WO2021243683A1 - 一种生物医用镁合金丝材的制备方法 - Google Patents

一种生物医用镁合金丝材的制备方法 Download PDF

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WO2021243683A1
WO2021243683A1 PCT/CN2020/094573 CN2020094573W WO2021243683A1 WO 2021243683 A1 WO2021243683 A1 WO 2021243683A1 CN 2020094573 W CN2020094573 W CN 2020094573W WO 2021243683 A1 WO2021243683 A1 WO 2021243683A1
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Prior art keywords
magnesium alloy
alloy sheet
stirring
wire
magnesium
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PCT/CN2020/094573
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English (en)
French (fr)
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马政
谭丽丽
杨柯
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四川镁合医疗器械有限责任公司
中国科学院金属研究所
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Priority to KR1020227039669A priority Critical patent/KR20230028224A/ko
Priority to EP20939466.7A priority patent/EP4163028A4/en
Priority to PCT/CN2020/094573 priority patent/WO2021243683A1/zh
Priority to JP2022574551A priority patent/JP2023530877A/ja
Publication of WO2021243683A1 publication Critical patent/WO2021243683A1/zh

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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • 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
    • A61L31/148—Materials at least partially resorbable by the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • 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

Definitions

  • the invention relates to the technical field of preparation of magnesium alloys as metallic materials, and in particular provides a preparation method of biomedical magnesium alloy wires.
  • Magnesium alloy wire as a degradable material with good biological safety, can be gradually degraded and metabolized in the body after the implantation function is realized until it disappears, avoiding secondary removal operations, and has broad application prospects in the field of biomedicine. It is used as an implant material for cardio-sternal connection, orthopedic cartilage connection, general surgery gastrointestinal anastomosis, tracheal stent support, esophageal stent support, and duodenal food filtration.
  • 201710159114.4 discloses a preparation method of equal channel angular extrusion combined with multi-pass drawing to obtain a magnesium-zinc alloy wire with better mechanical and corrosion properties than simple drawing.
  • the equal channel angular extrusion process The size of the prepared magnesium wire is limited, and the material processing loss is large, which is not suitable for large-scale production.
  • this patent introduces a rolling process to replace the drawing process during the initial processing period when the size of the material is large, changes the force of the material in plastic deformation, and improves the performance of the magnesium alloy to a certain extent. Formability and processing efficiency. When the magnesium alloy is rolled into a thin plate, the mechanical stirring process is introduced.
  • the principle is that a stirring needle with a threaded cylinder is mechanically stirred from the center of one end of the plate to the center of the other end, using the relative movement of the stirring needle and the material. Make the material undergo strong plastic deformation, so as to achieve the purpose of improving the microstructure and performance of the material.
  • the schematic diagram is shown in Figure 1. The area through the mechanical stirring process can be used as the final material of the wire after being machined or can be drawn in the next step.
  • the purpose of the present invention is to provide a preparation method for the medical magnesium alloy wire in view of the difficulty in preparing and forming the magnesium alloy wire, and the end-use properties such as strength, plasticity and corrosion resistance are difficult to meet the requirements of the medical wire.
  • a method for preparing biomedical magnesium alloy wire changing the traditional drawing process of metal wire, combining rolling, mechanical stirring, and drawing trinity process, to achieve the optimization of the preparation of magnesium alloy wire and the improvement of the overall performance, including The steps are as follows:
  • step (3) Homogenizing heat treatment of the slab in step (2), the heat treatment temperature is 250 ⁇ 400°C, and the time is 2 ⁇ 5h;
  • the slab in step (3) is processed by hot rolling into a magnesium alloy sheet with a thickness of 70-100 mm, a width of 540-730 mm and a length of 400-1200 mm.
  • the time is 3 ⁇ 6h;
  • the magnesium alloy sheet in step (4) is processed by hot rolling into a magnesium alloy sheet with a thickness of 10-20 mm, a width of 540-730 mm, and a length of 400-1200 mm.
  • the temperature of the metal during hot rolling is 440-470°C. Heating time is 2 ⁇ 5h;
  • the magnesium alloy sheet in step (5) is processed by hot rolling into a magnesium alloy sheet with a thickness of 2-8mm, a width of 540-730mm, and a length of 400-1200mm.
  • the temperature of the metal during hot rolling is 380-440°C. Heating time is 2 ⁇ 4h;
  • step (9) Multi-pass drawing the bar in step (8) into a wire, with annealing heat treatment during the drawing process, the temperature is 280 ⁇ 320°C, the time is 10 ⁇ 60min, the deformation of a single pass is 15-25%, the drawing speed is 0.01-0.05m/s.
  • the other alloying elements are Zn: 0.2% to 2.5%, and Nd: 0.2% to 2.5% in terms of weight percentage.
