnesium alloy crystal grains are effectively refined, and fine and dispersedly distributed Mg is mainly used 17 Sr 2 The existence of the phase is beneficial to improving the mechanical property of the magnesium alloy. The crystal grains of the magnesium alloy are refined, and meanwhile, the formation of a corrosion product film in the corrosion process is promoted, so that the barrier protection effect is achieved, and the corrosion resistance of the magnesium alloy is improved.
Specifically, the tensile strength of the degradable magnesium alloy is 350-420 MPa, the yield strength is 290-356 MPa, the Vickers hardness is 45-52, the elongation is more than 30%, and the average corrosion rate of 96h is 0.09-0.21 mg/(cm) 2 H). Therefore, the degradable magnesium alloy has good mechanical property, hardness and corrosion resistance.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy is characterized by sequentially comprising the following steps of:
1) according to the weight percentage, pure magnesium, Sr powder, Mg-Nd intermediate alloy, Mg-Zr intermediate alloy, Mg-Sc intermediate alloy and Mg-Sm intermediate alloy are mixed;
2) preheating a crucible and a casting mold to over 170 ℃, cooling to 70-80 ℃, coating ZnO coating, heating the crucible to 670-800 ℃, adding pure magnesium and Sr powder, and scattering a covering agent;
3) heating to 850-950 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring, removing slag, then spreading covering agent, and keeping the temperature for 30-40 minutes;
4) heating to 980-1000 ℃, adding Mg-Zr intermediate alloy and Mg-Sm intermediate alloy, stirring, removing slag, scattering solvent again, and keeping the temperature for 20-30 minutes;
5) reducing the temperature to 850-950 ℃, adding a refining agent for refining, standing for 25-35 minutes, reducing the temperature to 780-870 ℃, pouring the melt into a steel die with the preheating temperature of 190-210 ℃, and cooling at room temperature to obtain an ingot;
6) annealing, extruding or forging the cast ingot, and carrying out solution treatment to obtain magnesium alloy;
preferably, in step 2), the crucible is heated to 750 ℃, and in step 4), the holding time is 30 minutes, and after refining in step 5), the crucible is left to stand for 30 minutes.
Preferably, in the step 6), the extrusion temperature during extrusion is 270-450 ℃, and the extrusion ratio is 10-80.
Preferably, in the step 6), the forging is firstly carried out at 300-550 ℃ for 5-55 hours, and then the forging is carried out at 270-450 ℃, wherein the forging rate is 10-50%.
Preferably, in the step 6), the solution treatment temperature is 500-580 ℃, and the treatment time is 8-14 hours.
Compared with the prior art, the invention has the advantages that: the biodegradable magnesium alloy adopts the principle of multi-element and small-amount alloying, avoids adding heavy rare earth elements which can be gathered in the brain of a human body, selects and adds light rare earth elements Nd and Sm which are nontoxic to the human body, rare earth elements Sc and alloying elements Zr and Sr, and improves the mechanical property and the corrosion resistance of the magnesium alloy. In addition, the alloying element Sr can promote bone formation and inhibit bone resorption, and Sr which is locally released along with the degradation of the magnesium alloy can promote bone healing.
