CN115287476A - Preparation method and application of medical magnesium alloy capable of being uniformly degraded - Google Patents
Preparation method and application of medical magnesium alloy capable of being uniformly degraded Download PDFInfo
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- CN115287476A CN115287476A CN202210768195.9A CN202210768195A CN115287476A CN 115287476 A CN115287476 A CN 115287476A CN 202210768195 A CN202210768195 A CN 202210768195A CN 115287476 A CN115287476 A CN 115287476A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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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
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- 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
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Abstract
The invention discloses a preparation method of a medical magnesium alloy capable of being uniformly degraded, which comprises the following steps: s1) weighing each material according to the mass percentage of the designed components; s2) smelting the materials weighed in the S1) under a protective atmosphere, refining, and finally casting into a cast ingot; s3) homogenizing the ingot casting obtained in the S2); s4) carrying out extrusion deformation treatment on the cast ingot treated in the S3) to obtain a magnesium alloy; and S5) annealing the extruded magnesium alloy obtained in the step S4), and air-cooling to obtain the medical magnesium alloy with uniform corrosion characteristics and uniform degradation. The alloy of the invention is subjected to component design, heat treatment and extrusion to obtain the alloy with uniform corrosivity and mechanical properties. The medical magnesium alloy can meet the requirements of medical application fields such as cardiovascular stents, medical bone nails and anastomosis nails on material corrosion performance and mechanical property, has uniformly distributed grain structures, and shows excellent strong plasticity and corrosion resistance.
Description
Technical Field
The invention belongs to the field of degradable medical materials, and particularly relates to a preparation method of a medical magnesium alloy capable of being uniformly degraded.
Background
At present, the magnesium alloy has good biocompatibility and density which is close to human compact bone (1.75 g/cm < 3 >), and the elastic modulus is also close to human bone (10-40 GPa), so that the stress shielding effect can be avoided. In addition, the magnesium alloy also has good biodegradability, and compared with stainless steel and titanium alloy, the magnesium alloy avoids the pain caused by secondary operation. However, although medical polymer materials can also be degraded, they have poor mechanical properties and are difficult to be used as support materials. The magnesium alloy as a biomedical material has the characteristics of excellent mechanical property and degradability and absorbability, and has great potential as a degradable medical material. However, magnesium alloys are chemically reactive and corrode too quickly in the human environment, resulting in premature loss of mechanical properties and loss of fixation and support of the implant site.
Therefore, it is necessary to develop a novel medical magnesium alloy having uniform degradation.
Disclosure of Invention
In order to overcome the defects of too fast degradation and uneven corrosion of the medical magnesium alloy, the invention aims to provide a preparation method of the medical magnesium alloy capable of being degraded uniformly, and the alloy has good corrosion resistance and mechanical property.
The invention is realized by the following technical scheme: a preparation method of medical magnesium alloy capable of being uniformly degraded comprises the following steps:
s1) weighing each material according to the mass percent of the designed components, wherein the material contains Gd, and the mass percent of the Gd is less than 1%;
s2) smelting the materials weighed in the S1) under a protective atmosphere, refining, and finally casting into a cast ingot;
s3) homogenizing the ingot casting obtained in the S2);
s4) carrying out extrusion deformation treatment on the cast ingot treated in the S3) to obtain a magnesium alloy;
and S5) annealing the extruded magnesium alloy obtained in the step S4), and air-cooling to obtain the medical magnesium alloy with uniform corrosion characteristics and uniform degradation.
The S4) and the S5) are necessary steps in the process, the sequence of the two steps cannot be changed, otherwise, the medical magnesium alloy capable of being uniformly degraded cannot be obtained, and the components of the magnesium alloy are combined with the components to realize that the alloy matrix has uniformly distributed alpha-Mg grain structure and Mg3Zn3Gd2 precipitated phase, which are all indispensable.
Further, the matrix of the uniformly degradable medical magnesium alloy has uniformly distributed alpha-Mg grain structure and Mg3Zn3Gd2 precipitated phase, and the size of the alpha-Mg grain structure is 8-15 mu m; and the potential difference between the Mg3Zn3Gd2 precipitated phase and the magnesium alloy matrix is 0.13-0.14 v.
