CN112472868B - 一种可降解的Mg-Nd-Zn-Sc生物医用镁合金及其制备方法 - Google Patents
一种可降解的Mg-Nd-Zn-Sc生物医用镁合金及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种可降解的Mg‑Nd‑Zn‑Sc生物医用镁合金及其制备方法,其化学成分按质量百分比计为:Nd:1.0‑3.0%,Zn:0.3‑0.7%,Sc:2.0‑8.0%,其余为Mg和不可避免的杂质元素。本发明经过350‑450℃,挤压比为11~30挤压加工,发明的合金中Zn含量较少,而Nd的电位和Mg接近,Sc在镁基体中的固溶度较大,添加的Sc能够完全固溶,能够通过第二相强化和固溶强化的方式提升合金的力学性能,不会引起严重的电偶腐蚀,而且由于Sc在腐蚀时形成的氧化钪与原来疏松的氢氧化镁一起形成较为致密的钝化层在一定程度上保护基体免受腐蚀。
Description
技术领域
本发明主要应用与生物医用材料领域,属于金属材料的设计与制造领域,具体涉及一种可降解的Mg-Nd-Zn-Sc生物医用镁合金及其制备方法。
背景技术
镁合金具有优异的生物相容性和优异的成骨能力,被广泛认为是可生物降解的骨植入物的候选材料,另外由于其生物可降解性能,也被认为作为血管支架材料有巨大潜力。此外,镁合金的杨氏模量(41–45 GPa)与人体骨骼(20Gpa)相似,因此可以避免“应力屏蔽效应”促进骨骼生长,相比较之下不锈钢约为200GPa,钛合金约为100GPa。此外,由于镁合金有良好的生物可降解性能,相比于不锈钢和钛合金,避免了二次手术的痛苦和危险,而聚乳酸等高分子材料虽然可降解,但由于其力学性能差,难以作为支架承受较大的负重,在降解过程中易产生酸性物质,使局部pH值降低,引起组织的无菌炎症。近年来,随人们生活水平的提高及饮食结构的变化,由于摄入大量高糖高脂的食物而导致的心脑血管疾病已成为威胁人类健康的首要疾病之一。早在20世纪,微创介入治疗血管疾病技术开始得到应用,随后被公认是治疗心脑血管疾病最有效的手段之一;血管支架植入手术应运而生,迅速发展,正在广泛应用于心血管疾病介入治疗。而在骨科方面,骨固定,骨修复和骨植入也是治疗相关疾病的重要手段,因此作为可降解植入物的镁合金有巨大的市场潜力和应用前景。
镁合金作为外科医用材料早期临床应用证实了其用于生物医用材料的可行性,但镁基体腐蚀过快,需进一步研究改善。通过合金化和合适的加工工艺处理得到性能优异的生物医用镁合金。对于医用镁合金,合金化元素同时必须对人体有良好的生物相容且对机体无毒害作用。虽然Al能够明显提升镁合金的机械性能,但Al元素具有神经毒性,会引发老年痴呆,稀土元素Ce、La以及一些其他重金属对细胞毒性影响很大,因而不予考虑这些元素。目前常用于生物镁合金中的合金化元素有:Zn、Ca、Mn、Zr、Si、Y、Nd等。迄今为止,作为外科手术植入物(主要包括各类型的血管支架,呼吸道和肠胃支架,骨植入和骨修复材料)和整形外科设备,已对大量含稀土元素(RE)的二元,三元镁合金进行了广泛的研究。据报道,WE43(Y含量为4 wt%,稀土金属含量为3 wt%)合金具有优异的机械性能和良好的耐腐蚀性。与WE43相关的骨植入器件的临床实验已经在欧洲进行,到目前为止,临床随访相对令人满意。另外,其他基于Mg-RE的合金,例如Mg-Y,Mg-Nd,Mg-Dy,Mg-Zn-Gd,Mg-Zn-Y-Nd,和Mg-Nd-Zn-Zr等合金已经通过体外和体内测试。
