阅读说明：本技术 生物体内可降解高强韧医用Zn-Cu-Mn-Zr合金 (Biodegradable high-strength and high-toughness medical Zn-Cu-Mn-Zr alloy in organism ) 是由 黄华 牛佳林 柯贵州 袁广银 于 2019-08-26 设计创作，主要内容包括：本发明公开了一种生物体内可降解高强韧医用Zn-Cu-Mn-Zr合金；含Zn、Cu、Mn和Zr元素,且Cu的含量大于0、小于等于4％,Mn的含量大于0、小于等于2％,Zr的含量大于0、小于等于2％,其余为Zn。本发明的合金材料在模拟体液中的腐蚀速率为35～71μm/year,同时呈现均匀腐蚀降解模式；在室温且拉伸应变速率为1×10~(-3)条件下拉伸性能为：屈服强度200～420MPa,抗拉强度210～440MPa,延伸率20～65％。对金黄色葡萄球菌和大肠杆菌抗菌率在90％以上。在380℃下保温0.5小时后在真应变5％-15％阶段应变硬化指数n大于等于0.2；且无明显的细胞毒性,生物相容性较好。(The invention discloses a medical Zn-Cu-Mn-Zr alloy with high toughness and degradability in a living body; contains Zn, Cu, Mn and Zr, wherein the content of Cu is more than 0 and less than or equal to 4 percent, the content of Mn is more than 0 and less than or equal to 2 percent, the content of Zr is more than 0 and less than or equal to 2 percent, and the balance is Zn. The corrosion rate of the alloy material in simulated body fluid is 35-71 mu m/year, and a uniform corrosion degradation mode is presented; at room temperature and tensile strain rate of 1X 10 ‑3 Tensile Properties under ConditionComprises the following steps: the yield strength is 200-420 MPa, the tensile strength is 210-440 MPa, and the elongation is 20-65%. The antibacterial rate to staphylococcus aureus and escherichia coli is more than 90%. Keeping the temperature at 380 ℃ for 0.5 hour, and then keeping the strain hardening index n at the stage of true strain 5-15% to be more than or equal to 0.2; and has no obvious cytotoxicity and good biocompatibility.)

1. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material is characterized by comprising Zn, Cu, Mn and Zr elements, wherein the Cu content is more than 0 and less than or equal to 4 percent by weight, the Mn content is more than 0 and less than or equal to 2 percent by weight, the Zr content is more than 0 and less than or equal to 2 percent by weight, and the balance is Zn.

2. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1, wherein the alloy material comprises the following components in percentage by weight: 1.5 to 3.5 percent of Cu, 0.5 to 1.5 percent of Mn, 0.5 to 1.0 percent of Zr, and the balance of Zn.

3. The in vivo degradable high toughness medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1 or 2, wherein the purity of Zn is 99.995% or more, the purity of Cu is 99.9% or more, the purity of Mn is 99.99% or more, and the purity of Zr is 99.99% or more.

4. The in vivo degradable high strength medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1 or 2, wherein the total amount of inclusion elements other than Zn, Cu, Mn, Zr is not more than 0.1 wt%.

5. The in-vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1 or 2, wherein the corrosion rate of the alloy material in C-SBF simulated body fluid is 35-71 μm/year, and the corrosion degradation mode of the alloy material in the simulated body fluid is uniform corrosion.

6. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material according to claim 1 or 2, wherein the alloy material is at room temperature and tensile strainRate of 1X 10^-3The tensile mechanical properties under the conditions were: the yield strength is 200-420 MPa, the tensile strength is 210-440 MPa, and the elongation is 20-65%.

7. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1 or 2, wherein the antibacterial rate of the alloy material to Staphylococcus aureus and Escherichia coli is above 90%.

8. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material as claimed in claim 1 or 2, wherein the alloy material is preserved at 380 ℃ for 0.5 hour. The strain hardening index n is higher than 0.2 at the stage of true strain 5% -15%.

9. The in vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material according to claim 1 or 2, which is used for preparing an in-plant apparatus.