Further, the tensile strength of the medical magnesium alloy capable of being uniformly degraded at room temperature is as follows: 229-247 MPa, yield strength: 138-158 MPa, and the room temperature elongation is as follows: 19 to 28 percent. After the artificial body fluid is soaked in the simulated body fluid for 480 hours, the weight loss rate is 0.218-0.354 mm/year.
Further, the mass percentages of the elements of the materials in the S1) are as follows: 1.5 to 2.0% of Zn, mn:0.3 to 0.6%, gd:0.45 to 0.79 percent, sr:0.15 to 0.3 percent, and the balance of Mg and inevitable impurity elements.
Furthermore, the sum of the mass percent of the unavoidable impurity elements is less than 0.015 percent, and the mass percent of Fe, ni and Cu in the unavoidable impurities is less than 0.005 percent, 0.005 percent and 0.005 percent respectively.
Further, the specific process in S2) is as follows:
firstly, the temperature is kept at 750-780 ℃ for 30-60 min, the materials are stirred for 5-10 min after being melted, then the temperature is reduced to 720-740 ℃ for refining for 5-10 min, the temperature is raised to 750-780 ℃ after refining, standing is carried out for 6-8 min, and the temperature of the melt is reduced to 700-720 ℃ for casting.
Further, the homogenization treatment in the step S3) adopts two-stage homogenization heat treatment, and the process parameters are as follows: the temperature is 350-480 ℃, and the heat preservation time is 16-24 h.
Further, the extrusion deformation temperature in the step S4) is 400 ℃, the extrusion ratio is 16:1.
further, the temperature of the annealing treatment in the S5) is 200-250 ℃, and the heat preservation time is 0.5-1 h.
Further, the respective materials of S1) were high purity magnesium ingot with a purity of 99.99%, high purity zinc ingot with a purity of 99.99%, mg-5% by weight of Mn, mg-25% by weight of Gd and Mg-20% by weight of Sr intermediate alloy, respectively.
The medical magnesium alloy which can be uniformly degraded and prepared by the method is applied to preparation of cardiovascular stents, medical bone nails and anastomosis nails.
The invention has the following beneficial effects:
(1) The uniform degradable medical magnesium alloy prepared by the invention has uniform grain structure and uniformly distributed Mg3Zn3Gd2 precipitated phase, wherein the potential difference between the Mg3Zn3Gd2 and the magnesium alloy matrix is 0.13-0.14 v, and the driving force of galvanic corrosion is small. After rare earth Gd element is added into the magnesium alloy, the hydration of the corrosion film layer is reduced in the corrosion process, the stability of the corrosion product layer is improved, the compactness of the corrosion film layer is improved, and the matrix is protected to a certain extent.
(2) The invention has uniform corrosivity and mechanical property through component design, heat treatment and extrusion forming. The obtained alloy can meet the requirements of medical application fields such as cardiovascular stents, medical bone nails and anastomosis nails on the corrosion performance and mechanical property of materials.
(3) The preparation method of the medical magnesium alloy capable of being uniformly degraded is simple, low in cost and capable of realizing industrial production.
Drawings
Fig. 1 is a flow chart of a preparation method of the medical magnesium alloy capable of being uniformly degraded.
FIG. 2 is a schematic representation of the metallographic microstructure of the alloy prepared in example 1 by the method of the invention.
FIG. 3 is a schematic representation of the metallographic microstructure of an alloy prepared by the method of example 2 of the present invention.
FIG. 4 is a schematic representation of the metallographic microstructure of the alloy prepared in example 3 using the method of the invention.
FIG. 5 is a schematic representation of the metallographic microstructure of the alloy prepared in example 4 by the method of the invention.
FIG. 6 is a TEM microstructure of an alloy obtained by the preparation of example 1 according to the method of the invention.
FIG. 7 is a TEM microstructure of an alloy obtained by the preparation of example 2 according to the method of the invention.
FIG. 8 is a TEM microstructure of an alloy obtained by the preparation of example 3 according to the method of the invention.
FIG. 9 is a TEM microstructure of an alloy obtained by the preparation of example 4 according to the method of the invention.
FIG. 10 is a 3D plot of the alloy prepared by example 1 of the method of the present invention after 480h immersion in simulated body fluid with corrosion products removed.
FIG. 11 is a 3D plot of the alloy prepared in example 2 using the method of the present invention after 480h immersion in simulated body fluid with corrosion products removed.
