CN108642359B - High-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material and preparation method thereof - Google Patents
High-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material and preparation method thereof Download PDFInfo
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- CN108642359B CN108642359B CN201810879128.8A CN201810879128A CN108642359B CN 108642359 B CN108642359 B CN 108642359B CN 201810879128 A CN201810879128 A CN 201810879128A CN 108642359 B CN108642359 B CN 108642359B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- 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
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- 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
Abstract
The invention discloses a high-strength degradable biomedical Mg-Zn-Zr-Fe alloy material and a preparation method thereof. The magnesium alloy comprises the following components in percentage by mass: zn5.0-6.0%, Zr0.5-1.0%, Fe0.01-0.09%, and the balance Mg and inevitable impurities. The preparation method comprises smelting, casting homogenization treatment, hot extrusion and artificial aging treatment to obtain the biomedical magnesium alloy plate, bar and wire meeting the service requirements of the biological body fluid environment. The magnesium alloy is added with alloy elements harmless to a human body, and the magnesium alloy has no toxicity to the human body after being degraded in the body, excellent mechanical property, good mechanical property and processability and proper corrosion rate. The high-strength degradable biomedical Mg-Zn-Zr-Fe alloy material has the tensile strength of more than or equal to 360MPa and the yield strength of more than or equal to 320MPa, and is suitable for preparing medical materials such as bone nails and the like.
Description
Technical Field
The invention belongs to the field of biomedical multi-element magnesium alloy, and particularly relates to an Mg-Zn-Zr-Fe multi-element magnesium alloy material which can be absorbed in a biological body.
Background
Currently, the biological implantation metal materials widely used in clinical applications mainly include stainless steel, cobalt-chromium alloy, and titanium alloy. None of these metallic materials are degradable and their implants must be removed by a secondary operation after the functional recovery of the human tissue. Therefore, the degradable metal material has better development prospect in the field of biomedical materials in the future. The degradable metal materials currently under development are: magnesium alloys, iron alloys, and zinc alloys. Magnesium alloys have good biocompatibility, mechanical compatibility and other advantages, and have become a research hotspot in the field of biomedical materials in recent years. The advantages of magnesium are embodied as follows: (1) it is a mineral element necessary for human body, and can be discharged through urine when excessive, thus causing no toxic reaction; (2) the Young modulus is close to that of human bones, and the application of the related implant material can effectively relieve the stress shielding effect.
In recent years, researchers developed a series of degradable magnesium alloys, such as the invention patent Mg-Zn-Fe ternary magnesium alloy material absorbable in vivo (patent No. 200510111793.5), the invention patent Mg-Zn-Ca-Fe multi-element magnesium alloy material absorbable in vivo (patent No. 200510111792.0), the invention patent Mg-Zn-Zr-Mn magnesium alloy for biomedical use and its preparation method (application No. 201510870718.0), the invention patent degradable Mg-Zn-Zr-Sc alloy for biomedical use and its preparation method (application No. 201410101431.7), and the invention patent biodegradable corrosion-resistant Mg-Zn-Zr alloy for biomedical use and its preparation method (application No. 201310275808.6). The above patent adds Mn, Sc, Fe, Ca, Zr and other elements to Mg-Zn alloy to refine crystal grains and improve the corrosion resistance of the alloy. However, the tensile strength of the alloy is generally below 300MPa, and the alloy can only be used for manufacturing medical instruments with long implantation time. The requirements of the sports injury treatment and rehabilitation with shorter recovery period cannot be met, and the requirement that the material not only meets good biocompatibility, but also has higher degradation rate and higher tensile strength and yield strength is met.
Industrially, ZK60 series magnesium alloy (Mg- (5.5-6.0) Zn- (0.3-0.9) Zr, wt%) has wide application due to high strength. However, researches show that the excessively high Zn (more than 8 percent) content can cause the surface film of the magnesium alloy to loosen and fall off, and the corrosion resistance of the magnesium alloy is reduced; and the elongation of the magnesium alloy also decreases as the Zn content increases. Therefore, the ZK60 alloy with lower plasticity and poorer corrosion resistance has limited application in the biomedical field.