  • the mechanical stirring process is that the direction of mechanical stirring is carried out along the plate rolling direction, the speed of the stirring needle is 80-120mm/min, and the rotation speed is 400 ⁇ 1200rpm, using 15 ⁇ 25mm diameter concave shaft shoulder bottom center with 1 ⁇ 5mm diameter stirring needle, the inclination angle between the axis of the stirring needle and the normal line of the magnesium alloy sheet workpiece surface is 2.6 ⁇ 3°, the amount of downward pressure during stirring Keep it at 0.1 ⁇ 0.2mm.
  • step (7) the agitating plastic deformation zone of the mechanical stirring process is machined to prepare the wire as a final product, or as an intermediate product, it is processed into a multi-pass drawing process. Wire.
  • the design idea of the present invention is:
  • the present invention changes the traditional drawing process, cooperates with the rolling and mechanical stirring process, firstly reduces the forming difficulty of the magnesium alloy by rolling, ensures the mass production of the material, and provides the possibility for the subsequent mechanical stirring process; and then adopts the mechanical stirring process .
  • To further improve the microstructure of the alloy increase the strength, plasticity, corrosion resistance and subsequent drawing performance of the alloy; finally, the final target wire is achieved through a small amount of drawing process.
  • the above synergistic effect ensures that the wire has good plastic formability, as well as medical mechanical strength and corrosion resistance.
  • the present invention also provides a method for preparing biomedical magnesium alloy wire, which includes the following contents:
  • the mechanical stirring process is that the direction of mechanical stirring is carried out along the plate rolling direction, the speed of the stirring needle is 80-120mm/min, the rotating speed is 400-1200rpm, and the bottom center of the concave shaft shoulder with a diameter of 15-25mm is adopted. Equipped with a stirring needle with a diameter of 1 to 5 mm, the inclination angle between the axis of the stirring needle and the normal line of the surface of the magnesium alloy sheet workpiece is 2.6 to 3°, and the downward pressure during stirring is maintained at 0.1 to 0.2 mm.
  • the present invention also provides a method for preparing magnesium alloy sheet material, which includes the following operation steps:
  • step (3) Homogenizing heat treatment of the slab in step (2), the heat treatment temperature is 250 ⁇ 400°C, and the time is 2 ⁇ 5h;
  • the slab in step (3) is processed by hot rolling into a magnesium alloy sheet with a thickness of 70-100 mm, a width of 540-730 mm and a length of 400-1200 mm.
  • the time is 3 ⁇ 6h;
  • the magnesium alloy sheet in step (4) is processed by hot rolling into a magnesium alloy sheet with a thickness of 10-20 mm, a width of 540-730 mm, and a length of 400-1200 mm.
  • the temperature of the metal during hot rolling is 440-470°C. Heating time is 2 ⁇ 5h;
  • the magnesium alloy sheet in step (5) is processed by hot rolling into a magnesium alloy sheet with a thickness of 2-8mm, a width of 540-730mm, and a length of 400-1200mm.
  • the temperature of the metal during hot rolling is 380-440°C.
  • the heating time is 2 to 4 hours, and the magnesium alloy sheet is obtained.
  • the invention also provides the magnesium alloy wire prepared by the above method.
  • the invention also provides the magnesium alloy sheet prepared by the above method.
  • the present invention also provides an implant in the body, the raw material of which includes the above-mentioned magnesium alloy sheet, or includes a material prepared directly or indirectly from the above-mentioned magnesium alloy sheet.
  • the present invention also provides an in vivo implant, the raw material of which includes the above-mentioned magnesium alloy wire, or a material prepared directly or indirectly from the above-mentioned magnesium alloy wire.
  • the internal implants include staples, surgical sutures, cosmetic threads, skin nails, nerve connecting wires, non-vascular stents, peripheral vascular stents, patches, vascular staplers, bone screws, bone plates, and vascular clips.
  • the bone plates and vascular clips are mainly made of magnesium alloy plates as raw materials. .
  • the raw material of the implant in the body may also include coating materials.
  • the coating material can be used to regulate the degradation rate of the wire in the body.
  • the coating material includes, but is not limited to, magnesium phosphate coating, magnesium oxide coating, magnesium carbonate coating or degradable polymer coating.
  • the invention combines rolling, mechanical stirring and drawing processes to prepare magnesium alloy wire in a large-scale and refined manner, and finally obtain ultra-fine equiaxed crystals.
  • the quantity and size of the second phase of the material are greatly reduced and most of them are dissolved in magnesium.
  • the strength, plasticity and corrosion resistance of the wire have been greatly improved. Therefore, through the improvement of the plasticity, the subsequent drawing process becomes easy, and drawing can be performed even at room temperature.