FIG. 12 is a 3D plot of the alloy prepared in example 3 using the method of the present invention after 480h immersion in simulated body fluid with corrosion products removed.
FIG. 13 is a 3D plot of the alloy prepared by example 4 using the method of the present invention after 480h immersion in simulated body fluid with corrosion products removed.
Detailed Description
The invention is further illustrated by the following figures and specific examples, which are not to be construed as limiting the invention to the following examples, other technical solutions being equivalent in the field of application also falling within the scope of the invention, which is defined by the claims.
As shown in fig. 1, the preparation method of the medical magnesium alloy capable of being uniformly degraded provided by the invention specifically comprises the following steps:
s1) weighing each material according to the mass percent of the designed components, wherein the material contains Gd, and the mass percent of the Gd is less than 1%;
s2) smelting the materials weighed in the S1) under a protective atmosphere, refining, and finally casting into an ingot;
s3) homogenizing the ingot casting obtained in the S2);
s4) carrying out extrusion deformation treatment on the cast ingot treated in the S3) to obtain a magnesium alloy;
and S5) annealing the extruded magnesium alloy obtained in the step S4), and air-cooling to obtain the medical magnesium alloy with uniform corrosion characteristics and uniform degradation.
The matrix of the uniformly degradable medical magnesium alloy has uniformly distributed alpha-Mg grain structure and Mg3Zn3Gd2 precipitated phase, and the size of the alpha-Mg grain structure is 8-15 mu m; and the potential difference between the Mg3Zn3Gd2 precipitated phase and the magnesium alloy matrix is 0.13-0.14 v.
The tensile strength of the medical magnesium alloy capable of being uniformly degraded at room temperature is as follows: 229-247 MPa, yield strength: 138-158 MPa, and the room temperature elongation is as follows: 19 to 28 percent. After the artificial body fluid is soaked in the simulated body fluid for 480 hours, the weight loss rate is 0.218-0.354 mm/year.
The mass percentages of the elements of the materials in the S1) are as follows: 1.5 to 2.0% of Zn, mn:0.3 to 0.6%, gd:0.45 to 0.79 percent, sr:0.15 to 0.3 percent, and the balance of Mg and inevitable impurity elements.
The sum of the mass percent of the inevitable impurity elements is less than 0.015 percent, and the mass percent of Fe, ni and Cu in the inevitable impurity elements is less than 0.005 percent, 0.005 percent and 0.005 percent.
The specific process in the S2) comprises the following steps:
firstly, the temperature is kept at 750-780 ℃ for 30-60 min, the materials are stirred for 5-10 min after being melted, then the temperature is reduced to 720-740 ℃ for refining for 5-10 min, the temperature is raised to 750-780 ℃ after refining, standing is carried out for 6-8 min, and the temperature of the melt is reduced to 700-720 ℃ for casting.
The homogenization treatment in the step S3) adopts two-stage homogenization heat treatment, and the process parameters are as follows: the temperature is 350-480 ℃, and the heat preservation time is 16-24 h.
The extrusion deformation temperature in the S4) is 400 ℃, the extrusion ratio is 16:1.
the temperature of the annealing treatment in the S5) is 200-250 ℃, and the heat preservation time is 0.5-1 h.
The respective materials of S1) were respectively a high purity magnesium ingot with a purity of 99.99%, a high purity zinc ingot with a purity of 99.99%, mg-5% by weight of Mn, mg-25% by weight of Gd and Mg-20% by weight of Sr master alloy.
The medical magnesium alloy which can be uniformly degraded and is prepared by the method is applied to the fields of cardiovascular stents, medical bone nails and anastomosis nail medical appliances.