On the other hand, the application of magnesium alloy biomaterials is mainly problematic in that the corrosion rate is too fast, particularly the impurity content is one of the most important factors influencing the corrosion resistance of magnesium alloys, especially the contents of harmful elements such as Fe, Ni, Cu and Co in the alloys need to be controlledBelow allowable limit (maximum soluble limit of Fe, Cu and Ni 3 elements in Mg is 170X 10-6，1000×10-6，5×10-6) So as to effectively improve the corrosion resistance of the alloy.
Disclosure of Invention
In order to overcome the defects of the existing biomedical magnesium alloy, the invention provides a high-strength rapidly-degradable Mg-Zn-Zr-Fe alloy which can be applied to an organism implantation material and a preparation method thereof. The alloy has high tensile strength and yield strength, good biocompatibility and rapid degradation performance, and can be used as an interventional instrument for sports injury treatment and rehabilitation.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material, which consists of the following elements in percentage by weight: 5.0 to 6.0 percent of Zn, 0.5 to 1.0 percent of Zr, 0.01 to 0.09 percent of Fe, less than 0.01 percent of Al, less than 0.005 percent of Ni and less than 0.005 percent of Cu. The balance being Mg and unavoidable impurities thereof.
The research of the application finds that: in the Mg-Zn-Zr alloy, 0.01-0.09% of Fe is added, and because Fe and Mg do not form an intermediate phase, Fe and Zr play a role of nucleation particles simultaneously in the casting process, the grain size can be refined, the structure segregation is improved, and the corrosion resistance of the magnesium alloy is improved. However, since the corrosion of Mg is adversely affected by the increase of Fe content, the content of zinc in the magnesium alloy is increased, and the following results are found: when the Zn content is 5.0-6.0%, the performance of the surface film can be effectively improved, the allowable concentration of harmful impurities Fe, Ni and Cu in the alloy can be increased, and the influence of Fe on Mg corrosion is reduced, so that the magnesium alloy with excellent tensile strength, yield strength and proper degradation speed is obtained.
In some embodiments, the alloy material has a tensile strength of greater than or equal to 360MPa, a yield strength of greater than or equal to 320MPa, and an elongation of greater than or equal to 14%; in a 37 ℃ Hank's simulated body fluid, the corrosion rate is less than or equal to 0.28 mg-cm-2·day-1。
In some embodiments, the impurity elements are, by mass: al is less than 0.01%, Ni is less than 0.005%, and Cu is less than 0.005%.
The invention also provides a preparation method of the high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material, which comprises the following steps:
smelting magnesium ingots, zinc ingots, iron and Mg-30% Zr intermediate alloy, and casting into ingots;
homogenizing the cast ingot, and extruding into a plate, a rod or a wire;
and (4) carrying out artificial aging treatment and air cooling on the extruded plate, rod and wire to obtain the steel plate.
In some embodiments, the specific steps of "melting, pouring into an ingot" are: the magnesium ingot, the zinc ingot, the iron and the Mg-30% Zr intermediate alloy are subjected to heat preservation at 780-800 ℃ for 40-60 min, stirred for 5-10 min after the raw materials are melted, then cooled to 730-750 ℃ for refining for 20-30 min, heated to 750-780 ℃ after refining, kept stand for 30-40 min, and cast into ingots at 710-730 ℃.
In some embodiments, the homogenization treatment is carried out at 400-420 ℃, the heat preservation time is 16-18h, and then water cooling is carried out at 50-60 ℃.
The Mg-30% Zr intermediate alloy in the present application can be prepared by the method of rare metals and hard alloys in the thesis 2006,34(1):30-32 (Liujiaxiang, Yangqingshan, Liuzhuanping, Chenweiping, He Bining), or can be prepared by using a commercially available product.
In some embodiments, the specific conditions of the extrusion are: the extrusion temperature is 250-300 ℃, and the extrusion speed is 0.1-5 mm/s.
In some embodiments, the artificial aging treatment is carried out under the conditions of heat preservation at 150-160 ℃ for 24-36 h and air cooling.
The invention also provides the high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material prepared by any one of the methods.
The invention also provides application of any one of the Mg-Zn-Zr-Fe alloy materials in preparation of tissue engineering scaffold materials for treating and recovering sports injury.
The invention has the advantages of
(1) The Mg-Zn-Zr-Fe alloy of the invention selects Mg, Zn, Zr and Fe with good biocompatibility, and the degradation of the alloy does not produce harm to organisms.