  • the good strength, plasticity and corrosion resistance of magnesium alloy wire can meet the requirements of clinical use and broaden the scope of clinical application of magnesium alloy wire.
  • FIG. 1 is a schematic diagram of the mechanical stirring process.
  • 1 magnesium alloy sheet 1 stirring plastic deformation zone, 2 stirring needle.
  • Figure 2 shows the morphology of staples prepared from magnesium alloy wire.
  • Figure 3 shows the metallographic structure of magnesium alloy wire.
  • Figure 4 shows the TEM morphology of magnesium alloy wire.
  • Figure 5 is a schematic view of the end face of the stirring pin structure with a concave shoulder. Among them, (a) the bottom end surface of the concave shoulder is stepped, (b) the bottom end surface of the concave shoulder is spiral; in the figure, 3 stirring pins, 4 concave shoulder.
  • the present invention prepares plates from magnesium, zinc, and neodymium alloys through smelting, casting, rolling and other processes. After regional machining, it is used as the final product of the wire or it is drawn in multiple passes to finally form the wire of the required diameter.
  • the traditional drawing preparation process is changed from the preparation process of magnesium alloy wire, and rolling is introduced. Preparation, mechanical stirring process, combined with subsequent drawing, can improve the forming performance of magnesium alloy wire, and finally can be processed into a thin wire with a minimum diameter of 0.1mm.
  • the severe plastic deformation caused by mechanical stirring allows the material to obtain fine equiaxed grains, introduces dislocation strengthening materials, and improves the plasticity of the material through the solid solution of the second phase, and at the same time improves the corrosion resistance of the alloy.
  • the Mg-2Zn-0.5Nd alloy is composed of 2% Zn, 0.5% Nd by weight, and the balance is Mg.
  • Preparation method In terms of weight percentage, pure magnesium, 2% Zn, 0.5% Nd are smelted into liquid metal, and cast into slabs to remove surface defects and impurities. The slabs are subjected to homogenization heat treatment at 300°C for 5 hours, and then through hot rolling ( The furnace temperature is 480°C, the heating time is 4h), and it is processed into a magnesium alloy sheet with a thickness of 70mm, a width of 540mm and a length of 400mm; then it is processed into a thickness of 10mm, a width of 540mm, and a length of 10mm by hot rolling (the furnace temperature is 440°C, and the heating time is 4h). 400mm magnesium alloy sheet; then the sheet is processed into a magnesium alloy sheet with a thickness of 2mm, a width of 540mm and a length of 400mm by hot rolling (with a furnace temperature of 440°C and a heating time of 2h).
  • the magnesium alloy sheet 1 is processed by a mechanical stirring process.
  • the direction of mechanical stirring is along the rolling direction of the sheet.
  • the stirring needle 3 travels along the horizontal stirring direction at a speed of 100mm/min and a rotation speed of 800rpm.
  • the 20mm diameter concave shaft shoulder is equipped with a 2mm diameter stirring needle 3 at the bottom center.
  • the inclination angle between the axis of the stirring needle 3 and the normal line of the surface of the magnesium alloy plate 1 workpiece is about 2.8° (this inclination angle is beneficial to the extension of the stirring needle Into the material for friction and stirring, the inclination direction of the stirring needle 3 is opposite to the direction of stirring, and the downward pressure in the stirring is maintained at 0.15mm; thus, it is processed into a band area with strong plastic deformation (stirring plastic deformation zone 2 ), the area is cut and machined into a rod with a diameter of ⁇ 2mm, and the rod is drawn, with annealing heat treatment during the drawing process, the temperature is 280°C, the time is 20min, and the deformation of a single pass is about 20% , The drawing speed is 0.05m/s, and finally a wire with a diameter of 0.3mm is formed.
  • the U-shaped staple prepared from the wire is shown in Figure 2, and the microstructure of the wire is shown in Figure 3.
  • the grains of the wire are equiaxed crystals, and the TEM morphology of the wire is shown in Figure 4, and the grains of the alloy
  • the size is small, the size is between 500nm-1 ⁇ m, dislocations are formed inside the crystal grains, and the alloy is further strengthened, and the second phase size produced is extremely small, only 50-100nm.
  • the center of the bottom end surface of the concave shoulder 4 is installed with the stirring needle 3, and the junction between the concave shoulder 4 and the stirring needle 3 is recessed, which increases the contact area between the concave shoulder 4 and the surface of the plate.
  • the softened material under the end of the concave shoulder 4 is subjected to an inward force, so that the concave shoulder 4 and the plasticized material are tightly coupled together.
  • Degradation rate (Hank's solution, soaked for 30 days, 37°C): 0.33mm/year.
