CN114921700B - Biodegradable Mg-Zn-Ca-Re alloy - Google Patents
Biodegradable Mg-Zn-Ca-Re alloy Download PDFInfo
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- C22C23/00—Alloys based on magnesium
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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
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Abstract
The invention relates to the technical field of biomedical metal material preparation, in particular to a degradable magnesium alloy material which is prepared by designing a magnesium-zinc-calcium- (rare earth). The alloy consists of the following components in percentage by mass: zn:1.5 to 2.5 percent of Ca:0.2 to 0.3 percent, 0.2 to 0.4 percent of Re, and the balance of magnesium and a very small amount of impurities; the Re is Sc and/or Sm. The magnesium alloy obtains superfine single-digit micron-sized grains through extrusion deformation at a lower temperature, so that good corrosion resistance and high strength or plasticity are obtained. When the lower-temperature extrusion deformation is carried out, the extrusion temperature is controlled to be 275-290 ℃. The invention successfully extrudes the plate strip with excellent performance and good surface quality at a lower temperature (275-290 ℃), reduces extrusion cost and is convenient for industrialized application.
Description
Technical Field
The invention relates to the technical field of biomedical metal material preparation, in particular to a degradable magnesium alloy material which is prepared by designing a magnesium-zinc-calcium- (rare earth).
Background
The magnesium alloy has good biocompatibility, is one of major elements inferior to calcium, sodium and potassium in human body, can activate various enzymes, participates in a series of metabolism processes in the body, and has great application prospect in biomedical degradable metal materials.
However, magnesium has poor plastic formability, which is easy to cause processing difficulty, and as a temporary implant material, the magnesium has a fast corrosion degradation rate and cannot support tissue healing, so that alloying and thermal deformation are necessary to further improve the comprehensive performance. By combining the advantages of rich resources of magnesium, rare earth and the like in China, and selecting nutrient elements possessed by human bodies and rare earth elements with good strengthening effect to microalloy the magnesium, the comprehensive performance of the alloy can be improved on the basis of keeping the biocompatibility of the alloy. Wherein, the rare earth element improves the mechanical strength and corrosion resistance of the alloy by purifying the solution and separating out stable dispersed phase. Extrusion is the most common deformation processing mode in magnesium alloy, the three-way compressive stress is the strongest, the plastic deformation capability of the alloy can be exerted to the greatest extent, the alloy structure is further refined, the defects of cast alloy are reduced, and the alloy performance is improved.
At present, the developed biomedical magnesium alloy mainly focuses on Mg-Al, mg-Zn, mg-Ca, mg-Sr, mg-Si, mg-Zr, mg-Li and Mg-RE series alloys.
Wherein the Al element is mainly formed by forming compact Al on the surface of the alloy 2 O 3 The film improves the corrosion resistance of the magnesium alloy, and aluminum has better strengthening effect in magnesium, so that the mechanical property of the alloy can be effectively improved. However, elemental aluminum has proven to be neurotoxic and is not suitable for use in human biomedical materials. Zn is a nutrient element of human body, and plays a role in improving alloy plasticity mainly by solid solution strengthening in terms of material science. The addition of trace alkaline earth metal elements (Ca, sr and the like) can not only increase the biocompatibility of the alloy, but also improve the thermal stability of the alloy, reduce the generation of dendrites of the cast alloy, refine grains and improve the strength of the alloy. Si element and Mg are easy to generate Mg with higher melting temperature, higher hardness, lower density and lower thermal expansion coefficient 2 Si intermetallic compound can effectively strengthen magnesium alloy. However, this phase tends to cause strong galvanic corrosion. Zr is mainly used as a grain refiner in magnesium, but Ca can be added to better replace Zr to achieve the effect of refining grains. The addition of Li element can change the structure of the alloy, and the joint addition of Li and Zn can better improve the yield strength, ultimate tensile strength and elongation of the magnesium alloy.