(2) According to the Mg-Zn-Zr-Fe alloy and the preparation method thereof, by adding a proper amount of Fe element, the structure is refined, and the component segregation is improved, so that the strength is improved, and the material has excellent tensile strength, yield strength and degradation speed. The method is particularly suitable for preparing the implantation instrument for treating and recovering sports injury with shorter recovery period;
on the other hand, 5-6% of Zn is added, so that the performance of the surface film is improved, and the allowable concentration of Fe in the alloy is increased.
(3) The preparation method of the Mg-Zn-Zr-Fe alloy has low cost and simple process, and is easy to realize large-scale process production.
(4) The grain size of the extruded material is less than 10 mu m, the grain size is small, the structure segregation is small, and the mechanical and corrosion resistance properties are excellent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 shows the microstructure of an Mg-Zn-Zr-Fe extruded bar alloy.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The invention relates to a high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy, which comprises the following alloy elements in percentage by mass: zn5.0-6.0%, Zr0.5-1.0%, Fe0.01-0.09%, and the balance Mg and inevitable impurities.
In the Mg-Zn-Zr-Fe alloy, the impurity elements have the following mass percentages: al is less than 0.01%, Ni is less than 0.005%, and Cu is less than 0.005%.
The invention discloses a preparation method of a high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy, which comprises the following steps:
(1) weighing raw materials according to a ratio, wherein the raw materials adopt high-purity magnesium ingots, high-purity zinc ingots, high-purity iron and Mg-30% Zr intermediate alloy, smelting the raw materials under the condition of argon protection through a vacuum induction furnace, preserving heat at 780-800 ℃ for 40-60 min, stirring for 5-10 min after the raw materials are all melted, then cooling to 730-750 ℃, refining for 20-30 min, heating to 750-780 ℃ after refining, standing for 30-40 min, and casting into ingots at 710-730 ℃;
(2) homogenizing the cast ingot at 400-420 ℃, keeping the temperature for 16-18h, and cooling with water at 50-60 ℃;
(3) extruding the homogenized alloy into plates, rods and wires by an extruder under the conditions that the extrusion temperature is 250-300 ℃ and the extrusion speed is 0.1-5 mm/s;
(4) and (3) carrying out artificial aging treatment on the extruded plates, rods and wires at 150-160 ℃, keeping the temperature for 24-36 h, and carrying out air cooling.
The extrusion ratio of the extruder is selected according to the size of the required material.
The furnace was washed at least 2 times with argon before melting.
Mg in the high-purity magnesium ingot is more than or equal to 99.99 percent, and the rest is impurities; zn in the high-purity zinc ingot is more than or equal to 99.99 percent, and the balance is impurities; fe in the high-purity iron powder is more than or equal to 99.98 percent, and the balance is impurities; the mass percent of Zr in the Mg-30% Zr intermediate alloy is 29-31%, the mass percent of impurities is less than 0.005%, and the balance is Mg.
Example 1
The Mg-Zn-Zr-Fe alloy elements comprise the following components in percentage by mass: 5.8% of Zn, 0.65% of Zr, 0.03% of Fe, 0.005% of Al, 0.004% of Ni, 0.004% of Cu and the balance of Mg.
The raw materials are as follows: an Mg ingot with a purity of 99.995%, a Zn ingot with a purity of 99.993%, an Fe ingot with a purity of 99.987%, and an Mg — Zr master alloy with Zr at 29.8% by mass (0.004% by mass of impurities).
Weighing raw materials according to a ratio, smelting the raw materials by a vacuum induction furnace under the protection of argon, preserving heat at 800 ℃ for 60min, stirring for 5min after the raw materials are all molten, then cooling to 730 ℃, refining for 25min, heating to 760 ℃ after refining, standing for 30min, and casting into ingots at 710 ℃;
homogenizing the cast ingot at 420 ℃, keeping the temperature for 16h, and cooling with water at 60 ℃;
extruding the homogenized alloy into a rod by an extruder under the conditions that the extrusion temperature is 250 ℃ and the extrusion speed is 0.1mm/s, wherein the extrusion ratio is 30;
and (3) carrying out artificial aging treatment on the extruded plate, rod and wire at 150 ℃, keeping the temperature for 24h, and cooling in air.
The bar microstructure of the alloy is shown in FIG. 1, with an average grain size of about 7 μm; (ii) a The tensile strength of the alloy at room temperature is 368MPa, the yield strength is 335MPa, and the elongation is 14%. (ii) a In a 37 ℃ Hank's simulated body fluid (composition shown in Table 1), the corrosion rate was 0.26 mg-cm-2·day-1The etching mode is uniform etching.
