CN104862566A - High-strength high-plasticity medical magnesium alloy, and preparation method and applications thereof - Google Patents
High-strength high-plasticity medical magnesium alloy, and preparation method and applications thereof Download PDFInfo
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Abstract
本发明公开了一种高强高塑性医用镁合金及其制备方法和应用,属于医用镁合金材料技术领域。通过在镁基体中复合添加Zn、Nd、Mn作为合金元素,并对镁合金进行挤压加工,使镁合金的塑性变形能力显著提高,并通过提高合金中Zn元素的含量,使镁合金的抗拉强度得到大幅度提高。新型医用镁合金组分质量百分比为:0.2-6.0Zn,0.5-2.0Nd,0.5Mn,限制杂质含量重量百分比为:Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。本发明合金铸锭在400~550℃,10小时均匀化处理后,在390℃挤压,挤压比36:1,润滑剂为动物油。本发明合金的室温抗拉强度最高可达到300MPa,延伸率最高可达到37%。The invention discloses a high-strength and high-plasticity medical magnesium alloy, a preparation method and application thereof, and belongs to the technical field of medical magnesium alloy materials. By adding Zn, Nd, and Mn as alloy elements in the magnesium matrix, and extruding the magnesium alloy, the plastic deformation ability of the magnesium alloy is significantly improved, and by increasing the content of Zn element in the alloy, the resistance of the magnesium alloy is improved. The tensile strength has been greatly improved. The weight percentage of the new medical magnesium alloy components is: 0.2-6.0Zn, 0.5-2.0Nd, 0.5Mn, and the weight percentage of the restricted impurity content is: Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. The alloy ingot of the present invention is subjected to homogenization treatment at 400-550° C. for 10 hours, and then extruded at 390° C. with an extrusion ratio of 36:1, and the lubricant is animal oil. The room temperature tensile strength of the alloy of the invention can reach up to 300MPa, and the elongation can reach up to 37%.
Description
技术领域technical field
本发明涉及镁合金材料技术领域,具体涉及一种高强高塑性医用镁合金及其制备工艺和应用,该镁合金用作可降解金属植入材料。The invention relates to the technical field of magnesium alloy materials, in particular to a high-strength and high-plasticity medical magnesium alloy and its preparation process and application. The magnesium alloy is used as a degradable metal implant material.
背景技术Background technique
近年来,镁合金作为新一代可降解生物医用材料,已成为生物材料研究的前沿课题。与传统的惰性金属植入材料(如不锈钢、钴铬合金、钛合金等)相比,镁合金可以在患者治疗康复之后完全降解,不需二次手术取出,减少了患者的痛苦与费用。镁合金具有金属材料所具备的良好的机械性能和加工性能,同时镁是一种人体所必须的微量元素,参与人体多项生理活动,因此镁表现出优良的生物相容性。很多研究结果表明,镁合金还有多种生物功能化作用。因此镁合金以其优异的综合性能,有望成为理想的可降解金属植入材料。In recent years, magnesium alloy, as a new generation of biodegradable biomedical materials, has become a frontier topic in biomaterials research. Compared with traditional inert metal implant materials (such as stainless steel, cobalt-chromium alloy, titanium alloy, etc.), magnesium alloy can be completely degraded after the patient recovers from treatment, and does not require secondary surgery to remove it, reducing the pain and cost of the patient. Magnesium alloys have the good mechanical properties and processing properties of metal materials. At the same time, magnesium is an essential trace element for the human body and participates in many physiological activities of the human body. Therefore, magnesium exhibits excellent biocompatibility. Many studies have shown that magnesium alloys also have a variety of biological functions. Therefore, magnesium alloy is expected to become an ideal biodegradable metal implant material due to its excellent comprehensive properties.