Example 1:
the paint is prepared from the following components in percentage by mass: 1.7% of Zn, 0.45% of Mn, 0.45% of Gd, 0.15% of Sr and the balance of Mg and inevitable impurity elements. The preparation method comprises the following steps:
s1) weighing materials according to mass percent, wherein the materials comprise high-purity magnesium ingots, high-purity zinc ingots, mg-5 percent of Mn intermediate alloy, mg-25 percent of Gd intermediate alloy and Mg-20 percent of Sr intermediate alloy;
s2) ingot casting and smelting: smelting under the protection of high-purity argon, heating pure magnesium to 720 ℃ for melting, then adding Mg-5% Mn master alloy and Mg-25% Gd master alloy in order, raising the melt temperature to 740 to 760 ℃ for 10 to 20 minutes, cooling to 720 ℃ and adding pure zinc and Mg-20 Sr master alloy, stirring sufficiently at 720 ℃ for 5 to 10 minutes, refining for degassing and removing surface dross, casting to a graphite mold;
s3) casting the alloy melt obtained in the S2) into an ingot at 720 ℃ through gravity casting;
s4) homogenizing heat treatment: s3) putting the cast ingot into a vacuum heat treatment furnace filled with high-purity argon for protection, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, then heating to 420 ℃ at the same heating rate, preserving heat for 20 hours, and then processing into an extruded blank;
s5) hot extrusion: preheating an extrusion blank at 400 ℃ for 0.5-1 h, coating molybdenum disulfide lubricating grease on the surface, and extruding by an extruder at the extrusion temperature of 400 ℃ in an extrusion ratio of 16;
s6) annealing treatment: and keeping the temperature of the extruded material at 200 ℃ for 0.5h, and cooling in air.
The magnesium alloy obtained in this example S6) had a room-temperature yield strength of 138MPa, a room-temperature tensile strength of 229MPa, and a room-temperature elongation of 28%. After soaking in simulated body fluid for 480h, the weight loss rate is 0.218mm/year, and the metallographic microstructure of the obtained magnesium alloy is shown in figure 2; TEM microstructure of the alloy, as shown in fig. 6; the 3D morphology of the alloy after corrosion products were removed after 480h immersion in simulated body fluid is shown in FIG. 10.
Example 2:
the coating is prepared from the following components in percentage by mass: 1.85% of Zn, 0.45% of Mn, 0.6% of Gd, 0.15% of Sr and the balance of Mg and inevitable impurity elements. The preparation method comprises the following steps:
s1) weighing materials according to mass percent, wherein the materials comprise high-purity magnesium ingots, high-purity zinc ingots, mg-5 percent of Mn intermediate alloy, mg-25 percent of Gd intermediate alloy and Mg-20 percent of Sr intermediate alloy;
s2) ingot casting and smelting: smelting under the protection of high-purity argon, heating pure magnesium to 720 ℃ for melting, then sequentially adding Mg-5 percent Mn intermediate alloy and Mg-25 percent Gd intermediate alloy, raising the temperature of the melt to 740-760 ℃ for heat preservation for 10-20 minutes, cooling to 720 ℃, adding pure zinc and Mg-20 percent Sr intermediate alloy, fully stirring for 5-10 minutes at 720 ℃, refining, degassing, removing surface scum, and casting to a graphite mold;
s3) casting the alloy melt obtained in the S2) into an ingot at 720 ℃ through gravity casting;
s4) homogenizing heat treatment: s3) putting the cast ingot into a vacuum heat treatment furnace filled with high-purity argon for protection, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, then heating to 460 ℃ at the same heating rate, preserving heat for 20 hours, and then processing into an extruded blank;
s5) hot extrusion: preheating an extrusion blank at 400 ℃ for 0.5-1 h, coating molybdenum disulfide lubricating grease on the surface, and extruding by an extruder at the extrusion temperature of 400 ℃ and the extrusion ratio of 16;
s6) annealing treatment: and keeping the temperature of the extruded material at 200 ℃ for 1h, and cooling in air.
The magnesium alloy obtained in this example S6) had a room-temperature yield strength of 154MPa, a room-temperature tensile strength of 233MPa, and a room-temperature elongation of 24%. After soaking in simulated body fluid for 480h, the weight loss rate is 0.287mm/year.
The metallographic microstructure of the obtained magnesium alloy is shown in fig. 3; TEM microstructure of the alloy, as shown in fig. 7; the 3D morphology of the alloy after corrosion product removal after 480h immersion in simulated body fluid is shown in FIG. 11.