作为稀土元素之一,钪(Sc)元素已广泛应用在航空航天和其他工业领域如铝合金的强化等方面。此外,在镁合金中添加Sc还具有一些独特的优势。它有利于晶粒细化,可以进一步提高镁合金的强度和塑性。由于Sc在α-Mg中有很高的固溶度(24.5wt%),因此可以通过固溶强化来提高镁合金的强度。就腐蚀而言,Sc加入镁基体后不会形成第二相,且氧化形成的Sc2O3能够和Mg(OH)2共同形成较为致密的钝化层从而保护基体。在熔炼铸造过程中,Sc的存在能净化合金熔体并减少杂质(Fe,Ni,Cu等)的含量,从而进一步降低镁合金的腐蚀速率,提高机械性能。此外,Mg-Sc合金是迄今为止发现的唯一一种存在形状记忆镁基合金。这一发现可能会扩展其在可降解形状记忆生物医学植入物中的潜在应用,例如在一定条件下可在体内自扩张的各类支架,体温下的形状恢复钉等。根据郑玉峰等人的研究,体外生物降解试验表明,Sc2O3分布在内部腐蚀层中,而Mg(OH)2则分布在外部腐蚀层中。双层腐蚀产物可有效提高Mg-Sc合金的耐蚀性。单相的Mg-Sc合金对MC3T3细胞系无细胞毒性作用。Mg-Sc合金均显示出优异的血液相容性,而没有血小板聚集。β相Mg-30 wt%Sc合金具有形状记忆效应,具有出色的机械性能,具有优异的体内降解性能(0.06 mm y-1)。使用Mg-30 wt%Sc合金。植入24周后观察到令人满意的骨整合,有限的氢释放,维持了机械完整性。
发明内容
本发明提供了一种可降解的Mg-Nd-Zn-Sc生物医用镁合金及其制备方法的目的在于提高镁合金的机械性能,降低其腐蚀速率,通过在镁锌合金中添加稀土元素Nd、Sc制备镁合金,使其铸态获得等轴晶,晶粒进一步细化,使其铸态力学性能抗拉强度达205MPa,屈服强度达97MPa,延伸率达21%。经过热挤压处理获得平均晶粒3-5μm的Mg-Nd-Zn-Sc合金并出现大量的均匀、弥散分布的第二相颗粒,满足生物医用镁合金的性能要求。
为了达到上述目的,本发明采用如下技术方案:
本发明提供了一种可降解的Mg-Nd-Zn-Sc生物医用镁合金,其化学成分按质量百分比计为:Nd:1.0-3.0%,Zn: 0.3-0.7%, Sc: 2.0-8.0%,其余为Mg和不可避免的杂质元素。
如上述的可降解的Mg-Nd-Zn-Sc生物医用镁合金,该Mg-Nd-Zn-Sc生物医用镁合金材料半连续铸造后,其组织特征为等轴晶,经过350-450℃,挤压比为11~30挤压,其基体中均匀弥散分布大量的MgNd颗粒相,Sc完全固溶到基体中。
如上述的可降解的Mg-Nd-Zn-Sc生物医用镁合金,按Mg-Nd-Zn-Sc生物医用镁合金材料的组成且Nd、Zn、Sc的重量百分含量过量10~20%准备炉料,然后熔炼制成普通Mg-Nd-Zn-Sc镁合金;其中Mg、Zn、Nd、Sc的炉料分别为高纯镁锭、高纯锌锭、Mg-Nd中间合金和Mg-Sc中间合金。
如上述的可降解的Mg-Nd-Zn-Sc生物医用镁合金,所述Mg-Nd中间合金为Mg-30wt%Nd中间合金,Mg-Sc中间合金为Mg-30%Sc中间合金。
本发明还提供了一种可降解的Mg-Nd-Zn-Sc生物医用镁合金的制备方法,包括以下步骤:
第一步 铸态Mg-Nd-Zn-Sc合金的制备
(1)将坩埚、扒渣工具、搅拌棒以及模具加热到200~250℃,然后取出,刷上铸造用涂料,然后放入烘箱烘干,同时预热烘干炉料;为防止镁合金的氧化和燃烧,在整个熔炼过程中一直通有保护气体,采用的保护气体为二氧化碳和六氟化硫的混合气体,其中二氧化碳和六氟化硫的体积比为97:3;
(2)将清理干净的坩埚放入电阻炉中,设定温度为450℃,待炉温达到时,通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3;
(3)通入混合保护气20min后加入烘干的高纯镁锭,同时升温至720℃;待炉料高纯镁锭完全熔化后,向坩埚中加入烘干的Mg-Sc中间合金,加热10-15min后,将温度升至800℃,开始计时保温,保温时间为90min;保温结束后,加入烘干的Mg-Nd中间合金,同时降温至720℃,加热10-15min后加入烘干的高纯锌锭,加热10-15min后进行搅拌,搅拌速度均匀,方向逆时针且不要碰触坩埚内壁和底部,搅拌时间为3min,静置10min后扒渣并再次静置15min;