随着镁合金作为生物材料研究应用领域中的不断拓展,对镁合金各方面的性能要求也越来越高,越来越多样化。例如,镁合金作为可降解心血管支架材料,支架在使用过程中要经历较大的塑性变形,在体内服役过程中,支架需要对发生病变狭窄部位的血管提供持续足够的支撑力,这就要求镁合金必须有足够的强度;作为可降解的缝合线材料,缝合线在使用时的打结过程也要求镁合金必须具备优良的塑性变形能力,同时缝合线还必须具备较高的强度,对伤口提供足够的张力固定伤口;镁合金作为可降解骨钉、骨板或骨填充材料使用时,对镁合金的强度要求也比较高。但是密排六方晶体结构使镁合金的塑形变形性能非常有限,而且强度较低,必须通过合理的合金化设计与热处理制度,以及优化的加工工艺等方式去提高镁合金的塑性变形能力和强度。With the continuous expansion of the field of research and application of magnesium alloys as biomaterials, the performance requirements for magnesium alloys are becoming higher and higher and more diverse. For example, magnesium alloy is used as a degradable cardiovascular stent material. The stent will undergo large plastic deformation during use. Magnesium alloy must have sufficient strength; as a degradable suture material, the knotting process of suture also requires magnesium alloy to have excellent plastic deformation ability, and suture must also have high strength. Provide sufficient tension to fix the wound; when magnesium alloys are used as degradable bone nails, bone plates or bone filling materials, the strength requirements for magnesium alloys are relatively high. However, due to the close-packed hexagonal crystal structure, the plastic deformation performance of magnesium alloys is very limited, and the strength is low. It is necessary to improve the plastic deformation ability and strength of magnesium alloys through reasonable alloying design, heat treatment system, and optimized processing technology. .
发明内容Contents of the invention
本发明的目的在于提供一种高强高塑性医用镁合金及其制备工艺和应用,该合金既有良好的塑性变形能力,又有较高的强度,且无毒性。The object of the present invention is to provide a high-strength and high-plasticity medical magnesium alloy and its preparation process and application. The alloy not only has good plastic deformation ability, but also has relatively high strength and is non-toxic.
本发明的技术方案是:Technical scheme of the present invention is:
一种高强高塑性医用镁合金,按重量百分比计,其化学成分为:Zn0.2-6.0%,Mn0.15-0.5%(优选为0.5%),Nd0.5-2.0%,限制杂质元素含量为:Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。A high-strength and high-plasticity medical magnesium alloy, by weight percentage, its chemical composition is: Zn0.2-6.0%, Mn0.15-0.5% (preferably 0.5%), Nd0.5-2.0%, limit the content of impurity elements It is: Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg.
本发明合金的制备工艺包括如下步骤:The preparation technology of alloy of the present invention comprises the steps:
(1)均质化处理:将镁合金铸锭在真空热处理炉中于400~550℃进行均质化热处理10个小时,从而使铸锭的成分与组织均匀化,然后水冷,形成过饱和固溶体;(1) Homogenization treatment: The magnesium alloy ingot is subjected to homogenization heat treatment at 400-550°C for 10 hours in a vacuum heat treatment furnace to homogenize the composition and structure of the ingot, and then water-cooled to form a supersaturated solid solution ;
(2)挤压处理:挤压前铸锭在炉中于390℃预热2个小时,然后在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,从而获得所述医用镁合金。(2) Extrusion treatment: before extrusion, the ingot is preheated in the furnace at 390°C for 2 hours, and then extruded at 380°C, the extrusion ratio is 36:1, the extrusion speed is 4m/min, and animal oil is used as lubricating oil , so as to obtain the medical magnesium alloy.
上述步骤(1)中所述镁合金铸锭的制备步骤如下:The preparation steps of the magnesium alloy ingot described in the above step (1) are as follows:
(a)配料:针对不同的成分设计,先进行配料,配料中包括纯度为99.99%的Mg锭,纯度为99.99%的Zn锭,纯度为99.99%的Mg-30Nd中间合金,电解Mn粉;(a) Ingredients: According to different composition designs, the ingredients are prepared first, including Mg ingots with a purity of 99.99%, Zn ingots with a purity of 99.99%, Mg-30Nd master alloys with a purity of 99.99%, and electrolytic Mn powder;
(b)合金熔炼及浇铸:在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃;待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀;在合金熔炼过程中,持续通入保护性气体;降温至700℃静置15-30分钟,使夹杂物沉降,然后撇去表层浮渣,浇铸至石墨模具中,石墨模具略带喇叭口,防止较大的缩孔的出现,最后获得高纯净度的医用镁合金铸锭。(b) Alloy smelting and casting: add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C; Continue smelting at 720°C for 30 minutes, stirring twice to make the melt uniform; during alloy smelting, continuously feed protective gas; cool down to 700°C and let stand for 15-30 minutes to allow inclusions to settle, then skim off The surface scum is cast into a graphite mold, which has a slightly flared mouth to prevent the occurrence of large shrinkage cavities, and finally obtain a high-purity medical magnesium alloy ingot.