  • the Mg-0.2Zn-2.0Nd alloy has components in weight percentage: 0.2% Zn, 2.0% Nd, and the balance is Mg.
  • Preparation method In terms of weight percentage, pure magnesium, 0.2% Zn, 2.0% Nd are smelted into liquid metal, cast into slabs, surface defects and impurities are removed, and the slabs are homogenized heat treatment at 320°C for 5h, and pass hot rolling ( The furnace temperature is 480°C, the heating time is 4h), and it is processed into a magnesium alloy sheet with a thickness of 70mm, a width of 540mm and a length of 400mm; then it is processed into a thickness of 10mm, a width of 540mm, and a length of 10mm by hot rolling (the furnace temperature is 440°C, and the heating time is 4h). 400mm magnesium alloy sheet; then the sheet is processed into a magnesium alloy sheet with a thickness of 2mm, a width of 540mm, and a length of 400mm through hot rolling (with a furnace temperature of 440°C and a heating time of 2h).
  • the magnesium alloy sheet 1 is processed by a mechanical stirring process.
  • the direction of mechanical stirring is along the rolling direction of the sheet.
  • the stirring needle 3 travels along the horizontal stirring direction at a speed of 100mm/min and a rotation speed of 800rpm.
  • a 20mm diameter concave shaft shoulder bottom center is equipped with a 2mm diameter stirring needle 3 ( Figure 5)
  • the inclination of the axis of the stirring needle 3 and the normal line of the surface of the magnesium alloy plate 1 workpiece is about 2.8 °
  • the inclination direction of the stirring needle 3 and The direction of stirring is reversed, and the downward pressure during stirring is maintained at 0.15mm; thus, a strip area with strong plastic deformation (stirring plastic deformation zone 2) is processed, and this area is cut and machined into a rod with a diameter of ⁇ 2mm.
  • the bar is drawn, and annealing heat treatment is performed during the drawing process.
  • the temperature is 280°C
  • the time is 20min
  • the single pass deformation is about 20%
  • the drawing speed is 0.05m/s
  • the final diameter is 0.6mm. Of wire.
