CN112813324B - Precipitation strengthening type implantable magnesium alloy and preparation process thereof - Google Patents
Precipitation strengthening type implantable magnesium alloy and preparation process thereof Download PDFInfo
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- CN112813324B CN112813324B CN201911129586.0A CN201911129586A CN112813324B CN 112813324 B CN112813324 B CN 112813324B CN 201911129586 A CN201911129586 A CN 201911129586A CN 112813324 B CN112813324 B CN 112813324B
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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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 relates to a precipitation strengthening type biomedical magnesium alloy capable of being degraded in vivo and a preparation process thereof. The weight percentages of the components are as follows: 5.0-6.0% of Zns, 1.0-2.0% of Yb, 0.3-0.5% of Zrs and the balance of Mg; submicron-scale second phases are dispersed in the magnesium matrix. Firstly, alloy ingot casting is smelted according to the designed components, the equiaxial, uniform and fine initial crystal grains are ensured, then the second phase is ensured to be fully dissolved into a matrix through solid solution treatment, and then the submicron-order second phase is fully dispersed and precipitated through aging treatment. The magnesium alloy prepared by the process has the advantages of corrosion resistance, high strength, good biocompatibility and complete in-vivo degradation, and is suitable for biological implants such as vascular stents, bone nails and bone plates which simultaneously require certain strength and corrosion service period. According to the invention, a heavy rare earth element ytterbium (Yb) is introduced into an alloy system to regulate and control the appearance and distribution of a precipitated phase, so that the corrosion resistance of a matrix alloy is effectively improved while a matrix is precipitated and strengthened by virtue of fine second phase dispersion, and the problem of over-rapid corrosion in biomedical applications is solved. The preparation process is universal and efficient, and has good popularization prospect.
Description
Technical Field
The invention belongs to the technical field of biological alloy processing, and particularly relates to a precipitation-strengthened biomedical implantable magnesium alloy material and a preparation process thereof.
Background
Magnesium alloys have attracted much attention in the field of biomedical implant materials due to their excellent biocompatibility, degradability, and density and elastic modulus similar to those of human bones. Researches show that the bracket, the bone plate and the like prepared by the magnesium alloy are not only harmless after being implanted into a human body, but also can be gradually degraded in the biological environment of the human body, so that the patient is free from the pain of secondary operations, and the magnesium alloy bracket, the bone plate and the like have obvious advantages in the field of clinical application. However, the higher degradation rate of magnesium alloy often leads to the loss of mechanical integrity before the end of the service period, which greatly limits the further popularization and application of magnesium alloy materials in the field of biomedical materials. Therefore, research and development of novel corrosion-resistant implantable magnesium alloys have become a research hotspot.
Precipitation strengthening is one of common and effective strengthening means of magnesium alloy, and through reasonable design of alloy components and effective control of a heat treatment process, submicron precipitated phases are fully dispersed and precipitated in a matrix (rich in high hydrogen evolution overpotential elements), the strengthening effect of the precipitated phases is fully exerted, the cathode process is retarded, the local corrosion tendency is inhibited, and finally the mechanical property of the magnesium alloy material is greatly improved and the corrosion resistance of the magnesium alloy material is improved.
Although other widely used methods for improving the corrosion resistance of implantable magnesium alloys have shown some efficacy, they have various disadvantages. For example, the film coating method may have loose or poor combination of the film layer, requires addition of a complexing agent, and has extremely high energy consumption, thus increasing the production cost; meanwhile, the complex process results in short production period and is not suitable for large-scale production; the requirement for equipment is high, and the maintenance cost of the instrument is increased, so that the method has great limitation in the field of industrial application. The large plastic deformation method has the disadvantages of uneven tissue structure of the prepared material, low production efficiency, inapplicability to large-scale production, limited material size and specification, difficulty in preparing large-size samples, high cost and complex process line. Element addition method: the addition of multiple alloy elements has good improvement on the corrosion resistance of the biomedical magnesium alloy, but also brings different problems, such as: excessive Zn can reduce the corrosion resistance of the magnesium alloy; al is neurotoxic and can inhibit the growth of a matrix; the addition of part of rare earth elements can cause cell proliferation and thrombus; fe and Cu cause the corrosion resistance of the magnesium alloy to be lowered.