该医用镁合金用作可降解金属植入材料,如可降解心血管支架材料、可降解的缝合线材料、可降解骨钉、骨板或骨填充材料等。The medical magnesium alloy is used as a degradable metal implant material, such as a degradable cardiovascular stent material, a degradable suture material, a degradable bone nail, a bone plate or a bone filling material and the like.
本发明镁合金设计原理如下:The magnesium alloy design principle of the present invention is as follows:
本发明涉及一种新型含Zn、Mn以及稀土元素Nd的高强高塑性变形镁合金,是将金属元素Zn、Mn和稀土元素Nd作为合金元素加入镁中形成。Zn元素在镁基体中有较高的溶解度,有明显的固溶强化作用,可显著提高材料的强度;少量Mn元素的加入有助于消除杂质Fe对镁合金耐蚀性能的影响;Nd元素一方面可以细化变形镁合金再结晶晶粒,而且还能减弱变形镁合金织构强度。通过Zn、Mn、Nd三种合金元素的共同作用,可提高镁合金的强度与塑性及其耐蚀性能。将铸态镁合金在400~550℃均匀化处理10个小时,然后水冷,获得成分与组织均匀的镁合金挤压坯料。挤压前镁合金于390℃预热2小时,挤压温度380℃,挤压比36:1,挤压出口速度4m/min,得到直径10mm的镁合金棒材,其既有极高的塑性变形性能和很高的抗拉伸强度,还有非常好的耐腐蚀性能。The invention relates to a novel high-strength and high-plastic deformation magnesium alloy containing Zn, Mn and rare earth element Nd, which is formed by adding metal elements Zn, Mn and rare earth element Nd into magnesium as alloy elements. Zn element has high solubility in the magnesium matrix and has obvious solid solution strengthening effect, which can significantly improve the strength of the material; the addition of a small amount of Mn element helps to eliminate the influence of impurity Fe on the corrosion resistance of magnesium alloys; Nd element a On the one hand, it can refine the recrystallized grains of the deformed magnesium alloy, and it can also weaken the texture strength of the deformed magnesium alloy. The strength, plasticity and corrosion resistance of magnesium alloys can be improved through the joint action of the three alloying elements Zn, Mn and Nd. The as-cast magnesium alloy is homogenized at 400-550° C. for 10 hours, and then water-cooled to obtain a magnesium alloy extrusion billet with uniform composition and structure. The magnesium alloy is preheated at 390°C for 2 hours before extrusion, the extrusion temperature is 380°C, the extrusion ratio is 36:1, and the extrusion exit speed is 4m/min to obtain a magnesium alloy rod with a diameter of 10mm, which has extremely high plasticity Deformation properties and high tensile strength, as well as very good corrosion resistance.
本发明有益效果如下:The beneficial effects of the present invention are as follows:
1、本发明通过在镁基体中复合添加Zn、Nd、Mn作为合金元素,并对镁合金进行挤压加工,使镁合金的塑性变形能力显著提高,并通过提高合金中Zn元素的含量,使镁合金的抗拉强度得到大幅度提高。1. The present invention adds Zn, Nd, and Mn as alloying elements in the magnesium matrix, and extrudes the magnesium alloy, so that the plastic deformation ability of the magnesium alloy is significantly improved, and by increasing the content of the Zn element in the alloy, the The tensile strength of magnesium alloy has been greatly improved.
2、本发明制备的新型含Zn、Mn以及稀土元素Nd的高强高塑性变形镁合金,其棒材室温抗拉强度最高可达到300MPa,断裂延伸率最高可达到37%。2. The novel high-strength and high-plastic deformation magnesium alloy containing Zn, Mn and rare earth element Nd prepared by the present invention has a room-temperature tensile strength of up to 300 MPa and a maximum elongation at break of 37%.