Rare earth elements are commonly used as alloying elements of magnesium, so that the high-temperature strength and creep resistance of the magnesium alloy can be improved. Wherein Y, ce, la and Nd are the most commonly used rare earth elements in magnesium-rare earth alloys. However, light rare earth elements Ce, la and the like have larger cytotoxicity, heavy rare earth elements Y and the like are easy to gather in the brain, and the harm of the rare elements to human bodies is easy to be aggravated when the light rare earth elements Ce, la and the like are used as biomedical materials. The addition of a small amount of light rare earth elements does not obviously increase the density of the rare earth, and can also keep good biocompatibility of the alloy. The rare earth elements Sc and the light rare earth elements Sm and Nd have better biocompatibility, and have larger solid solubility in magnesium, thus having good strengthening effect.
The invention relates to a biodegradable magnesium alloy and a preparation method thereof, wherein the patent application number is 202010068093.7, and the invention discloses a biodegradable Mg-Zn-Y-Nd-Ca magnesium alloy which comprises the following components in percentage by weight: 0.5% of Zn, 3.2-4.5% of Y, 2.0-3.0% of Nd, less than or equal to 0.6% of Ca, and less than or equal to 0.05% of impurity content, and the balance of Mg. In the patent, the magnesium alloy is cast, then subjected to annealing and T6 heat treatment to reach the tensile strength of 206-231 MPa and the hardness of 42-47, but the deformation processing condition of the alloy is not further studied. And the rare earth content in the patent exceeds 5.2%, so that the rare earth alloy has high economic cost.
The invention relates to a biodegradable Mg-Nd-Zr-Sr-Sc-Sm alloy and a preparation method thereof, wherein the patent application number is 202111552512.5, and the disclosed biodegradable Mg alloy comprises the following components in percentage by weight: : nd: 4-5%, zr:1 to 1.5 percent, sr:2 to 2.5 percent, sc:1.2 to 2 percent, sm:0.8 to 2.8 percent, the content of other unavoidable impurities is less than or equal to 0.1 percent, and the balance is Mg. The magnesium alloy is annealed, extruded or forged, the tensile strength of the magnesium alloy obtained after solution treatment reaches 350-420 MPa, the yield strength reaches 290-356 MPa, the Vickers hardness is 45-52, the elongation is more than 30%, and the average corrosion rate for 96 hours is 0.09-0.21 mg/(cm) 2 H), has better mechanical and corrosion resistance. However, the test time of corrosion resistance is short, the extrusion temperature (270 ℃ to 450 ℃) and the extrusion ratio (10 to 80) are large, the reference range is large, the rare earth element content is increased, the types are more, and the cost is increased.
The consumption of the deformed magnesium alloy in the current market is smaller than that of the cast magnesium alloy. However, wrought magnesium alloys have the effect that cast magnesium alloys are difficult to replace. Many wrought magnesium alloys do not contain Ca and many Ca-containing magnesium alloys lack attempts at the wrought process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-alloying and low-cost biodegradable Mg-Zn-Ca- (Sc/Sm) alloy, and the mechanical property and the corrosion resistance of the alloy are improved through the cooperation of components and a preparation process.
The biodegradable magnesium alloy adopts a principle of multiple small quantity, adopts rare earth and non-rare earth elements to carry out alloying, avoids adding heavy rare earth elements which are easy to gather in brain, and selects and adds light rare earth elements Sm or rare earth elements Sc which are lighter in toxicity to human bodies, and human nutrition elements Zn and Ca. The invention optimizes the extrusion process of Ca-containing magnesium alloy, processes the biodegradable magnesium alloy through extrusion deformation at low temperature, refines the crystal grains of the alloy, improves the alloy strength, ensures that the alloy is corroded more uniformly and slowly at the same time with fine crystal grains, and obtains excellent biomedical degradable material, thus being especially suitable for preparing bone fixing materials.