10. The use according to claim 9, wherein the endograft instrument comprises an endosteal, vascular stent, staple, vascular clamp, or the like.

Technical Field

The invention relates to a medical Zn-Cu-Mn-Zr alloy with high toughness and degradability in a living body, in particular to a medical zinc alloy material with high toughness and processing hardening and ageing resistance, which is suitable for being used for preparing a degradable internal implantation instrument in the living body.

Background

At present, the materials for preparing the internal implantation instrument which are widely applied clinically are mostly inert materials, such as stainless steel, titanium alloy and the like. The materials have good stability in human body, good biocompatibility and good forming performance. However, the general problems of the implantation instruments made of the materials are that: after implantation, the implant exists as a foreign body, and anti-rejection medicines such as vascular stent products need to be taken for a long time; after the corresponding diseases are recovered, the bone plates and bone nails need to be taken out through secondary operations. This increases both the pain and the burden of medical costs for the patient and also increases a large amount of surgical work for the clinician.

In recent years, the degradable medical metal material has attracted wide attention, not only inherits the good mechanical property and machinability of the metal material, but also can be degraded and metabolized in a human body, and has great advantages when being applied to instruments such as orthopedic internal fixation or vascular stents and the like. The zinc alloy has good biological safety, moderate degradation speed in human body and good application prospect. At present, the researches on degradable zinc alloy mainly comprise pure zinc, Zn-Mg base system and other series. Of these, the most representative is the study of the scholars Bowen et al on the simulation of stent degradation behavior by pure zinc filaments, which shows that the zinc filaments implanted into the abdominal aorta of rats show ideal degradation behavior and the corrosion products also show good biocompatibility. This shows that zinc has certain feasibility as a degradable stent material, however, pure zinc has poor mechanical properties, and is difficult to meet the requirements for preparing stents, and the yield strength of the tube prepared from high-purity zinc is only about 80MPa, and the elongation is about 10%, so that the mechanical properties of pure zinc need to be improved. Meanwhile, the melting point of the zinc alloy is low, and the structural stability of the zinc alloy at room temperature is poor, so that the zinc alloy is easy to age, and the obvious mechanical property reduction of the zinc alloy medical instrument is caused in the storage or use process. In addition, the zinc alloy has poor processing and hardening capacity due to poor tissue stability in the deformation process at room temperature, and the processing difficulty of the zinc alloy micro-tube for the vascular stent is increased. Therefore, the method improves the mechanical property of the zinc alloy through alloying, optimizes the ageing resistance and the work hardening capacity of the alloy, and simultaneously ensures better corrosion degradation and biocompatibility of the zinc alloy, thereby being the key for wide application of the zinc alloy as a degradable medical implant material.

Through the search of the prior patent literature, the patent numbers: ZL201510512800.6, biodegradable medical zinc-copper alloy and a preparation method and application thereof; patent application No.: 201910291761.X, a Zn-Ge-X ternary biomedical material and a preparation method thereof; patent application No.: 201710363125.4, a biomedical Zn-Mn-Cu zinc alloy and a preparation method thereof; patent application No.: 201811544472.8A method for preparing medical zinc alloy bar with superplasticity. These patents report new zinc alloy materials, the combination of which is yet to be further improved, particularly in terms of improving the aging resistance and work hardening capacity of the alloy.

Disclosure of Invention

The invention aims to solve the problems of aging and low work hardening capacity of zinc alloy in view of improving the comprehensive performance of biomedical zinc alloy in clinical practical requirements, and provides a medical Zn-Cu-Mn-Zr alloy which can be degraded in vivo and has high toughness; the alloy has excellent mechanical property, ideal uniform corrosion resistance, good biocompatibility, aging resistance and higher processing and hardening capacity, and is suitable for preparing degradable endosteal implant instruments and implant instruments such as vascular stents, anastomosis nails, vascular clamps and the like.