  • the grain of the wire is equiaxed, the grain size of the alloy is small, the size is between 500nm and 1 ⁇ m, dislocations are formed inside the grains, and the alloy is further strengthened, and the second phase size produced is extremely small, only 50 ⁇ 100nm.
  • Degradation rate (Hank's solution, soaked for 30 days, 37°C): 0.36mm/year.
  • the results of the examples show that the present invention improves the wire forming performance by introducing rolling and mechanical stirring processes, so that the alloy grains are significantly refined, the size of the second phase is greatly reduced, and most of the wires are dissolved in the matrix.
  • the strength, especially the elongation, is greatly improved, and better corrosion resistance is obtained, which meets the performance requirements of medical magnesium alloy wires.

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Abstract

本发明涉及金属材料镁合金的制备技术领域，特别提供一种生物医用镁合金丝材的制备方法。将镁、锌、钕合金经熔炼、铸造、轧制等工艺制备出板材，将上述板材经过特殊的机械搅拌工艺制备一道与板材同等厚度的加工区，将该加工区域机加工处理后作为丝材的最终产品或者再进行多道次拉拔，最终形成所需直径的丝材。本发明通过引入轧制和机械搅拌工艺，改善丝材成形性能，使得合金晶粒显著细化，第二相尺寸大幅度减小且多数固溶于基体中，得到的丝材强度尤其是延伸率得到大幅提高，并且获得较好的耐蚀性能，满足医用镁合金丝材的性能要求。

Description

一种生物医用镁合金丝材的制备方法 技术领域
本发明涉及金属材料镁合金的制备技术领域，特别提供一种生物医用镁合金丝材的制备方法。
背景技术
镁合金丝材作为一种可降解并具有良好生物安全性的材料，可在实现植入功能后在体内逐渐降解代谢直至消失，避免二次取出手术，在生物医用领域有广阔的应用前景，可作为心外科胸骨连接、整形外科软骨连接、普外科肠胃吻合、气管支架支撑、食道支架支撑和十二指肠食物过滤等植入材料。
镁合金丝材的强度、塑性及腐蚀速率是其实现医学应用的关键。镁细丝材是通过拉拔形成，其显微组织、力学性能和耐腐蚀性能在此过程并未得到改善，另外镁合金丝材不同的添加元素影响其拉丝成形性能。中国专利申请号201810068159.5公布一种大挤压比碎晶结合拉拔的方式制备一种Mg-Zn-Mn-X(X＝Ag、Sr、Ca、Bi)合金丝，获得的丝材直径小、显微组织均匀且力学性能良好。中国专利申请号201710159114.4公布一种等径角挤压结合多道次拉拔的制备方式，获得一种力学和腐蚀性能优于单纯拉拔获得的镁锌合金丝材，然而等径角挤压工艺制备镁丝尺寸有限，且材料加工损耗较大，不适于规模生产。本专利在常规拉拔镁合金丝材的基础上，在材料尺寸较大的初加工期间，引入轧制工艺替代拉拔工艺，改变材料在塑性变形中的受力情况，一定程度改善镁合金的成形性能和加工效率。当镁合金轧制成薄板时，再引入机械搅拌工艺，其原理是由一个带螺纹圆柱体的搅拌针从板材的一端中心处机械搅拌到另一端中心处，利用搅拌针和材料的相对运动，使得材料发生强烈的塑性变形，从而达到改善材料的微观组织及性能的目的，其示意图见图1。通过机械搅拌工艺的区域进行机加工处理后可作为丝材的最终材料或者可进行下一步拉拔。
发明内容
本发明的目的是针对镁合金丝材制备成形困难，最终使用性能如强度、塑性和耐腐蚀性能难以达到医用丝材的要求，特提供一种用于医用镁合金丝材的制备方法。
本发明的技术方案是：
一种生物医用镁合金丝材的制备方法，改变传统金属丝材拉拔工艺，结合轧制、机械搅拌、拉拔三位一体的工艺，实现镁合金丝材制备的优化和整体使用性能的提升，包括如下操作步骤：
(1)将纯镁和其他合金元素按比例熔炼成液态金属，搅拌均匀，去除熔渣；
(2)将步骤(1)中的合金溶液浇铸成扁锭，去除表面缺陷和杂质；
(3)将步骤(2)中的扁锭均匀化热处理，热处理温度为250～400℃，时间为2～5h；
(4)将步骤(3)中的扁锭通过热轧，加工成厚70～100mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为470～510℃，加热时间为3～6h；
(5)将步骤(4)中的镁合金板材通过热轧，加工成厚10～20mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为440～470℃，加热时间为2～5h；