In view of the above, the invention aims to explore a precipitation strengthening type implantable magnesium alloy and a preparation process thereof, the process utilizes the reasonable combination of component design, smelting and heat treatment processes to ensure that submicron precipitated phases are uniformly dispersed and precipitated, the corrosion resistance of a matrix is fully exerted, and simultaneously the uniform corrosion and the formation of a compact corrosion layer are promoted by the dispersed and precipitated submicron precipitated phases, and the improvement of mechanical property and corrosion resistance is obtained.
Disclosure of Invention
The invention aims to provide a precipitation strengthening type implantable magnesium alloy and a preparation process thereof.
The invention aims to fully play the good biocompatibility of Mg, the aging strengthening effect of Zn, the improvement effect of Yb on the second phase form and the oxide film structure and the grain refining effect of Zr by taking Mg-Zn-Yb-Zr alloy as an object under the premise of determining that the low-content Yb addition has no definite biological toxicity in a previous test from the viewpoint of biological safety. The alloy components and the Yb addition amount are optimized, and the novel medical magnesium alloy and the preparation process thereof are developed. On the basis of fully researching the alloy precipitation behavior of the system, the size, distribution and form of a precipitated phase are adjusted through solid solution and aging treatment, the mechanical property of the system is greatly improved through the dispersion precipitation effect of a fine second phase, the problem of excessively high biological corrosion rate in clinical application is solved, and the comprehensive performance requirements of the system as a biological implantation material such as a bone plate, a bone nail, an intravascular stent and the like are met.
Therefore, the technical problem to be solved by the invention is to overcome the disadvantages of the medical implanted magnesium alloy production technology in the background technology, to design and smelt Mg-Zn-Yb-Zr alloy cast ingots with proper component proportion from the perspective of biocompatibility, toughness and corrosion resistance of the medical magnesium alloy, to determine the preferable solid solution and aging process suitable for the system as-cast alloy, to realize the improvement of toughness and biological corrosion resistance by the aging precipitation strengthening of the second phase, and to meet the degradation rate requirement of the biomedical material implanted in a short time.
The purpose of the invention is realized by the following technical scheme:
firstly, by optimizing the design of alloy elements and by means of a reasonable smelting and casting process, the refining effect of Zr and Yb on the solidification structure of the magnesium alloy is fully exerted, the melt is purified, and the quality of an initial ingot blank is improved from the source; then carrying out solid solution treatment on the casting blank under the protection of gas, fully dissolving the second phase back and eliminating segregation; and then carrying out aging treatment to fully disperse and precipitate the submicron-order second phase, thereby obtaining the magnesium alloy lump material with good corrosion resistance. The method is based on the selection of alloy components, the control of the initial state of the blank and the optimization of heat treatment parameters, combines solid solution and precipitation strengthening, and prepares the precipitation strengthening type implantable rare earth magnesium alloy with low cost and short flow.
In order to achieve the technical purpose, the invention provides the following specific technical scheme (as shown in figure 1): smelting → solid solution → aging;
1) the meltingComprises the following steps: at SF6＋CO2In the gas protection, alloy ingots are prepared by smelting components of Zn5.0-6.0%, Yb 1.0-2.0%, Zr0.3-0.5% and the balance of Mg, the smelting temperature is 770 ℃, the alloy ingots are fully molten and then kept stand at 720 ℃ for 20 min, slag is removed, and then the alloy ingots are discharged for casting and are naturally cooled to room temperature;
2) the solid solution is as follows: preserving heat for 24-36 hours in an environment of 400 ℃ and filling argon to ensure that a second phase distributed along a crystal boundary is fully dissolved back into a matrix, ensuring that a blank is not oxidized during solid solution, and then cooling to room temperature by water;
3) the aging is as follows: and heating the blank subjected to the solution treatment to 200 ℃ in an argon environment along with a furnace, preserving the heat for 16-20 hours, and finally uniformly dispersing and precipitating a submicron-grade second phase in a magnesium matrix.
Further, the total amount of inclusion elements of the precipitation-strengthened implantable magnesium alloy other than Mg, Yb, Zn, Zr is no greater than 0.4 wt.%.