The purpose of the invention is realized by the following technical scheme:

in a first aspect, the invention relates to a medical Zn-Cu-Mn-Zr alloy material with high toughness and degradability in a living body, which contains Zn, Cu, Mn and Zr, wherein the weight percentage content of Cu is more than 0 and less than or equal to 4 percent, the weight percentage content of Mn is more than 0 and less than or equal to 2 percent, the weight percentage content of Zr is more than 0 and less than or equal to 2 percent, and the balance is Zn.

In order to obtain the best comprehensive mechanical property and biological corrosion and compatibility, the weight percentages of the components of the alloy are further limited as follows: 1.5 to 3.5 percent of Cu, 0.5 to 1.5 percent of Mn, 0.5 to 1.0 percent of Zr, and the balance of Zn. Meanwhile, the content of inclusion elements except Zn, Cu, Mn and Zr is strictly controlled, and the total impurity percentage is not more than 0.1 percent.

Wherein the purity of Zn is more than or equal to 99.995%, the purity of Cu is more than or equal to 99.9%, the purity of Mn is more than or equal to 99.99%, and the purity of Zr is more than or equal to 99.99%.

The corrosion rate of the alloy material in C-SBF simulated body fluid is 35-71 mu m/year, and meanwhile, the corrosion degradation mode of the alloy material in the simulated body fluid is uniform corrosion. Meets the requirement of the implanted material on the corrosion performance.

The alloy material of the invention has a tensile strain rate of 1 x 10 at room temperature^-3The tensile mechanical properties under the conditions were: the yield strength is 200-420 MPa, the tensile strength is 210-440 MPa, and the elongation is 20-65%. Meets the requirement of the internal implantation material on mechanical property.

The antibacterial rate of the alloy material of the invention to staphylococcus aureus and escherichia coli is above 90%.

The alloy material of the invention is kept at 380 ℃ for 0.5 hour. The strain hardening index n is higher than 0.2 at the stage of true strain 5% -15%.

The functions of the alloying elements in the invention are respectively introduced as follows:

the addition of Cu can effectively improve the strength and the plasticity of the zinc alloy, provide the effects of solid solution strengthening and second phase strengthening for the alloy, and greatly improve the antibacterial property and the ageing resistance of the alloy. In addition, Cu is also a trace nutrient element necessary for human bodies, the world health organization recommends that each kilogram of adult should take 0.03 milligram every day, and pregnant women and infants should double, and Cu is a component element of various proteins of the human bodies and has important influence on the development and functions of a plurality of organs such as central nerves, immune systems, brains, livers, hearts and the like. The content of Cu in a human body is about 100-150 mg, the Cu is a second necessary trace metal element in the human body, and the lack of Cu can cause osteoporosis, anemia, coronary heart disease, infertility and the like. The Cu also has the biological effects of good antibacterial capacity, promotion of endothelialization and the like.

The addition of Mn improves the strength and plasticity of the zinc alloy and provides good work hardening capacity for the alloy; mn is also one of the essential trace nutrient elements of human body, Mn deficiency of human body can affect the normal growth and development of skeleton, influence the metabolism of sugar, cause neurasthenia syndrome, accelerate human body aging and other serious consequences, and meanwhile, the research also finds that Mn can be used for treating the serious consequences of Mn deficiency²⁺Has antiviral effect.

Zr is also a nontoxic trace element existing in human bodies, and the Zr is mainly added for refining the structure of the zinc alloy, further improving the strength and the plasticity of the alloy and optimizing the corrosion performance of the alloy.

The effect of pure addition of Cu, Mn or Zr in the zinc alloy is related in the early stage, but the addition of the single alloy element Cu, Mn or Zr cannot ensure that the alloy has ageing resistance, excellent work hardening characteristic and excellent toughness. Researches find that when three elements are simultaneously added and controlled within a certain component range, the in-vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material with ageing resistance and good work hardening capacity can be obtained.

According to the invention, the zinc alloy is strengthened by preferably selecting the alloy elements with good biocompatibility, the crystal grains are refined, the strength, the plasticity and the deformability are improved, and the ageing resistance and the work hardening capacity of the zinc alloy are improved; the zinc alloy is further strengthened and toughened through extrusion deformation and heat treatment processes.