(6)将步骤(5)中的镁合金板材通过热轧，加工成厚2～8mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为380～440℃，加热时间为2～4h；
(7)将步骤(6)中的镁合金板材通过机械搅拌工艺进行加工，制备一道与镁合金板材同等厚度的搅拌塑性变形区；
(8)将步骤(7)镁合金板材中的搅拌塑性变形区切割下来，机加工成直径Φ2～8mm的棒材；
(9)将步骤(8)中的棒材进行多道次拉拔加工成丝材，拉拔过程中配合退火热处理，温度为280～320℃，时间为10～60min，单道次变形量为15～25％，拉拔速度在0.01～0.05m/s。
所述的生物医用镁合金丝材的制备方法，步骤(1)中，按重量百分比计，其他合金元素为Zn：0.2％～2.5％，Nd：0.2％～2.5％。
所述的生物医用镁合金丝材的制备方法，步骤(7)中，机械搅拌工艺为，机械搅拌的方向沿板材轧制方向进行，搅拌针行进的速度为80～120mm/min，转速为400～1200rpm，采用直径15～25mm的下凹轴肩底部中心设有直径1～5mm的搅拌针，搅拌针轴线与镁合金板材工件表面法线的倾角为2.6～3°，搅拌中的下压量保持为0.1～0.2mm。
所述的生物医用镁合金丝材的制备方法，步骤(7)中，机械搅拌工艺的搅拌塑性变形区经过机加工制备丝材作为最终产品，或者作为中间产品再进行多道次拉拔加工成丝材。
本发明的设计思想是：
针对目前镁合金拉丝形成性不佳，最终产品性能难以达到医用材料的力学性能和腐蚀性能等问题。本发明改变传统拉拔工艺，协同轧制、机械搅拌处理工艺，首先通 过轧制降低镁合金的成形困难，保证材料的规模化生产，并为后续的机械搅拌工艺提供可能；再通过机械搅拌工艺，进一步改善合金的显微组织，提高合金的强度、塑性和耐腐蚀性能及后续拉拔性能；最后，通过少量的拉拔工艺达到最终的目标丝材。以上协同作用，保证丝材具有良好的塑性成形性，以及医用的力学强度和耐腐蚀性能。
本发明还提供了一种生物医用镁合金丝材的制备方法，它包括如下内容：
A、对镁合金板材进行机械搅拌，制备一道与镁合金板材同等厚度的搅拌塑性变形区；
B、以搅拌塑性变形区制备直径Φ2～8mm的棒材；
C、棒材拉拔加工成丝材；
其中，所述机械搅拌工艺为，机械搅拌的方向沿板材轧制方向进行，搅拌针行进的速度为80～120mm/min，转速为400～1200rpm，采用直径15～25mm的下凹轴肩底部中心设有直径1～5mm的搅拌针，搅拌针轴线与镁合金板材工件表面法线的倾角为2.6～3°，搅拌中的下压量保持为0.1～0.2mm。
本发明还提供了一种镁合金板材的制备方法，包括如下操作步骤：
(1)将纯镁和其他合金元素按比例熔炼成液态金属，搅拌均匀，去除熔渣；
(2)将步骤(1)中的合金溶液浇铸成扁锭，去除表面缺陷和杂质；
(3)将步骤(2)中的扁锭均匀化热处理，热处理温度为250～400℃，时间为2～5h；
(4)将步骤(3)中的扁锭通过热轧，加工成厚70～100mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为470～510℃，加热时间为3～6h；
(5)将步骤(4)中的镁合金板材通过热轧，加工成厚10～20mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为440～470℃，加热时间为2～5h；
(6)将步骤(5)中的镁合金板材通过热轧，加工成厚2～8mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为380～440℃，加热时间为2～4h，即得镁合金板材。本发明还提供了上述方法制备的镁合金丝材。
本发明还提供了上述方法制备的镁合金板材。
本发明还提供了一种体内植入物，其原料包括上述的镁合金板材，或者包括上述镁合金板材直接或间接制备的材料。
本发明还提供了一种体内植入物，其原料包括上述的镁合金丝材，或者包括上述镁合金丝材直接或间接制备的材料。
其中，所述体内植入物包括吻合钉、外科缝合线、美容线、皮钉、神经连接丝、非血管支架、外周血管支架、补片、血管吻合器、骨螺钉、接骨板、血管夹。其中，接骨板、血管夹主要是以镁合金板材为原料制备。。
另外，体内植入物的原料还可以包括涂层材料。
涂层材料可以是用以调控丝材在体内的降解速度。所述涂层材料包括但不限于磷酸镁涂层、氧化镁涂层、碳酸镁涂层或可降解的高分子涂层。
本发明的优点及有益效果是：
本发明结合轧制、机械搅拌及拉拔工艺，能够规模化、精细化制备镁合金丝材，最终获得超细等轴晶，材料第二相的数量尺寸大幅度减小且大多固溶于镁基体中，丝材的强度、塑性和耐腐蚀性得到大幅度提升。从而，通过塑性的提高，使得后续拉拔工艺变得容易甚至在室温下亦可以进行拉拔。镁合金丝材良好的强度、塑性和耐腐蚀性能能够满足于临床使用要求，扩宽镁合金丝材的临床应用范围。
附图说明
图1为机械搅拌工艺示意图。图中，1镁合金板材，2搅拌塑性变形区，3搅拌针。
图2为由镁合金丝材制备的吻合钉形貌。
图3为镁合金丝材的金相组织。
图4为镁合金丝材的TEM形貌。
图5为具有下凹轴肩的搅拌针结构端面示意图。其中，(a)下凹轴肩的底部端面为阶梯形，(b)下凹轴肩的底部端面为螺旋形；图中，3搅拌针，4下凹轴肩。