Compared with the prior art, the method has the beneficial effects that:
1. the precipitation strengthening type Mg-Zn-Yb-Zr implantable magnesium alloy has the advantages that the room-temperature tensile strength reaches more than 290 MPa, the degradation rate in SBF simulated body fluid is one to two orders of magnitude lower than that of ZK60, the size of a second phase is smaller than 1 mu m, and the mechanical property and the corrosion resistance of the magnesium alloy are greatly improved;
2. the precipitation strengthening Mg-Zn-Yb-Zr implantable magnesium alloy selects nutrient elements with good biocompatibility as alloy components, strictly limits the addition amount, and can be used for biological implants such as bone plates, bone nails, intravascular stents and the like.
The magnesium alloy material provided by the invention has the advantages of novel component design, excellent mechanical property, excellent corrosion resistance, excellent biocompatibility, complete degradation in vivo, simple and feasible preparation technology, and capability of enabling the magnesium alloy to generate excellent effect in the field of medical implant materials, particularly achieving remarkable improvement on corrosion resistance compared with similar technology, and no report of preparing similar precipitation strengthening type rare earth magnesium alloy by utilizing rare earth Yb and comprehensively applying a heat treatment process is searched at present. By implementing the scheme, the magnesium alloy can obtain excellent mechanical property, corrosion resistance and biocompatibility after solid solution and aging, the application field of the magnesium alloy material is greatly expanded, and the defects of high coating energy consumption, complex process, high equipment requirement and the like are effectively avoided. The method has the advantages of short flow, simple operation, high efficiency, low cost, easily obtained raw materials and equipment, and the like, and has wide application prospect in the field of medical implant materials.
Drawings
Fig. 1 is a process flow diagram of a precipitation-strengthened implantable magnesium alloy and a preparation process thereof according to the present invention.
FIG. 2 is a surface topography of a Mg-5.8Zn-2.0Yb-0.5Zr (wt.%) precipitation-strengthened implantable magnesium alloy prepared by the techniques of the present application after soaking for 10 days and removing corrosion products.
Detailed Description
The technical solutions of the present invention are further illustrated below by specific examples, but are not intended to limit the scope of the present invention (note: the percentages in the following examples are by weight).
The first embodiment is as follows:
the magnesium alloy comprises the following components in percentage by weight: zn5.8%, Yb2.0%, Zr0.5% and the balance Mg.
The preparation process of the precipitation strengthening type implantable magnesium alloy comprises the following three steps of smelting, solid solution and aging:
1) the smelting comprises the following steps: at SF6＋CO2In the gas protection, components of Zn5.8%, Yb2.0%, Zr0.5% and the balance of Mg are smelted to prepare an alloy ingot, the smelting temperature is 770 ℃, the alloy ingot is fully melted and then is kept stand at 720 ℃ for 20 min, slag is removed, and then the alloy ingot is taken out of a furnace for casting and is naturally cooled to room temperature;
2) the solid solution is as follows: keeping the temperature for 24 hours in an environment of 400 ℃ and filling argon to ensure that the second phase distributed along the grain boundary is fully dissolved back into the matrix, ensuring that the blank is not oxidized during solid solution, and then cooling the blank to room temperature by water;
3) the aging is as follows: heating the blank after the solution treatment to 200 ℃ in an argon environment along with a furnace, preserving the heat for 16 h, and finally uniformly dispersing and precipitating a second phase with the particle size of submicron in a magnesium matrix.
Further, the precipitation strengthening type implantable magnesium alloy and the preparation process thereof are characterized in that the total content of inclusion elements except Mg, Yb, Zn and Zr is not more than 0.4 wt.%.
The precipitation-strengthened Mg-5.8Zn-2.0Yb-0.5Zr implantable magnesium alloy finally prepared by the preparation process has the tensile strength at room temperature of 297 MPa, the elongation after forging is about 8.9 percent, and the degradation rate in SBF simulated body fluid is lower by one order of magnitude than that of ZK60, as shown in figure 2, the surface topography of the alloy after being soaked for 10 days and corrosion products are removed, and the alloy has good biocompatibility (the cell survival rate is more than 108 percent after the 10 percent leaching liquor is cultured for 24 hours, and the hemolysis rate is less than 1.72 percent).
Example two:
the magnesium alloy comprises the following components in percentage by weight: zn6.0%, Yb1.0%, Zr0.5% and the balance Mg; the submicron-scale second phase is dispersed in the magnesium matrix.