3、本发明镁合金作为可降解心血管支架材料,支架在使用过程中能够承受大的塑性变形,在体内服役过程中,镁合金支架具有足够的强度对发生病变狭窄部位的血管提供持续足够的支撑力;其作为可降解的缝合线材料时,镁合金的优良塑性变形能力符合缝合线在打结过程中的要求,同时缝合线还具备较高的强度,对伤口提供足够的张力固定伤口;该镁合金的强度使其符合作为可降解骨钉、骨板或骨填充材料时的强度要求。3. The magnesium alloy of the present invention is used as a degradable cardiovascular stent material. The stent can withstand large plastic deformation during use. In the process of in vivo service, the magnesium alloy stent has sufficient strength to provide continuous and sufficient support for blood vessels at the site of lesion stenosis. Supporting force; when it is used as a degradable suture material, the excellent plastic deformation ability of magnesium alloy meets the requirements of the suture during the knotting process, and the suture also has high strength, providing sufficient tension for the wound to fix the wound; The strength of the magnesium alloy makes it suitable for use as a degradable bone nail, bone plate or bone filling material.
具体实施方式Detailed ways
以下将结合实施例对本发明作进一步描述。The present invention will be further described below in conjunction with examples.
实施例1:Example 1:
镁合金的成分设计(重量百分比)为:0.2Zn、0.5Mn、2.0Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为200MPa,断裂延伸率达到37%。The composition design (percentage by weight) of the magnesium alloy is: 0.2Zn, 0.5Mn, 2.0Nd, the weight percent of the restricted impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After all the ingredients are melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue smelting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 200MPa, and the elongation at break reaches 37%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.09mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到82%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight change of samples before and after immersion, the corrosion rate of magnesium alloy was calculated to be 0.09mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 82%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例2:Example 2:
合金的成分设计(重量百分比)为:1.0Zn、0.5Mn、2.0Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待合金全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为225MPa,断裂延伸率达到33%。The composition design (weight percentage) of the alloy is: 1.0Zn, 0.5Mn, 2.0Nd, the weight percentage of the limiting impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After the alloy is completely melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue melting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 225MPa, and the elongation at break reaches 33%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.15mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到83%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight change of the sample before and after immersion, the corrosion rate of the magnesium alloy was calculated to be 0.15mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 83%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例3:Example 3:
合金的成分设计(重量百分比)为:2.0Zn、0.5Mn、2.0Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待合金全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度240MPa,断裂延伸率达到35%。The composition design (weight percentage) of the alloy is: 2.0Zn, 0.5Mn, 2.0Nd, the weight percentage of the limiting impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After the alloy is completely melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue melting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 240MPa, and the elongation at break reaches 35%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟,通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.21mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到82%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, 200g/L chromic acid solution was used to ultrasonically clean the soaked sample surface for 3 minutes. By comparing the weight change of the sample before and after immersion, the corrosion rate of the magnesium alloy was calculated to be 0.21mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 82%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例4:Example 4:
镁合金的成分设计(重量百分比)为:4.0Zn、0.5Mn、2.0Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为260MPa,断裂延伸率达到30%。The composition design (percentage by weight) of the magnesium alloy is: 4.0Zn, 0.5Mn, 2.0Nd, the weight percent of the restricted impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After all the ingredients are melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue smelting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 260MPa, and the elongation at break reaches 30%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.25mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到84%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight changes of the samples before and after immersion, the corrosion rate of the magnesium alloy was calculated to be 0.25mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 84%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例5:Example 5:
镁合金的成分设计(重量百分比)为:2Zn、0.5Mn、0.5Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为230MPa,断裂延伸率达到25%。The composition design (percentage by weight) of the magnesium alloy is: 2Zn, 0.5Mn, 0.5Nd, the weight percent of the restricted impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After all the ingredients are melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue smelting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 230MPa, and the elongation at break reaches 25%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.06mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到88%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight change of samples before and after immersion, the corrosion rate of magnesium alloy was calculated to be 0.06mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 88%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例6:Embodiment 6:
镁合金的成分设计(重量百分比)为:4.0Zn、0.5Mn、0.5Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为270MPa,断裂延伸率达到23%。The composition design (percentage by weight) of the magnesium alloy is: 4.0Zn, 0.5Mn, 0.5Nd, the weight percent of the restricted impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After all the ingredients are melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue smelting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 270MPa, and the elongation at break reaches 23%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.12mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到86%,高于75%的细胞毒性一级标准,说明材料无毒性。Prepare deformed magnesium alloy immersion test samples by wire cutting, sample diameter 10mm, thickness 3mm, use 2000# sandpaper to grind the sample surface until bright, conduct immersion experiments in Hank's solution, immersion ratio 1.25ml/cm 2 , replace Hank's solution every day, After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight changes of the samples before and after immersion, the corrosion rate of the magnesium alloy was calculated to be 0.12mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 86%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
实施例7:Embodiment 7:
镁合金的成分设计(重量百分比)为:6.0Zn、0.5Mn、0.5Nd,限制杂质元素的重量百分比Fe<0.006%,Cu<0.005%,Ni<0.006%,其余为Mg。按上述成分配制合金,在熔炼炉中加入预热的Mg锭、Zn锭、电解Mn粉,合金熔炼温度为700℃。待各成分全部熔化后,加入Mg-30Nd中间合金,将温度升高至720℃继续熔炼30分钟,其间搅拌两次使熔体均匀,同时持续加保护气体保护。降温到700℃静止20分钟,使夹杂物沉降,撇去熔体表层浮渣,然后浇铸成铸锭,用车床将铸锭进一步切割直径60mm、长度150mm的圆柱形挤压坯料。将挤压坯料在500℃下置于真空热处理炉中进行均质化处理,水冷,然后在390℃预热2小时,在380℃挤压,挤压比36:1,挤压速度4m/min,采用动物油作为润滑油,获得直径为10mm的镁合金棒材。截取部分棒材加工为M10Φ5的标准拉伸试样,三个平行样,对材料的力学性能进行测试。该合金的室温抗拉强度为300MPa,断裂延伸率达到20%。The composition design (percentage by weight) of the magnesium alloy is: 6.0Zn, 0.5Mn, 0.5Nd, the weight percent of the restricted impurity elements is Fe<0.006%, Cu<0.005%, Ni<0.006%, and the rest is Mg. Prepare the alloy according to the above ingredients, add preheated Mg ingot, Zn ingot, and electrolytic Mn powder into the melting furnace, and the alloy melting temperature is 700°C. After all the ingredients are melted, add Mg-30Nd master alloy, raise the temperature to 720°C and continue smelting for 30 minutes, stir twice to make the melt uniform, and continue to add protective gas protection at the same time. Cool down to 700°C and stand still for 20 minutes to allow the inclusions to settle, skim off the scum on the surface of the melt, and then cast it into an ingot, and use a lathe to further cut the ingot into a cylindrical extrusion billet with a diameter of 60mm and a length of 150mm. Place the extruded billet in a vacuum heat treatment furnace at 500°C for homogenization, water cooling, then preheat at 390°C for 2 hours, and extrude at 380°C with an extrusion ratio of 36:1 and an extrusion speed of 4m/min , using animal oil as lubricating oil to obtain magnesium alloy rods with a diameter of 10mm. Cut part of the bar and process it into a standard tensile sample of M10Φ5, three parallel samples, and test the mechanical properties of the material. The tensile strength of the alloy at room temperature is 300MPa, and the elongation at break reaches 20%.
通过线切割制备变形镁合金浸泡实验样品,样品直径10mm,厚度3mm,用2000#砂纸把样品表面磨至光亮,在Hank’s溶液中进行浸泡实验,浸泡比例1.25ml/cm2,每天更换Hank’s溶液,经过3周的浸泡实验,利用200g/L的铬酸溶液超声清洗浸泡后的样品表面3分钟。通过比较浸泡前后样品重量变化,计算镁合金的腐蚀速率为0.35mm/year。另外细胞毒性试验表明,实验细胞L929的成活率达到81%,高于75%的细胞毒性一级标准,说明材料无毒性。The deformed magnesium alloy soaking test sample was prepared by wire cutting. The sample diameter was 10mm and the thickness was 3mm. The surface of the sample was polished with 2000# sandpaper until it was bright, and the soaking test was carried out in Hank's solution. The soaking ratio was 1.25ml/cm 2 , and Hank's solution was replaced every day. After 3 weeks of immersion experiment, the soaked sample surface was ultrasonically cleaned with 200 g/L chromic acid solution for 3 minutes. By comparing the weight change of the sample before and after immersion, the corrosion rate of the magnesium alloy was calculated to be 0.35mm/year. In addition, the cytotoxicity test shows that the survival rate of the experimental cell L929 reaches 81%, which is higher than the first level standard of cytotoxicity of 75%, indicating that the material is non-toxic.
Claims (9)
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