Aiming at different requirements of orthopedic implant instruments such as endophytes, vascular stents, anastomosis nails and vascular clamps on material performance, firstly, an ingot is prepared by a conventional casting process, and then different extrusion (or rolling) thermal deformation processes and heat treatment processes are utilized to further refine and homogenize the tissue of the alloy, so that the mechanical property of the alloy is further improved, the corrosion rate and the biocompatibility of the alloy are regulated and controlled, and finally, the biodegradable high-strength and toughness zinc alloy material with different performance combinations can be obtained.

Therefore, in a second aspect, the invention also relates to an application of the in-vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material in preparation of an endosseous plant apparatus. The endosteal implant instrument comprises a vascular stent, an anastomosis nail and a vascular clamp.

As one embodiment of the present invention, preparing an endosteal implant device includes the steps of:

ingot casting: according to the components and the weight percentage content, the raw materials are taken for smelting, the smelting is carried out in a resistance furnace, and the smelting temperature is controlled at 600-650 ℃; casting the molten and refined alloy liquid into a cast ingot in a semi-continuous casting mode;

thermal solution treatment: carrying out solution treatment on the cast ingot at the temperature of 380 ℃ and 400 ℃ for 24 h;

hot extrusion deformation: extruding the cast ingot after the solution treatment into a bar material according to the extrusion temperature of 140-180 ℃ and the extrusion ratio of 9-25;

and (3) heat treatment regulation: keeping the temperature of the extruded bar at 380 ℃ for 0.5 hour; obtaining an alloy material having a work hardening index n higher than 0.20 within 5% -10% of the engineering strain;

molding: and preparing the endosteal plant device by the alloy material obtained by regulating and controlling the heat treatment.

Compared with the prior art, the invention has the following beneficial effects:

(1) the zinc alloy can be naturally degraded in vivo, and can disappear from the body in a certain time after reaching the medical effect, so that the pain and burden of a patient caused by a secondary operation are avoided.

(2) The medical zinc alloy does not contain toxic elements in component design, avoids the adverse effects of toxic elements such As Al element, Hg element, As element, Cd element and the like, and has good biocompatibility.

(3) After the zinc alloy is extruded or rolled and deformed, the structure is uniform, the zinc alloy has high strength and plasticity, and simultaneously, trace Cu exists in the material in the degradation process²⁺、Mn²⁺、Zr²⁺The product has certain biological effects of resisting bacteria and viruses, promoting vascular endothelialization, etc.

(4) The zinc alloy has good comprehensive mechanical properties, particularly good ageing resistance and suitable work hardening capacity.

Detailed Description

The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.

Raw materials of each group of zinc alloy (unit: weight%) shown in Table 1 were melted in a resistance furnace at a melting temperature of 600-650 ℃. The purity of Zn in the raw material was 99.995%, the purity of Cu was 99.9%, the purity of Mn was 99.99%, and the purity of Zr was 99.99%. And casting the molten and refined alloy into an ingot in a semi-continuous casting mode. Then the cast ingot is extruded into a bar by adopting certain extrusion temperature and extrusion ratio (table 1). Then, a sample with the diameter of 14mm multiplied by the thickness of 3mm is cut from the extrusion rod by adopting a wire cut electrical discharge machining mode, and a C-SBF simulated body fluid immersion experiment is carried out at the temperature of 37 +/-0.5 ℃ to test the corrosion degradation rate of the alloy. And cutting a sheet-shaped tensile sample for tensile mechanical property test, wherein the gauge length area of the tensile sample is 10mm multiplied by 3mm multiplied by 1.6 mm. The antibacterial effect of the alloy was evaluated using staphylococcus aureus and escherichia coli.