The preparation process of the precipitation strengthening type implantable magnesium alloy comprises three steps of smelting, solid solution and aging (as shown in figure 1):
1) the smelting comprises the following steps: at SF6＋CO2In the gas protection, components of Zn6.0%, Yb1.0%, Zr0.5% and the balance of Mg are smelted to prepare an alloy ingot, the smelting temperature is 770 ℃, the alloy ingot is fully melted and then is kept stand at 720 ℃ for 20 min to remove slag, and then the alloy ingot is taken out of a furnace for pouring and is naturally cooled to room temperature;
2) the solid solution is as follows: keeping the temperature for 36 h in an environment of 400 ℃ and filled with argon to ensure that the second phase distributed along the grain boundary is fully dissolved back into the matrix, ensuring that the blank is not oxidized during solid solution, and then cooling to room temperature by water;
3) the aging is as follows: heating the blank after the solution treatment to 200 ℃ in an argon environment along with a furnace, preserving the heat for 16 h, and finally uniformly dispersing and precipitating a second phase with the particle size of submicron in a magnesium matrix.
Further, the precipitation strengthening type implantable magnesium alloy and the preparation process thereof are characterized in that the total content of inclusion elements except Mg, Yb, Zn and Zr is not more than 0.4 wt.%.
The precipitation-strengthened Mg-6.0Zn-1.0Yb-0.5Zr implantable magnesium alloy finally prepared by the preparation process has the room-temperature tensile strength of 270 MPa, the elongation after forging is about 10 percent, the degradation rate in SBF simulated body fluid is lower by one order of magnitude than that of ZK60, and the alloy has good biocompatibility (the cell survival rate is more than 114 percent after the 10 percent leaching solution is cultured for 24 hours, and the hemolysis rate is less than 1.89 percent).
Finally, the above embodiments are merely used to more clearly illustrate the working principle and process of the present invention, and do not limit the present invention. The invention is also applicable to other ZK60 Mg alloys with Yb content as defined in the present application, and the processing principle and processing steps are not different from the above examples, so that repeated examples are not required. The invention makes creative contribution to the prior art, aims to provide a precipitation strengthening type implantable magnesium alloy with good mechanical property and excellent corrosion resistance and a preparation process thereof, effectively expands the application field of the magnesium alloy and makes up the defects of the prior art. The alloy performance potential is effectively developed, and the preparation method has the advantages of short flow, high efficiency, good quality and very obvious beneficial effect.
Claims (2)
1. A preparation process of precipitation strengthening type implantable magnesium alloy is characterized by comprising the following steps: the magnesium alloy comprises the following components in percentage by weight: 5.0-6.0% of Zns, 1.0-2.0% of Yb, 0.3-0.5% of Zrs, and the balance of Mg; a second phase with the particle size of submicron order is dispersed and distributed in the magnesium matrix; the preparation process of the precipitation strengthening type implantable magnesium alloy comprises the following three steps of smelting, solid solution and aging:
1) the smelting comprises the following steps: at SF6＋CO2In the gas protection, alloy ingots are prepared by smelting components of Zn5.0-6.0%, Yb 1.0-2.0%, Zr0.3-0.5% and the balance of Mg, the smelting temperature is 770 ℃, the alloy ingots are fully melted and then kept stand at 720 ℃ for 20 min, slag is removed, and then the alloy ingots are discharged for casting and are naturally cooled to room temperature;
2) the solid solution is as follows: preserving heat for 24-36 hours in an environment of 400 ℃ and filling argon to ensure that a second phase distributed along a crystal boundary is fully dissolved back into a matrix, ensuring that a blank is not oxidized during solid solution, and then cooling to room temperature by water;
3) the aging is as follows: heating the blank subjected to the solution treatment to 200 ℃ in an argon environment along with a furnace, preserving the heat for 16 h, and finally dispersing and precipitating a second phase with a particle size of submicron in a magnesium matrix;
the prepared precipitation-strengthened Mg-Zn-Yb-Zr implantable magnesium alloy has the room-temperature tensile strength of more than 290 MPa, the degradation rate in SBF simulated body fluid is one to two orders of magnitude lower than that of ZK60, the size of the second phase is less than 1 mu m, and the mechanical property and the corrosion resistance of the magnesium alloy are greatly improved.
2. The process of claim 1, wherein the total amount of inclusion elements other than Mg, Yb, Zn, Zr is no greater than 0.4 wt.%.
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