Example 3:
the coating is prepared from the following components in percentage by mass: zn 2%, mn 0.5%, gd 0.75%, sr 0.15%, and the balance of Mg and inevitable impurity elements. The preparation method comprises the following steps:
s1) weighing the materials in mass percent using a high purity magnesium ingot, a high purity zinc ingot, mg-5% of a Mn master alloy, mg-25% of a Gd master alloy and Mg-20% of a Sr master alloy;
s2) ingot casting and smelting: smelting under the protection of high-purity argon, heating pure magnesium to 720 ℃ for melting, then adding Mg-5% Mn master alloy and Mg-25% Gd master alloy in order, raising the melt temperature to 740 to 760 ℃ for 10 to 20 minutes, cooling to 720 ℃ and adding pure zinc and Mg-20 Sr master alloy, stirring sufficiently at 720 ℃ for 5 to 10 minutes, refining for degassing and removing surface dross, casting to a graphite mold;
s3) casting the alloy melt obtained in the S2) into an ingot at 720 ℃ through gravity casting;
s4) homogenizing heat treatment: s3) putting the cast ingot into a vacuum heat treatment furnace filled with high-purity argon for protection, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, then heating to 480 ℃ at the same heating rate, preserving heat for 12 hours, and then processing into an extruded blank;
s5) hot extrusion: preheating an extrusion blank at 400 ℃ for 0.5-1 h, coating molybdenum disulfide lubricating grease on the surface, and extruding by an extruder at the extrusion temperature of 400 ℃ in an extrusion ratio of 16:1;
s6) annealing treatment: and keeping the temperature of the extruded material at 250 ℃ for 0.5h, and cooling in air.
The magnesium alloy obtained in this example S6) had a room-temperature yield strength of 152MPa, a room-temperature tensile strength of 242MPa, and a room-temperature elongation of 19%. After soaking in simulated body fluid for 480h, the weight loss rate is 0.309mm/year. The metallographic microstructure of the obtained magnesium alloy is shown in fig. 4; TEM microstructure of the alloy, as shown in fig. 8; the 3D morphology of the alloy after corrosion products were removed after 480h immersion in simulated body fluid is shown in FIG. 12.
Example 4:
the paint is prepared from the following components in percentage by mass: zn 2%, mn 0.35%, gd 0.75%, sr 0.3%, and the balance of Mg and unavoidable impurity elements. The preparation method comprises the following steps:
s1) weighing materials according to mass percent, wherein the materials comprise high-purity magnesium ingots, high-purity zinc ingots, mg-5 percent of Mn intermediate alloy, mg-25 percent of Gd intermediate alloy and Mg-20 percent of Sr intermediate alloy;
s2) ingot casting and smelting: smelting under the protection of high-purity argon, heating pure magnesium to 720 ℃ for melting, then adding Mg-5% Mn master alloy and Mg-25% Gd master alloy in order, raising the melt temperature to 740 to 760 ℃ for 10 to 20 minutes, cooling to 720 ℃ and adding pure zinc and Mg-20 Sr master alloy, stirring sufficiently at 720 ℃ for 5 to 10 minutes, refining for degassing and removing surface dross, casting to a graphite mold;
s3) casting the alloy melt obtained in the S2) into an ingot at 720 ℃ through gravity casting;
s4) homogenizing heat treatment: s3) putting the cast ingot into a vacuum heat treatment furnace filled with high-purity argon for protection, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 4h, then heating to 480 ℃ at the same heating rate, preserving heat for 12h, and then processing into an extruded blank;
s5) hot extrusion: preheating an extrusion blank at 400 ℃ for 0.5-1 h, coating molybdenum disulfide lubricating grease on the surface, and extruding by an extruder at the extrusion temperature of 400 ℃ and the extrusion ratio of 16;
s6) annealing treatment: and (4) preserving the heat of the extruded material at 250 ℃ for 0.5h, and cooling in air.
The magnesium alloy obtained in this example S6) had a room-temperature yield strength of 158MPa, a room-temperature tensile strength of 247MPa, and a room-temperature elongation of 20.5%. After soaking in simulated body fluid for 480h, the weight loss rate is 0.357mm/year. The metallographic microstructure of the obtained magnesium alloy is shown in fig. 5; TEM microstructure of the alloy, as shown in fig. 9; the 3D morphology of the alloy after corrosion products were removed after 480h immersion in simulated body fluid is shown in FIG. 13.
The preparation method of the medical magnesium alloy capable of being uniformly degraded is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core idea; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The following description is of the preferred embodiment for carrying out the present application, but is made for the purpose of illustrating the general principles of the application and is not to be taken in a limiting sense. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrases "comprising one of 8230; \8230;" 8230; "does not exclude the presence of additional like elements in articles of commerce or systems including such elements.