The invention solves the problems by adopting the following technical scheme: the alloy consists of the following components in percentage by mass: zn:1.5 to 2.5 percent of Ca:0.2 to 0.3 percent, 0.2 to 0.4 percent of Re, and the balance of magnesium and a very small amount of impurities (i.e. unavoidable impurities); the Re is Sc and/or Sm. The magnesium alloy obtains superfine single-digit micron-sized grains through extrusion deformation at a lower temperature, so that good corrosion resistance and high strength or plasticity are obtained. When the lower-temperature extrusion deformation is carried out, the extrusion temperature is controlled to be 275-290 ℃.
The invention relates to a biodegradable Mg-Zn-Ca-Re alloy; the alloy consists of the following components in percentage by mass: zn:1.9 to 2.2 percent of Ca:0.25 to 0.30 percent, 0.35 to 0.4 percent of Re, and the balance of magnesium and unavoidable impurities. The Re is preferably Sc.
The invention relates to a biodegradable Mg-Zn-Ca-Re alloy; which is prepared by the following steps
Step one
Obtaining an as-cast alloy through smelting and casting;
step two
Placing the as-cast alloy into a box-type resistance furnace, preserving heat at 300-500 ℃, preferably 350-450 ℃, more preferably 400 ℃ for 12-48 hours, preferably 18-36 hours, more preferably 24 hours, cooling to room temperature, and homogenizing;
step three
Heating the homogenized alloy to 260-350 ℃ and preserving the heat for 4-6 hours, and extruding at 260-300 ℃, preferably 275-290 ℃ and more preferably 280 ℃ to obtain the product.
As a preferable scheme, the biodegradable Mg-Zn-Ca-Re alloy is prepared; the smelting and casting process comprises the following steps:
(1) The high-purity magnesium ingot, the high-purity zinc, the Mg-Ca intermediate alloy, the Mg-30Sc intermediate alloy and the Mg-Sm intermediate alloy are used as raw materials, and the ingredients are mixed according to the low alloy ingredients.
(2) Smelting by adopting a vacuum medium-frequency induction furnace, introducing proportioning raw materials, heating the smelting furnace to 760-820 ℃, uniformly stirring after the raw materials are completely melted, preserving the temperature for 5-10 minutes at 740-760 ℃, removing slag, and finally casting on a tantalum crucible preheated to 180-200 ℃.
As a preferable scheme, the biodegradable Mg-Zn-Ca-Re alloy is prepared; the extrusion ratio is 25 to 10, preferably 22 to 15, and more preferably 18 to 19.
In the present invention, the extruder used comprises an XJ-800DT type metal profile extruder.
As a further preferred embodiment, the present invention is a biodegradable Mg-Zn-Ca-Re alloy; the alloy consists of the following components in percentage by mass: zn:1.9 to 2.2 percent of Ca:0.25 to 0.30 percent, sc0.35 to 0.4 percent, and the balance of magnesium and unavoidable impurities, and the average grain size of the product is 1.5 to 1.7 mu m after low-temperature extrusion.
As a further preferred embodiment, the present invention is a biodegradable Mg-Zn-Ca-Re alloy; the alloy consists of the following components in percentage by mass: zn:1.9 to 2.2 percent of Ca:0.25 to 0.30 percent, sc0.35 to 0.4 percent, and the balance of magnesium and unavoidable impurities, wherein the average grain size of the product is 1.5 to 1.7 mu m after low-temperature extrusion; the product has compressive strength of 485-490 MPa, tensile strength of 310-315 MPa, hardness of 70-72HBW, and corrosion rate of 0.6-0.65mm.a obtained by soaking in Hank's equilibrium solution at constant temperature of 37 ℃ for 30 days -1 。
Compared with the prior art, the invention adopts micro-alloying and low-temperature low-speed extrusion technology to obtain the calcium-containing magnesium alloy plate difficult to extrude, the grain size reaches the order of single-digit micron, more cold working characteristics inside the alloy are reserved, and the mechanical strength and corrosion resistance of the alloy are greatly improved. The method comprises the following steps:
(1) Compared with the traditional metal implantation material, the alloy has good biocompatibility and degradability, and can be used as a bone fixing material or an interventional therapy of a cardiovascular stent, thereby avoiding secondary operation extraction.