After the Zn-Cu-Mn-Zr alloy material is subjected to heat treatment and hot extrusion deformation, the alloy structure is obviously refined. The mechanical properties of the alloy can be regulated and controlled by adopting different hot extrusion processes within a certain composition range, and are shown in table 1; the performance of the alloy can be further optimized after the alloy is subjected to heat treatment regulation and control, and the table 2 shows. The corrosion rate in C-SBF simulated body fluid is 35-71 mu m/year, the corrosion mode of the material in the simulated body fluid is uniform corrosion, the requirement of an implanted material on corrosion degradation performance is met, and the alloy material has no obvious cytotoxicity, good biocompatibility and better antibacterial effect. Can meet the performance requirements of the implant materials for preparing the implant instruments such as the endosteal implant, the vascular stent, the anastomosis nail and the vascular clamp.

TABLE 1 chemical composition of the alloys and their mechanical properties and degradation rates

TABLE 2 mechanical properties of the alloys after heat treatment

Specific examples are shown in the following examples:

example 1

The alloy component Zn-1.5Cu-1.0Mn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength is 350MPa, the yield strength is 340MPa, and the elongation is 37%. The corrosion rate of the material under the environment of C-SBF simulated body fluid is 50 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 210MPa, the tensile strength is 280MPa, the elongation is 30 percent, and the strain hardening index n is 0.23 at the stage of 5 to 15 percent of true strain. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Examples2

The alloy component Zn-2.0Cu-0.5Mn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength is 360MPa, the yield strength is 348MPa, and the elongation is 32%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 53 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 220MPa, the tensile strength is 295MPa, the elongation is 26 percent, and the strain hardening index n is 0.24 at the stage of true strain 5-15 percent. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Example 3

The alloy component Zn-2.5Cu-0.75Mn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength is 375MPa, the yield strength is 360MPa, and the elongation is 33%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 53 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 240MPa, the tensile strength is 305MPa, the elongation is 26 percent, and the strain hardening index n is 0.23 at the stage of 5 to 15 percent of true strain. Alloy anti-agingThe capability is strong, the mechanical and corrosion performance of the alloy is tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Example 4

The alloy component Zn-3.0Cu-0.75Mn-1.0 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength is 385MPa, the yield strength is 362MPa, and the elongation is 35%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 52 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 277MPa, the tensile strength is 335MPa, the elongation is 28 percent, and the strain hardening index n is 0.24 at the stage of 5 to 15 percent of true strain. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Example 5

The alloy component Zn-3.0Cu-1.0Mn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength was 412MPa, the yield strength was 404MPa, and the elongation was 34%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 55 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. The extruded alloy is kept at 380 ℃ for 0.5 hourThen, the yield strength of the alloy is 284MPa, the tensile strength is 342MPa, the elongation is 27 percent, and the strain hardening index n is 0.25 at the stage of 5 to 15 percent of true strain. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Example 6

The alloy component Zn-3.0Cu-1.5Mn-0.8 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 180 ℃, and the extrusion ratio is 25. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength is 404MPa, the yield strength is 390MPa, and the elongation is 40%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 54 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 270MPa, the tensile strength is 334MPa, the elongation is 33 percent, and the strain hardening index n is 0.25 at the stage of 5 to 15 percent of true strain. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Example 7

The alloy component Zn-3.5Cu-1.0Mn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe round bar of (2) was extruded at a temperature of 140 ℃ and an extrusion ratio of 9. At room temperature and tensile strain rate of 1X 10^-3Under the test conditions, the mechanical properties obtained by the process are as follows: the tensile strength was 406MPa, the yield strength was 392MPa, and the elongation was 46%. The corrosion rate of the material in a C-SBF simulated body fluid environment is 57 mu m/year. The biological test result shows that the material has no obvious effectHas good cytotoxicity and biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the extruded alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 272MPa, the tensile strength is 336MPa, the elongation is 39 percent, and the strain hardening index n is 0.20 at the stage of 5 to 15 percent of true strain. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 2 percent.