It should be understood that the term "and/or" as used herein is merely a relationship that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. The preparation method of the medical magnesium alloy capable of being uniformly degraded is characterized by comprising the following steps:
s1) weighing each material according to the mass percent of the designed components, wherein the material contains Gd, and the mass percent of the Gd is less than 1%;
s2) smelting the materials weighed in the S1) under a protective atmosphere, refining, and finally casting into a cast ingot;
s3) homogenizing the ingot casting obtained in the S2);
s4) carrying out extrusion deformation treatment on the cast ingot treated in the S3) to obtain a magnesium alloy;
and S5) annealing the extruded magnesium alloy obtained in the step S4), and air-cooling to obtain the medical magnesium alloy with uniform corrosion characteristics and uniform degradation.
2. The method according to claim 1, wherein the matrix of the uniformly degradable medical magnesium alloy has a uniformly distributed α -Mg grain structure and Mg3Zn3Gd2 precipitated phases, wherein the α -Mg grain structure has a size of 8 to 15 μm; and the potential difference between the Mg3Zn3Gd2 precipitated phase and the magnesium alloy matrix is 0.13-0.14 v.
3. The method of claim 1, wherein the uniformly degradable medical magnesium alloy has a tensile strength at room temperature of: 229-247 MPa, and the yield strength is: 138-158 MPa, and the room temperature elongation is as follows: 19 to 28 percent; after the artificial body fluid is soaked in the simulated body fluid for 480 hours, the weight loss rate is 0.218-0.354 mm/year.
4. The method according to claim 1, wherein the mass percentages of the elements of the materials in S1) are as follows: 1.5 to 2.0% of Zn, mn:0.3 to 0.6%, gd: 0.45-0.79%, sr:0.15 to 0.3 percent, and the balance of Mg and inevitable impurity elements.
5. The method according to claim 4, wherein the sum of the mass percentages of the unavoidable impurity elements is <0.015%, and the unavoidable impurities are <0.005% of Fe, <0.005% of Ni, and <0.005% of Cu.
6. The method according to claim 1, wherein the specific process in S2) is:
firstly, preserving heat for 30-60 min at the temperature of 750-780 ℃, stirring for 5-10 min after materials are all melted, then cooling to 720-740 ℃, refining for 5-10 min, heating to 750-780 ℃ after refining, standing for 6-8 min, and cooling the melt to 700-720 ℃ for casting.
7. The method as claimed in claim 1, wherein the homogenization treatment in S3) adopts a two-stage homogenization heat treatment, and the process parameters are as follows: the temperature is 350-480 ℃, and the heat preservation time is 16-24 h.
8. The method as claimed in claim 1, wherein the extrusion deformation in S4) has a temperature of 400 ℃, an extrusion ratio of 16:1.
9. the method according to claim 1, wherein the temperature of the annealing treatment in S5) is 200-250 ℃ and the holding time is 0.5-1 h.
10. The medical magnesium alloy which is prepared by the method of any one of claims 1 to 9 and can be uniformly degraded is applied to the preparation of cardiovascular stents, medical bone nails and anastomosis nails.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1355533A (en) * | 1962-08-10 | 1964-03-20 | Magnesium Elektron Ltd | Magnesium-based alloys for nuclear reactors |
| CN103343273A (en) * | 2013-07-03 | 2013-10-09 | 北京科技大学 | Biomedical degradable corrosion-resistant Mg-Zn-Zr alloy and preparation method thereof |
| CN111826564A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院金属研究所 | Absorbable magnesium alloy cosmetic line and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1355533A (en) * | 1962-08-10 | 1964-03-20 | Magnesium Elektron Ltd | Magnesium-based alloys for nuclear reactors |
| CN103343273A (en) * | 2013-07-03 | 2013-10-09 | 北京科技大学 | Biomedical degradable corrosion-resistant Mg-Zn-Zr alloy and preparation method thereof |
| CN111826564A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院金属研究所 | Absorbable magnesium alloy cosmetic line and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUZHAO XU等: ""The influence of Gd content on the microstructure, mechanical properties, corrosion behavior and corrosion film deposition mechanisms of asextruded Mg–Zn–Mn–Sr–Gd alloys for biomedical applications"", 《J MATER SCI》 * |
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