(4)取出预热烘干后的模具并向其中通入保护气1min;
(5)取出坩埚,进行浇铸,脱模后即制得普通凝固态Mg-Nd-Zn-Sc合金;
第二步 挤压合金试样的制备
(1)将铸造好的合金坯料使用线切割机切下一个圆柱体,使用砂轮机打磨干净;
(2)将清理干净的坯料置于氧化铝粉末中放入保温炉中,在350-450℃条件下进行均匀化退火24h;
(3)将退火完成的坯料的氧化层再次打磨干净;
(4)将坯料放入涂上润滑剂放入模具中,将温度调到400℃,进行预热;待温度到达400℃之后,保温20min进行挤压,挤压比为11~30,挤压速率为1~4m/min,挤压过程中挤压筒、垫片、模具、坯料的温度分别为250℃,300℃,350℃,400℃;
(5)挤压结束后将挤压得到的棒材进行水冷得到目标产品。
与现有可降解镁合金生物医用材料相比,本发明优点在于:
在同种制备工艺状态下,与现有的可降解镁合金生物医用材料相比,本发明的Mg-Nd-Zn-Sc合金中全部选用对人体无害的金属元素和多元微量化理念来合成,不仅大幅度提高了合金的生物相容性,同时减少了合金中元素的偏聚,具有更好的耐腐蚀性, Nd作为合金表面活性元素,在结晶凝固过程中,在第二相与液相的固-液界面上,使第二相的生长停止,同时Sc元素在凝固过程中,促进形核,增大形核率,使晶粒得到明显细化。采用热挤压加工,可使镁合金的平均晶粒尺寸控制在3-5μm,细小的晶粒能够保证合金的塑性和材料强度同时得到提高,MgNd颗粒相弥散分布于基体中,且Sc完全固溶,与其他医用镁合金相比较减少了Zn的含量,降低了与基体的电位差,抑制了原电池的形成,减轻了电偶腐蚀,是材料在模拟体液中的腐蚀速率明显降低,且是均匀腐蚀。
在相同的热挤压制备工艺条件下,本发明方法制备的Mg-Nd-Zn-Sc合金室温下的抗拉强度达到290±20MPa,屈服强度达到225±20MPa,延伸率大于24%,自腐蚀电位为-1.45v到-1.55v之间,腐蚀电流密度为0.78-1.26×10-4A/cm2之间,其力学性能腐蚀性能满足生物医用镁合金要求。
附图说明
图1是挤压态Mg-1Nd-0.5Zn-2Sc合金的显微组织;
图2是挤压态Mg-1Nd-0.5Zn-2Sc合金的SEM和EDS分析图;
图3是挤压态Mg-1Nd-0.5Zn-2Sc合金XRD图;
图4分别是挤压态Mg-1Nd-0.5Zn-2Sc合金的拉伸断口宏观形貌;
图5分别是挤压态Mg-1Nd-0.5Zn-2Sc合金的拉伸断口微观形貌;
图6是挤压态Mg-1Nd-0.5Zn-2Sc合金在模拟体液中的电化学腐蚀测试结果图;
图7为挤压态Mg-1Nd-0.5Zn/Mg-1Nd-0.5Zn-2Sc合金做过电化学之后的表面腐蚀形貌图。
具体实施方式
下面结合实施例对本发明作进一步说明:
第一步 铸态Mg-3Nd-0.5Zn-2Sc合金的制备
Ⅰ 前期准备
本实验所需的一炉原料为:
高纯镁锭:350-600g
高纯锌锭:3-7g
Mg-30wt%Nd中间合金:20-85g
Mg-30%Sc中间合金:20-160g
为防止镁合金的氧化和燃烧,在整个熔炼过程中一直通有保护气体,本试验中采用的保护气体为二氧化碳和六氟化硫的混合气体,其中二氧化碳和六氟化硫的体积比为97:3;
Ⅱ 具体操作过程
(1)将坩埚、扒渣工具、搅拌棒以及模具加热到200~250℃,然后取出,刷上一层均匀薄薄的铸造用涂料,然后放入烘箱烘干,同时预热烘干炉料;
(2)将清理干净的钢坩埚放入电阻炉中,设定温度为450℃,待炉温达到时,通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3;
(3)通入混合保护气20min后加入烘干的高纯镁锭,同时升温至720℃;
(4)待炉料完全熔化后,向坩埚中加入烘干的Mg-Sc中间合金;
(5)10-15min后,将温度升至800℃,开始计时保温,保温时间为90min;