(2) Compared with other magnesium alloys, the alloy has the advantages that trace Sc or Sm rare earth elements are added besides Zn, ca and other human nutrition elements, so that the alloy is reinforced, the biocompatibility of the alloy is not lost, and the mechanical property and corrosion resistance of the alloy are greatly improved.
(3) The preparation process is simple. The invention considers the high melting point condition of rare earth elements, adopts magnesium-rare earth intermediate alloy for vacuum smelting, reduces the alloy smelting temperature, has simple smelting process, saves complex refining links, and saves cost and time.
(4) Compared with other extrusion processes, the preparation process is simpler, the magnesium alloy extrusion plate containing calcium is prepared, no redundant refining step is needed, the extrusion temperature is lower, the cost is lower, and the preparation process has good industrial application value. Meanwhile, the invention successfully extrudes the plate strip with excellent performance at a lower temperature (275-290 ℃ and 280 ℃ preferably), thereby reducing extrusion cost. After optimization, the biodegradable Mg-Zn-Ca-Re alloy is prepared; the alloy consists of the following components in percentage by mass: zn:1.9 to 2.2 percent of Ca:0.25 to 0.30 percent, sc0.35 to 0.4 percent, and the balance of magnesium and unavoidable impurities, wherein the average grain size of the product is 1.5 to 1.7 mu m after low-temperature extrusion; the product has compressive strength of 485-490 MPa, tensile strength of 310-315 MPa, hardness of 70-72HBW, and corrosion rate of 0.6-0.65 mm.a obtained by soaking in Hank's equilibrium solution for 30 days at constant temperature of 37 DEG C -1 。
Drawings
FIG. 1 is an XRD phase analysis of examples 1, 2, and 3 of the present invention;
FIG. 2 is a metallographic micrograph of an embodiment 1 of the present invention;
FIG. 3 is a metallographic micrograph of an embodiment 2 of the present invention;
FIG. 4 is a metallographic micrograph of an embodiment 3 of the present invention;
FIG. 5 is a graph of the Mg-Zn-Ca-Sc magnesium alloy extrusion sheet obtained at different extrusion temperatures according to the present invention;
FIG. 6 shows the macroscopic morphology of example 1 of the present invention after soaking in Hank's solution at a constant temperature of 37℃for 30 days;
FIG. 7 shows the macroscopic morphology of example 2 of the present invention after soaking in Hank's solution at a constant temperature of 37℃for 30 days;
FIG. 8 shows the macroscopic morphology of example 3 of the present invention after soaking in Hank's solution at a constant temperature of 37℃for 30 days;
FIG. 9 is a stretch-break topography of embodiment 1 of the present invention;
FIG. 10 is a stretch-break topography of embodiment 2 of the present invention;
FIG. 11 shows a stretch-break morphology according to example 3 of the present invention.
FIG. 12 is a graphical representation of the results obtained in comparative example 1 of the present invention when the extrusion temperature was about 360 ℃.
FIG. 13 is a graphical representation of the Mg-Zn-Ca product obtained in comparative example 2 at an extrusion temperature of about 260 ℃.