The biodegradable magnesium alloy realizes the regulation and control of the mechanical property and the degradation rate of the magnesium alloy through subsequent simple deformation processing treatment, namely extrusion or forging, obtains excellent mechanical property and corrosion resistance, is suitable for medical implantation, is particularly suitable for preparing bone repair materials, and has wide application prospect in the medical field. In addition, after the therapeutic effect is realized, the magnesium alloy can be naturally degraded in the human body and discharged out of the human body, so that secondary injury to the human body is avoided.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the preparation method of the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy comprises the following steps:
smelting by adopting a vacuum intermediate frequency induction furnace, burdening according to the components shown in the following table 1, preheating a crucible and a casting mold in a resistance furnace to over 170 ℃, cooling to 70 ℃, coating ZnO coating, heating the crucible to 750 ℃, adding pure magnesium (99.9 wt%) and Sr powder (99.8 wt%), scattering a covering agent, and keeping the temperature for about 20 minutes; when the temperature is heated to 900 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring and removing slag, then scattering covering agent, and keeping the temperature for 35 minutes; and (3) after the temperature is raised to 980 ℃, adding the Mg-Zr intermediate alloy and the Mg-Sm intermediate alloy, stirring, removing slag, scattering the solvent again, keeping the temperature for 30 minutes, reducing the temperature to 900 ℃, adding a refining agent for refining, standing for 30 minutes, cooling to 850 ℃, pouring the melt into a steel die with the preheating temperature of 190 ℃, and cooling at room temperature to obtain the ingot. And (3) preserving the heat of the cast ingot at 520 ℃ for 10 hours, annealing, cooling in air to 430 ℃ and extruding to obtain the magnesium alloy rod with the diameter of 10 mm. The solution treatment is carried out for 10 hours at 570 ℃, the furnace cooling is carried out, and the properties are shown in the following table 2.
Example 2:
this embodiment differs from embodiment 1 described above only in that: 1. the ingredients are different, and are shown in the following table 1 in detail; 2. the preparation method has different technological parameters, and specifically, the annealing treatment step comprises the following steps: and (3) keeping the temperature of the cast ingot at 480 ℃ for 10 hours, annealing, cooling in air to 400 ℃ for extrusion to obtain a magnesium alloy rod with the diameter of 10mm, carrying out solution treatment at 550 ℃ for 10 hours, and cooling along with the furnace. The properties of this example are shown in table 2 below.
Example 3:
this embodiment differs from embodiment 1 described above only in that: 1. the ingredients are different, and are shown in the following table 1 in detail; 2. the preparation method has different technological parameters, and specifically, the annealing treatment step comprises the following steps: keeping the temperature of the cast ingot at 450 ℃ for 10 hours, annealing, cooling in air to 350 ℃ for extrusion to obtain a magnesium alloy rod with the diameter of 10mm, carrying out solution treatment at 530 ℃ for 10 hours, and cooling along with the furnace. The properties of this example are shown in table 2 below.
Example 4:
this embodiment differs from embodiment 1 described above only in that: 1. the ingredients were varied as shown in table 1 below.
Example 5:
this embodiment differs from embodiment 1 described above only in that: 1. the ingredients were varied as shown in table 1 below.
Example 6:
this embodiment differs from embodiment 1 described above only in that: the preparation method has different technological parameters, and specifically,
preheating a crucible and a casting mold to over 170 ℃ in a resistance furnace, cooling to 75 ℃, coating ZnO coating, heating the crucible to 670 ℃, adding pure magnesium and Sr powder, scattering a covering agent, and keeping the temperature for about 20 minutes; when the temperature is heated to 850 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring and removing slag, then spreading covering agent, and preserving heat for 40 minutes; and (3) when the temperature is increased to 990 ℃, adding the Mg-Zr intermediate alloy and the Mg-Sm intermediate alloy, stirring, removing slag, scattering the solvent again, keeping the temperature for 25 minutes, reducing the temperature to 850 ℃, adding a refining agent for refining, standing for 25 minutes, reducing the temperature to 780 ℃, pouring the melt into a steel die with the preheating temperature of 200 ℃, and cooling at room temperature to obtain the ingot. Keeping the temperature of the cast ingot at 500 ℃ for 8 hours, annealing, cooling in air to 450 ℃ for extrusion at the extrusion ratio of 50 to obtain a magnesium alloy rod with the diameter of 10mm, carrying out solution treatment at 580 ℃ for 8 hours, and cooling along with the furnace. The properties of this example are shown in table 2 below.