TABLE 1 Hank's simulated humoral chemistry compositions (g/L) for experiments
Example 2
The Mg-Zn-Zr-Fe alloy elements comprise the following components in percentage by mass: 5.6% of Zn, 0.74% of Zr, 0.05% of Fe, 0.004% of Al, 0.003% of Ni, 0.004% of Cu and the balance of Mg.
The raw materials are as follows: an Mg ingot with a purity of 99.995%, a Zn ingot with a purity of 99.993%, an Fe ingot with a purity of 99.987%, and an Mg — Zr intermediate alloy with Zr at 30% by mass (impurity mass percentage of 0.004%).
Weighing raw materials according to a ratio, smelting the raw materials by a vacuum induction furnace under the protection of argon, preserving heat at 790 ℃ for 50min, stirring for 10min after the raw materials are all melted, then cooling to 750 ℃, refining for 30min, heating to 780 ℃, standing for 40min after refining, and casting into ingots at 720 ℃;
homogenizing the cast ingot at 410 ℃, keeping the temperature for 18h, and cooling with water at 55 ℃;
extruding the homogenized alloy into a rod by an extruder under the conditions that the extrusion temperature is 280 ℃ and the extrusion speed is 0.3mm/s, wherein the extrusion ratio is 20;
and (3) carrying out artificial aging treatment on the extruded plates, rods and wires at 155 ℃, keeping the temperature for 30h, and carrying out air cooling.
The average grain size of the alloy rods is about 6 μm; the tensile strength of the alloy at room temperature is 372MPa, the yield strength is 338MPa, and the elongation is 15%. (ii) a In a 37 ℃ Hank's simulated body fluid (composition shown in Table 1), the corrosion rate was 0.28 mg-cm-2·day-1The etching mode is uniform etching.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A high-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material is characterized by comprising the following elements in percentage by weight: 5.0-6.0% of Zn, 0.5-1.0% of Zr, 0.01-0.09% of Fe, less than 0.01% of Al, less than 0.005% of Ni and less than 0.005% of Cu; the balance being Mg and unavoidable impurities thereof.
2. The alloy material of claim 1, wherein the alloy material has a tensile strength of not less than 360MPa, a yield strength of not less than 320MPa, and an elongation of not less than 14%; in a 37 ℃ Hank's simulated body fluid, the corrosion rate is less than or equal to 0.28mg cm-2·day-1。
3. The preparation method of the high-strength rapidly-degradable biomedical Mg-Zn-Zr-Fe alloy material according to claim 1, is characterized by comprising the following steps:
smelting magnesium ingots, zinc ingots, iron and Mg-30% Zr intermediate alloy, and casting into ingots;
homogenizing the cast ingot, and extruding into a plate, a rod or a wire;
and (4) carrying out artificial aging treatment and air cooling on the extruded plate, rod and wire to obtain the steel plate.
4. The method of claim 3, wherein the step of melting and casting into an ingot comprises the steps of: the magnesium ingot, the zinc ingot, the iron and the Mg-30% Zr intermediate alloy are subjected to heat preservation at 780-800 ℃ for 40-60 min, stirred for 5-10 min after the raw materials are melted, then cooled to 730-750 ℃ for refining for 20-30 min, heated to 750-780 ℃ after refining, kept stand for 30-40 min, and cast into ingots at 710-730 ℃.
5. The method according to claim 3, wherein the homogenization treatment is carried out at 400 to 420 ℃ for 16 to 18 hours, and then water cooling is carried out at 50 to 60 ℃.
6. The method according to claim 3, wherein the specific conditions of the extrusion are: the extrusion temperature is 250-300 ℃, and the extrusion speed is 0.1-5 mm/s.
7. The method according to claim 3, wherein the artificial aging treatment is carried out under the conditions of heat preservation at 150-160 ℃ for 24-36 h and air cooling.
8. The high-strength rapidly-degradable biomedical Mg-Zn-Zr-Fe alloy material prepared by the method of any one of claims 3 to 7.
9. Use of the Mg-Zn-Zr-Fe alloy material according to claim 1 or 2 for the preparation of tissue engineering scaffold materials for sports injury treatment and rehabilitation.
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