Detailed Description
Example 1
The production process flow is as follows:
batching, vacuum smelting, homogenizing heat treatment, hot extrusion processing and finished product
The specific process is as follows: the preparation method comprises the steps of preparing materials according to the embodiment 1 shown in the table 1 by using a vacuum induction furnace, placing a high-purity magnesium (> 99.9%), high-purity zinc (> 99.9%) and Mg-20Ca (> 99.9%) intermediate alloy into a resistance furnace, heating to 780 ℃ to melt the alloy, preserving the heat at 760 ℃ for 5 minutes, casting the melt into a tantalum crucible preheated to 200 ℃, and cooling to room temperature to obtain an ingot. The main components of the cast ingot are detected as follows by mass percent: zn:2.08%, ca:0.28%, the balance of magnesium and very little impurity content. The ingot obtained was kept at 400℃for 24 hours, subjected to homogenization heat treatment, and then cooled to room temperature. The alloy was heated to 280℃and kept at temperature for 5 hours before extrusion, and extruded into a 10mm thick magnesium alloy sheet strip at 280℃at an extrusion ratio of 18.17, followed by sampling and testing, the properties of which are shown in tables 2 and 3.
The main second phase of the extruded product obtained in example 1 is Ca 2 Mg 6 Zn 3 The average grain size is 3.2 mu m, a large number of tough ridges and tough pit holes can be seen from the tensile fracture appearance of the alloy in FIG. 9, the fracture mode is through-crystal ductile fracture, and the strength and toughness of the alloy are good.
Example 2
The production process flow is as follows:
batching, vacuum smelting, homogenizing heat treatment, hot extrusion processing and finished product
The specific process is as follows: the preparation method comprises the steps of preparing materials according to example 2 shown in Table 1 by using a vacuum induction furnace, placing a high-purity magnesium (more than 99.9%), high-purity zinc (more than 99.9%), mg-20Ca (more than 99.9%) master alloy and a Mg-30Sc (more than 99.9%) master alloy into a resistance furnace, heating to 780 ℃ to melt the alloy, preserving the heat at 760 ℃ for 5 minutes, casting the melt into a tantalum crucible preheated to 200 ℃, and cooling to room temperature to obtain an ingot. The main components of the cast ingot are detected as follows by mass percent: zn:2.12%, ca:0.27%, sc:0.4%, the balance of magnesium and very little impurity content. The ingot obtained was kept at 400℃for 24 hours, subjected to homogenization heat treatment, and then cooled to room temperature. The alloy was heated to 280℃and kept at temperature for 5 hours before extrusion, and extruded into a 10mm thick magnesium alloy sheet strip at 280℃at an extrusion ratio of 18.17, followed by sampling and testing, the properties of which are shown in tables 2 and 3.
After 0.4% Sc was added as compared to the extruded Mg-2Zn-0.3Ca alloy of example 1, the extruded Mg-2Zn-0.3Ca-0.4Sc alloy of example 2 had a primary second phase of Ca 2 Mg 6 Zn 3 The addition of ScZn and Sc promotes the further refinement of the grains of the extruded alloy, the average grain size is 1.6 mu m, and the fine and uniform structure enables the grains to grow in the soaking processThe formed corrosion film is more compact and the corrosion resistance is improved. The compression strength, the tensile strength and the hardness of the alloy are respectively improved by 22.1 percent, 16.9 percent and 10.9 percent compared with those of the extruded Mg-2Zn-0.3Ca alloy, and the alloy has better performance than those of commercial AZ systems and WE systems. The strengthening mechanism comprises texture strengthening, grain boundary strengthening and precipitation strengthening. From fig. 10, it can be seen that the appearance of the tensile fracture of example 2 with high strength and low ductility is mainly based on crystal-through fracture, secondary cracks also appear, the fracture is relatively smooth, and the tensile fracture can bear larger stress.
Example 3
The production process flow is as follows:
batching, vacuum smelting, homogenizing heat treatment, hot extrusion processing and finished product
The specific process is as follows: the preparation method comprises the steps of preparing materials according to example 3 shown in Table 1 by using a vacuum induction furnace, placing a high-purity magnesium (> 99.9%), high-purity zinc (> 99.9%), mg-20Ca (> 99.9%) master alloy and a Mg-20Sm (> 99.9%) master alloy into a resistance furnace, heating to 780 ℃ to melt the alloy, preserving the heat at 760 ℃ for 5 minutes, casting the melt into a tantalum crucible preheated to 200 ℃, and cooling to room temperature to obtain an ingot. The main components of the cast ingot are detected as follows by mass percent: zn:1.96%, ca:0.29%, sm:0.35%, the balance being magnesium and very little impurity content. The ingot obtained was kept at 400℃for 24 hours, subjected to homogenization heat treatment, and then cooled to room temperature. The alloy is heated to 280 ℃ before extrusion, kept for 5 hours, extruded into a magnesium alloy plate strip with the thickness of 10mm at 280 ℃ and the extrusion ratio of 18.17, and then sampled and tested.