Example 7:
this embodiment differs from embodiment 1 described above only in that: the preparation method has different technological parameters, specifically,
preheating a crucible and a casting mold in a resistance furnace to over 170 ℃, cooling to 80 ℃, coating ZnO coating, heating the crucible to 800 ℃, adding pure magnesium and Sr powder, scattering a covering agent, and keeping the temperature for about 20 minutes; when the temperature is heated to 950 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring and removing slag, then scattering covering agent, and keeping the temperature for 30 minutes; and (3) after the temperature is raised to 1000 ℃, adding the Mg-Zr intermediate alloy and the Mg-Sm intermediate alloy, stirring, removing slag, scattering the solvent again, keeping the temperature for 20 minutes, reducing the temperature to 950 ℃, adding a refining agent for refining, standing for 35 minutes, reducing the temperature to 870 ℃, pouring the melt into a steel die with the preheating temperature of 210 ℃, and cooling at room temperature to obtain the ingot. Keeping the temperature of the cast ingot at 500 ℃ for 8 hours, annealing, cooling in air to 270 ℃ for extrusion at the extrusion ratio of 10 to obtain a magnesium alloy rod with the diameter of 10mm, carrying out solution treatment at 500 ℃ for 14 hours, and cooling along with the furnace. The properties of this example are shown in table 2 below.
Example 8:
this embodiment differs from embodiment 2 described above only in that: the preparation method has different technological parameters, and specifically,
preheating a crucible and a casting mold in a resistance furnace to over 170 ℃, cooling to 80 ℃, coating ZnO coating, heating the crucible to 800 ℃, adding pure magnesium and Sr powder, scattering a covering agent, and keeping the temperature for about 20 minutes; when the temperature is heated to 950 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring and removing slag, then spreading covering agent, and keeping the temperature for 30 minutes; and (3) heating to 1000 ℃, adding the Mg-Zr intermediate alloy and the Mg-Sm intermediate alloy, stirring, removing slag, scattering the solvent again, keeping the temperature for 20 minutes, cooling to 950 ℃, adding a refining agent for refining, standing for 35 minutes, cooling to 870 ℃, pouring the melt into a steel die with the preheating temperature of 210 ℃, and cooling at room temperature to obtain the ingot. Keeping the temperature of the cast ingot at 300 ℃ for 5 hours, then forging the cast ingot at 320 ℃ with the forging rate of 10 percent, carrying out solution treatment at 550 ℃ for 10 hours, and cooling the cast ingot along with the furnace.
Example 9:
this embodiment differs from embodiment 2 described above only in that: the preparation method has different technological parameters, the ingot is kept at 400 ℃ for 10 hours, then is forged at 270 ℃, the forging rate is 30 percent, and is subjected to solution treatment at 550 ℃ for 10 hours, and then is cooled along with the furnace. The properties of this example are shown in table 2 below.
Example 10:
this embodiment differs from embodiment 3 described above only in that: the preparation method has different technological parameters, and specifically,
preheating a crucible and a casting mold to over 170 ℃ in a resistance furnace, cooling to 75 ℃, coating ZnO coating, heating the crucible to 670 ℃, adding pure magnesium and Sr powder, scattering a covering agent, and keeping the temperature for about 20 minutes; when the temperature is heated to 850 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring and removing slag, then spreading covering agent, and keeping the temperature for 40 minutes; and (3) when the temperature is increased to 990 ℃, adding the Mg-Zr intermediate alloy and the Mg-Sm intermediate alloy, stirring, removing slag, scattering the solvent again, keeping the temperature for 25 minutes, reducing the temperature to 850 ℃, adding a refining agent for refining, standing for 25 minutes, reducing the temperature to 780 ℃, pouring the melt into a steel die with the preheating temperature of 200 ℃, and cooling at room temperature to obtain the ingot. Keeping the temperature of the cast ingot at 550 ℃ for 55 hours, then forging the cast ingot at 450 ℃, wherein the forging rate is 50%, carrying out solution treatment at 530 ℃ for 10 hours, and cooling the cast ingot along with the furnace. The properties of this example are shown in table 2 below.
The properties of this example are shown in table 2 below.