Comparative example 1

The alloy composition is Zn-3.5 Cu. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the product The extrusion temperature of the round bar is 220 ℃, and the extrusion ratio is 9. The mechanical properties obtained by the process are as follows: the tensile strength is 260MPa, the yield strength is 250MPa, and the elongation is 50%. The corrosion rate of the material in the c-SBF solution is 28 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is more than 85%. After the alloy is subjected to heat preservation at 380 ℃ for 0.5 hour, the yield strength of the alloy is 210MPa, the tensile strength is 220MPa, the elongation is 28 percent, and the work hardening index n within 5-10 percent of engineering strain is 0.09. The alloy has strong ageing resistance, and the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the change rate of the properties is within 5 percent. Therefore, the strength of the alloy is low, the work hardening index of the alloy is small, and the comprehensive performance of the alloy is far inferior to that of the alloy.

Comparative example 2

The alloy component Zn-0.5 Mn. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the product The extrusion temperature of the round bar is 220 ℃, and the extrusion ratio is 9. The mechanical properties obtained by the process are as follows: the tensile strength is 200 MPa, the yield strength is 160 MPa, and the elongation is 60%. The corrosion rate of the material in the c-SBF solution is 31 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is more than 70%. After the alloy is subjected to heat preservation for 0.5 hour at 380 ℃, the yield strength of the alloy is 130MPa, the tensile strength is 170MPa, the elongation is 42 percent, and the work hardening index n within 5 to 10 percent of engineering strain is 0.15. The alloy has poor ageing resistance, the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 10 percent. Therefore, the strength of the alloy is low, the work hardening index of the alloy is small, the anti-aging capability is poor, and the comprehensive performance is far inferior to that of the alloy.

Comparative example 3

The alloy composition Zn-0.5 Zr. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the product The extrusion temperature of the round bar is 220 ℃, and the extrusion ratio is 9. The mechanical properties obtained by the process are as follows: the tensile strength is 170MPa, the yield strength is 89 MPa, and the elongation is 32%. The corrosion rate of the material in the c-SBF solution is 23 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is more than 70%. After the alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 70MPa, the tensile strength is 135MPa, the elongation is 28 percent, and the work hardening index n within 5 to 10 percent of engineering strain is 0.14. The alloy has poor ageing resistance, the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 20 percent. It can be seen that the strength of the alloy is low, and at the same timeThe alloy has a small work hardening index, poor ageing resistance and much worse comprehensive performance than the alloy of the patent.

Comparative example 4

The alloy composition Zn-2.5Cu-0.5 Mn. Cutting a certain length of cast ingot, performing solution treatment at 400 ℃ for 24 hours, and extruding to obtain the productThe extrusion temperature of the round bar is 220 ℃, and the extrusion ratio is 9. The mechanical properties obtained by the process are as follows: the tensile strength is 340MPa, the yield strength is 310 MPa, and the elongation is 32%. The corrosion rate of the material in the c-SBF solution is 52 mu m/year. The biological test result shows that the material has no obvious cytotoxicity and good biocompatibility. The antibacterial rate of staphylococcus aureus and escherichia coli is over 90 percent. After the alloy is kept at 380 ℃ for 0.5 hour, the yield strength of the alloy is 260MPa, the tensile strength is 275MPa, the elongation is 35 percent, and the work hardening index n within 5 to 10 percent of engineering strain is 0.19. The alloy has strong ageing resistance, the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, and the performance change rate is within 3 percent. Therefore, the strength of the alloy is slightly low, the work hardening index of the alloy is smaller, the ageing resistance is better, and the comprehensive performance is inferior to that of the alloy.

In summary, the alloy material can further regulate and control the performance of the alloy under the fine adjustment of components or extrusion temperature and extrusion ratio, and meanwhile, the strain hardening index n is more than or equal to 0.20 at the stage of true strain 5-15% by annealing the sample by selecting a proper annealing process (such as 380 ℃ multiplied by 0.5h), so that the alloy material shows good work hardening capacity; meanwhile, the alloy has high strength and plasticity, the mechanical and corrosion properties of the alloy are tested after the alloy is placed at room temperature for 6 months, the change rate of the properties is within 2 percent, and the alloy has excellent ageing resistance and is an in-vivo degradable high-toughness medical Zn-Cu-Mn-Zr alloy material with work hardening and ageing resistance.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.