The specific components and properties of examples 1, 2, and 3 are shown in tables 1, 2, and 3.
Table 1 design composition (mass percent) of degradable magnesium alloy examples
Examples | Zn | Ca | Sc | Sm | Mg |
Example 1 | 2% | 0.3% | - | - | Allowance of |
Example 2 | 2% | 0.3% | 0.40% | - | Allowance of |
Example 3 | 2% | 0.3% | - | 0.4% | Allowance of |
TABLE 2 mechanical Properties of degradable magnesium alloys
TABLE 3 Corrosion resistance of degradable magnesium alloys
The test conditions and calculation methods for the corrosion rate corresponding to the corrosion current density in table 3 are:
electrokinetic polarization curve testing was performed on the alloy using an Interface1010 electrochemical workstation. And tangent to the cathode branches using Tafel extrapolation (SHI Z, LIU M, ATRENs A. Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation, corrosion Science,2010, 52:579-588.) to calculate corrosion current density J corr (mA·cm –2 ) And calculating the corresponding average corrosion rate P according to the corrosion current density J (mm·y -1 ):
P J =22.85J corr
The test conditions and calculation method of the corrosion rate corresponding to the weight loss in table 3 are:
measuring length, width and height of alloy and dry weight before soaking, placing sample in beaker at 20cm 2 The Hank's equilibrium solution is added in the ratio of/mL and soaked in a water bath for 30 days at the constant temperature of 37 ℃. Ultrasonic cleaning the sample with 200g/L chromic acid solution for 5 min after soaking, removing corrosion product formed on the surface of the alloy, drying, and measuring the weight of the sample with corrosion product removed to obtain total loss weight delta W (mg cm) -2 ·d -1 ) Average corrosion rate P of alloy W Calculated according to ASTM G31-72 (ASTM G1-90,Standard Practice for Preparing,Cleaning,and Evaluating Corrosion Test Specimens,annual book of ASTM standards,American Society for Testing and Materials,West Conshohocken,PA,1999), the formula is as follows:
wherein A is the surface area (cm) of the test sample 2 ) T is soaking time (day), ρ is density (g.cm) -3 )。
As can be seen from tables 2 and 3, the three extrusion state alloys prepared by the present invention have good mechanical properties and corrosion resistance, wherein the optimal content is example 2, namely Zn:2.12%, ca:0.27%, sc:0.40 percent, the balance of magnesium and a very small amount of impurity content, and the mechanical strength and the corrosion resistance of the alloy are optimal.
In the prior art CN 110468319A, although the biodegradable magnesium alloy containing rare earth and the preparation method thereof are designed, the proportion difference of raw materials is larger. The rare earth content of the comparative patent is added with 3 to 4.5 percent of Y and 2 to 3.5 percent of Nd, the added content is more, the rare earth elements added by the invention are less, but the corrosion resistance and the mechanical strength are higher than those of the comparative patent, and the extrusion temperature of the novel rare earth alloy extrusion die is lower, so that the cost is better saved.