具体实施方式
在具体实施过程中，本发明将镁、锌、钕合金经熔炼、铸造、轧制等工艺制备出板材，将上述板材经过特殊的机械搅拌工艺制备一道与板材同等厚度的加工区，将该加工区域机加工处理后作为丝材的最终产品或者再进行多道次拉拔，最终形成所需直径的丝材。针对镁合金丝材制备成形困难，最终使用性能如强度、塑性和耐腐蚀性能不足，难以达到医用丝材的要求等问题，从镁合金丝材的制备过程中改变传统拉拔制备工艺，引入轧制、机械搅拌工艺，再结合后续的拉拔，可以改善镁合金丝材的成形性能，最终可加工成最小直径为0.1mm的细丝。并且，通过机械搅拌带来的剧烈塑性变形，使得材料获得细小的等轴晶粒，引入位错强化材料，通过第二相的固溶提高材料的塑性，同时提高合金的耐蚀性能。
下面，结合附图对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
本实施例中，Mg-2Zn-0.5Nd合金，成分按重量百分比：2％Zn，0.5％Nd，余量为 Mg。
制备方法：按重量百分比计，将纯镁和2％Zn、0.5％Nd熔炼成液态金属，浇铸成扁锭，去除表面缺陷和杂质，扁锭在300℃做均匀化热处理5h，通过热轧(出炉温度480℃，加热时间为4h)，加工成厚70mm、宽540mm、长400mm的镁合金板材；接着通过热轧(出炉温度440℃，加热时间为4h)加工成厚10mm、宽540mm、长400mm的镁合金板材；接着板材通过热轧(出炉温度440℃，加热时间为2h)，加工成厚2mm、宽540mm、长400mm的镁合金板材。
如图1所示，将镁合金板材1通过机械搅拌工艺进行加工，机械搅拌的方向沿板材轧制方向进行，搅拌针3沿着水平搅拌行进方向行进的速度为100mm/min，转速为800rpm，采用直径20mm的下凹轴肩底部中心设有直径2mm的搅拌针3，搅拌针3轴线与镁合金板材1工件表面法线的倾角为2.8°左右(该倾角所起的作用是利于搅拌针伸进材料内部进行摩擦和搅拌，搅拌针3的倾斜方向与搅拌行进方向相反，搅拌中的下压量保持为0.15mm；从而，加工成一个具有强烈塑性变形的条带区域(搅拌塑性变形区2)，将该区域切割下来，机加工成直径Φ2mm的棒材，将棒材进行拉拔，拉拔过程中配合退火热处理，温度为280℃，时间为20min，单道次变形量为20％左右，拉拔速度在0.05m/s，最终形成直径0.3mm的丝材。
由该丝材制备的U形吻合钉见图2，丝材的显微组织见图3，该丝材的晶粒为等轴晶，丝材的透射电镜形貌见图4，合金的晶粒尺寸细小，尺寸在500nm～1μm之间，晶粒内部有位错形成，进一步强化合金，产生的第二相尺寸极小，仅为50～100nm。
如图5所示，下凹轴肩4的底部端面中心安装搅拌针3，下凹轴肩4与搅拌针3的交界处凹入，增大下凹轴肩4与板材表面的接触面积，能够让下凹轴肩4端部下方软化的材料受到向内方向的力的作用，从而使下凹轴肩4和塑化材料紧密地耦合在一起。
拉伸性能(GB/T 228-2002)：抗拉强度为320MPa，延伸率为15％。
降解速率(Hank's液，浸泡30天，37℃)：0.33mm/年。
实施例2
本实施例中，Mg-0.2Zn-2.0Nd合金，成分按重量百分比：0.2％Zn，2.0％Nd，余量为Mg。
制备方法：按重量百分比计，将纯镁和0.2％Zn、2.0％Nd熔炼成液态金属，浇铸成扁锭，去除表面缺陷和杂质，扁锭在320℃做均匀化热处理5h，通过热轧(出炉温度480℃，加热时间为4h)，加工成厚70mm、宽540mm、长400mm的镁合金板材；接着通过热轧(出炉温度440℃，加热时间为4h)加工成厚10mm、宽540mm、长400mm 的镁合金板材；接着板材通过热轧(出炉温度440℃，加热时间为2h)，加工成厚2mm、宽540mm、长400mm的镁合金板材。
如图1所示，将镁合金板材1通过机械搅拌工艺进行加工，机械搅拌的方向沿板材轧制方向进行，搅拌针3沿着水平搅拌行进方向行进的速度为100mm/min，转速为800rpm，采用直径20mm的下凹轴肩底部中心设有直径2mm的搅拌针3(图5)，搅拌针3轴线与镁合金板材1工件表面法线的倾角为2.8°左右，搅拌针3的倾斜方向与搅拌行进方向相反，搅拌中的下压量保持为0.15mm；从而，加工成一个具有强烈塑性变形的条带区域(搅拌塑性变形区2)，将该区域切割下来，机加工成直径Φ2mm的棒材，将棒材进行拉拔，拉拔过程中配合退火热处理，温度为280℃，时间为20min，单道次变形量为20％左右，拉拔速度在0.05m/s，最终形成直径0.6mm的丝材。
该丝材的晶粒为等轴晶，合金的晶粒尺寸细小，尺寸在500nm～1μm之间，晶粒内部有位错形成，进一步强化合金，产生的第二相尺寸极小，仅为50～100nm。
拉伸性能(GB/T 228-2002)：抗拉强度为360MPa，延伸率为21％。
降解速率(Hank's液，浸泡30天，37℃)：0.36mm/年。
实施例结果表明，本发明通过引入轧制和机械搅拌工艺，改善丝材成形性能，使得合金晶粒显著细化，第二相尺寸大幅度减小且多数固溶于基体中，得到的丝材强度尤其是延伸率得到大幅提高，并且获得较好的耐蚀性能，满足医用镁合金丝材的性能要求。

Claims (13)

  1. 一种生物医用镁合金丝材的制备方法，其特征在于，包括如下操作步骤：