Example 11:
this embodiment differs from embodiment 3 described above only in that: the preparation method has different technological parameters, and the annealing treatment step comprises the following steps: and (3) keeping the temperature of the cast ingot at 400 ℃ for 10 hours, annealing, cooling in air to 450 ℃ for extrusion at the extrusion ratio of 80 to obtain a magnesium alloy rod with the diameter of 10mm, carrying out solution treatment at 530 ℃ for 10 hours, and cooling along with the furnace.
Table 1 shows the composition (wt%) of the Mg-Nd-Zr-Sr-Sc-Sm degradable magnesium alloy in examples 1 to 5
Examples Nd Zr Sr Sc Sm Mg
Example 1 4.9 1.4 2.4 1.8 2.6 Allowance of
Example 2 4.5 1.2 2.2 1.4 2.0 Balance of
Example 3 4.2 1.0 2.1 1.2 1.3 Balance of
Example 4 4 1.5 2.5 1.5 0.8 Allowance of
Example 5 5 1.3 2 2 2.8 Balance of
Table 2 shows the mechanical properties and corrosion resistance of the Mg-Nd-Zr-Sr-Sc-Sm degradable magnesium alloys in examples 1 to 3, 6, 7, 9 and 10
Figure BDA0003418180790000071
The content of unavoidable impurities in each example in table 1 above is 0.1% or less. As can be seen from table 2 above, the magnesium alloy prepared by the present invention has high tensile strength, yield strength, elongation and corrosion resistance.

Claims (6)

1. The preparation method of the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy is characterized in that the Mg-Nd-Zr-Sr-Sc-Sm biodegradable magnesium alloy comprises the following components in percentage by weight: nd: 4-5%, Zr: 1 to 1.5%, Sr: 2-2.5%, Sc: 1.2-2%, Sm: 0.8-2.8%, the content of other inevitable impurities is less than or equal to 0.1%, and the balance is Mg, and the preparation method sequentially comprises the following steps:
1) mixing pure magnesium, Mg-Nd intermediate alloy, Mg-Zr intermediate alloy, Sr powder, Mg-Sc intermediate alloy and Mg-Sm intermediate alloy according to the weight percentage;
2) preheating a crucible and a casting mold to over 170 ℃, cooling to 70-80 ℃, coating ZnO coating, heating the crucible to 670-800 ℃, adding pure magnesium and Sr powder, and scattering a covering agent;
3) heating to 850-950 ℃, adding Mg-Sc intermediate alloy and Mg-Nd intermediate alloy, stirring, removing slag, then spreading covering agent, and keeping the temperature for 30-40 minutes;
4) heating to 980-1000 ℃, adding Mg-Zr intermediate alloy and Mg-Sm intermediate alloy, stirring, removing slag, scattering solvent again, and keeping the temperature for 20-30 minutes;
5) reducing the temperature to 850-950 ℃, adding a refining agent for refining, standing for 25-35 minutes, reducing the temperature to 780-870 ℃, pouring the melt into a steel die with the preheating temperature of 190-210 ℃, and cooling at room temperature to obtain an ingot;
6) and annealing, extruding or forging the cast ingot, and carrying out solution treatment to obtain the magnesium alloy.
2. The method of claim 1, wherein: the tensile strength of the degradable magnesium alloy is 350-420 MPa, the yield strength is 290-356 MPa, the Vickers hardness is 45-52, the elongation is more than 30%, and the average corrosion rate of 96h is 0.09-0.21 mg/(cm) 2 ·h)。
3. The method of claim 1, wherein: in the step 6), the extrusion temperature during extrusion is 270-450 ℃, and the extrusion ratio is 10-80.
4. The method of claim 1, wherein: in the step 6), the forging is firstly carried out at 300-550 ℃ for 5-55 hours, and then the forging is carried out at 270-450 ℃, wherein the forging rate is 10-50%.
5. The method of claim 1, wherein: in step 2), the crucible was heated to 750 ℃ and the holding time was 30 minutes in step 4), and the crucible was left to stand for 30 minutes after refining in step 5).
6. The method of claim 1, wherein: in the step 6), the solution treatment temperature is 500-580 ℃, and the treatment time is 8-14 hours.
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