After 0.4% Sm was added as compared with the extruded Mg-2Zn-0.3Ca alloy of example 1, the extruded Mg-2Zn-0.3Ca-0.4Sm alloy of example 3 had a major second phase of Ca 2 Mg 6 Zn 3 、(Mg,Zn) 3 Sm has an average grain size of 3.5. Mu.m. Coarse (Mg, zn) 3 The Sm second phase makes the contact area between the substrate and the corrosive solution larger, and the corrosion resistance is slightly reduced. But the plasticity of the Mg-2Zn-0.3Ca-0.4Sm alloy is obviously improved, and the specific elongation is improved by 33.3 percent. It can be seen from fig. 11 that the tensile fracture of example 3, which has a high elongation, has a flame morphology and contains a large number of ductile pits, which is typical of ductile fracture characteristics.
Comparative example 1
Other conditions were identical to example 2, except that an extrusion temperature of about 310-360℃was used, as a result of which: the sheet could not be obtained at all. The morphology of the specific product is shown in fig. 5 and 12, and fig. 12 is about 360 ℃ of the obtained product.
Comparative example 2
Other conditions were identical to example 2, except that an extrusion temperature of 260℃was used, as a result of which: the surface quality of the obtained plate was extremely poor (see FIG. 13), and then the surface quality of the plate was also poor by treating the as-cast product obtained in example 2 at 260 ℃.
It was also found during the development that only after Ca was added (especially when Ca content reached 0.3%); the extrusion temperature of the material becomes particularly sensitive. In the material system developed in the present invention, the extrusion is about 275-290 ℃. Outside this range, the sheet material has very poor surface quality or is not extruded at all (e.g., 240 ℃).
Claims (5)
1. A biodegradable Mg-Zn-Ca-Re alloy; the method is characterized in that: the alloy consists of the following components in percentage by mass: zn: 1.9-2.2%, ca: 0.25-0.30%, 0.35% -0.4% of Re, and the balance of magnesium and unavoidable impurities; the Re is Sc; the biodegradable Mg-Zn-Ca-Re alloy obtains superfine single-digit micron-sized grains through extrusion deformation at a lower temperature, so that good corrosion resistance and high strength are obtained;
the biodegradable Mg-Zn-Ca-Re alloy is prepared by the following steps:
step one
Obtaining an as-cast alloy through smelting and casting;
step two
Placing the as-cast alloy into a box-type resistance furnace, preserving heat for 18-30 hours at 400 ℃, cooling to room temperature, and carrying out homogenization treatment;
step three
Heating the homogenized alloy to 260-350 ℃ and preserving heat for 4-6 hours, and then extruding at 280 ℃ to obtain a product; the extrusion ratio is 18-19;
the product has compressive strength of 485-490 MPa, tensile strength of 310-315 MPa, hardness of 70-72HBW, and corrosion rate of 0.6-0.65 mma obtained by soaking in Hank's equilibrium solution at constant temperature of 37 ℃ for 30 days −1 。
2. A biodegradable Mg-Zn-Ca-Re alloy according to claim 1; the method is characterized in that: the smelting and casting process comprises the following steps:
(1) Taking high-purity magnesium ingots, high-purity zinc, mg-Ca intermediate alloy and Mg-30Sc intermediate alloy as raw materials, and mixing according to the low alloy components;
(2) Smelting by adopting a vacuum medium-frequency induction furnace, introducing proportioning raw materials, heating the smelting furnace to 760-820 ℃, uniformly stirring after the raw materials are completely melted, preserving the temperature for 5-10 minutes at 740-760 ℃, removing slag, and finally casting on a tantalum crucible preheated to 180-200 ℃.
3. A biodegradable Mg-Zn-Ca-Re alloy according to claim 1; the method is characterized in that: and (3) placing the as-cast alloy into a box-type resistance furnace, preserving heat for 24 hours at 400 ℃, cooling to room temperature, and carrying out homogenization treatment.
4. A biodegradable Mg-Zn-Ca-Re alloy according to claim 1; the method is characterized in that: the extruder used included an XJ-800DT type metal profile extruder.
5. A biodegradable Mg-Zn-Ca-Re alloy according to claim 1; the method is characterized in that: after low temperature extrusion at 280 ℃, the average grain size of the product is 1.5-1.7 mu m.
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