    (1)将纯镁和其他合金元素按比例熔炼成液态金属，搅拌均匀，去除熔渣；
    (2)将步骤(1)中的合金溶液浇铸成扁锭，去除表面缺陷和杂质；
    (3)将步骤(2)中的扁锭均匀化热处理，热处理温度为250～400℃，时间为2～5h；
    (4)将步骤(3)中的扁锭通过热轧，加工成厚70～100mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为470～510℃，加热时间为3～6h；
    (5)将步骤(4)中的镁合金板材通过热轧，加工成厚10～20mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为440～470℃，加热时间为2～5h；
    (6)将步骤(5)中的镁合金板材通过热轧，加工成厚2～8mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为380～440℃，加热时间为2～4h；
    (7)将步骤(6)中的镁合金板材通过机械搅拌工艺进行加工，制备一道与镁合金板材同等厚度的搅拌塑性变形区；
    (8)将步骤(7)镁合金板材中的搅拌塑性变形区切割下来，机加工成直径Φ2～8mm的棒材；
    (9)将步骤(8)中的棒材进行多道次拉拔加工成丝材，拉拔过程中配合退火热处理，温度为280～320℃，时间为10～60min，单道次变形量为15～25％，拉拔速度在0.01～0.05m/s。
  2. 按照权利要求1所述的生物医用镁合金丝材的制备方法，其特征在于，步骤(1)中，按重量百分比计，其他合金元素为Zn：0.2％～2.5％，Nd：0.2％～2.5％。
  3. 按照权利要求1所述的生物医用镁合金丝材的制备方法，其特征在于，步骤(7)中，机械搅拌工艺为，机械搅拌的方向沿板材轧制方向进行，搅拌针行进的速度为80～120mm/min，转速为400～1200rpm，采用直径15～25mm的下凹轴肩底部中心设有直径1～5mm的搅拌针，搅拌针轴线与镁合金板材工件表面法线的倾角为2.6～3°，搅拌中的下压量保持为0.1～0.2mm。
  4. 按照权利要求1所述的生物医用镁合金丝材的制备方法，其特征在于，步骤(7)中，机械搅拌工艺的搅拌塑性变形区经过机加工制备丝材作为最终产品，或者作为中间产品再进行多道次拉拔加工成丝材。
  5. 一种生物医用镁合金丝材的制备方法，其特征在于，它包括如下内容：
    A、对镁合金板材进行机械搅拌，制备一道与镁合金板材同等厚度的搅拌塑性变形区；
    B、以搅拌塑性变形区制备直径Φ2～8mm的棒材；
    C、棒材拉拔加工成丝材；
    其中，所述机械搅拌工艺为，机械搅拌的方向沿板材轧制方向进行，搅拌针行进的速度为80～120mm/min，转速为400～1200rpm，采用直径15～25mm的下凹轴肩底部中心设有直径1～5mm的搅拌针，搅拌针轴线与镁合金板材工件表面法线的倾角为2.6～3°，搅拌中的下压量保持为0.1～0.2mm。
  6. 一种镁合金板材的制备方法，其特征在于：包括如下操作步骤：
    (1)将纯镁和其他合金元素按比例熔炼成液态金属，搅拌均匀，去除熔渣；
    (2)将步骤(1)中的合金溶液浇铸成扁锭，去除表面缺陷和杂质；
    (3)将步骤(2)中的扁锭均匀化热处理，热处理温度为250～400℃，时间为2～5h；
    (4)将步骤(3)中的扁锭通过热轧，加工成厚70～100mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为470～510℃，加热时间为3～6h；
    (5)将步骤(4)中的镁合金板材通过热轧，加工成厚10～20mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为440～470℃，加热时间为2～5h；
    (6)将步骤(5)中的镁合金板材通过热轧，加工成厚2～8mm、宽540～730mm、长400～1200mm的镁合金板材，热轧时金属出炉温度为380～440℃，加热时间为2～4h，即得镁合金板材。
  7. 权利要求1～5任意一项所述方法制备的镁合金丝材。
  8. 权利要求6所述方法制备的镁合金板材。
  9. 一种体内植入物，其特征在于：其原料包括权利要求8所述的镁合金板材，或者包括由权利要求8所述镁合金板材制备的材料。
  10. 一种体内植入物，其特征在于：其原料包括权利要求7所述的镁合金丝材，或者包括由权利要求7所述镁合金丝材制备的材料。
  11. 根据权利要求9或10所述的体内植入物，其特征在于：所述体内植入物包括吻合钉、外科缝合线、美容线、皮钉、神经连接丝、非血管支架、外周血管支架、补片、血管吻合器、骨螺钉、接骨板、血管夹。
  12. 根据权利要求9-11任意一项所述所述的体内植入物，其特征在于：其原料还包括涂层材料。
  13. 根据权利要求12所述所述的体内植入物，其特征在于：所述涂层材料包括磷酸镁涂层、氧化镁涂层、碳酸镁涂层或可降解的高分子涂层。
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