(6)保温结束后,加入烘干的Mg-Nd中间合金,同时降温至720℃;
(7)10-15min后加入烘干的高纯锌锭;
(8)10-15min后进行搅拌,搅拌速度均匀,方向逆时针且不要碰触坩埚内壁和底部,搅拌时间为三min,静置10min后扒渣并再次静置15min;
(9)取出预热烘干后的模具并向其中通入保护气1min;
(10)取出坩埚,进行浇铸,脱模后即制得普通凝固态Mg-Nd-Zn-Sc合金。
第二步 挤压合金试样的制备
a、将铸造好的合金坯料使用线切割机切下一个圆柱体,使用砂轮机打磨干净;
b、将清理干净的坯料放入保温炉中,在350-450℃条件下置于氧化铝粉末中进行均匀化退火24h;
c、将退火完成的坯料的氧化层再次打磨干净;
d、将坯料放入涂上润滑剂放入模具中,将温度调到400℃,进行预热;
e、温度到达400℃之后,保温20min进行挤压,挤压比为11~30,挤压速率为1~4m/min,挤压过程中挤压筒、垫片、模具、坯料的温度分别为250℃,300℃,350℃,400℃;
f、挤压结束后将挤压得到的棒材进行水冷。
实施例1
合金的成分(质量量百分比)为:1.0%Nd,0.5%Zn, 2.0%Sc,其余元素为Mg。合金的制备工艺为:将钢制坩埚放入电阻炉预热至400℃保温10min,并通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3,加入高纯镁锭486.20g,并盖好炉盖,升温至720℃;待炉料完全熔化后,向坩埚中加入烘干的Mg-30Sc中间合金40.33g;10min后,将温度升至800℃,开始计时保温,保温时间为90min,保温结束后,加入烘干的Mg-30Nd中间合金20.17g,同时降温至720℃,15min后加入烘干的高纯锌锭3.3g,等到熔体完全融化保温10min,在720℃时浇入金属型模具中;将铸态样品切割成ϕ30的圆柱样品在400℃条件下进行挤压,挤压比为14。得到样品屈服强度为221MPa,抗拉强度为285MPa,延伸率为31%,在模拟体液中的电化学腐蚀测试结果可得,该合金的自腐蚀电位为-1.512V,腐蚀电流密度为0.89×10-4A/cm2。
实施例2
金的成分(质量量百分比)为:3.0%Nd,0.5%Zn, 4.0%Sc,其余元素为Mg。合金的制备工艺为:将钢制坩埚放入电阻炉预热至400℃保温10min,并通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3,加入高纯镁锭405.53g,并盖好炉盖,升温至720℃;待炉料完全熔化后,向坩埚中加入烘干的Mg-30Sc中间合金80.67g;10min后,将温度升至800℃,开始计时保温,保温时间为90min,保温结束后,加入烘干的Mg-30Nd中间合金60.50g,同时降温至720℃,15min后加入烘干的高纯锌锭3.3g,等到熔体完全融化保温10min,在720℃时浇入金属型模具中;将铸态样品切割成ϕ30的圆柱样品在400℃条件下进行挤压,挤压比为14。得到样品屈服强度为231MPa,抗拉强度为301MPa,延伸率为28%,在模拟体液中的电化学腐蚀测试结果可得,该合金的自腐蚀电位为-1.412V,腐蚀电流密度为1.13×10-4A/cm2。
实施例3
金的成分(质量量百分比)为:3.0%Nd,0.5%Zn, 8.0%Sc,其余元素为Mg。合金的制备工艺为:将钢制坩埚放入电阻炉预热至400℃保温10min,并通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3,加入高纯镁锭324.86g,并盖好炉盖,升温至720℃;待炉料完全熔化后,向坩埚中加入烘干的Mg-30Sc中间合金161.34g;10min后,将温度升至800℃,开始计时保温,保温时间为90min,保温结束后,加入烘干的Mg-30Nd中间合金60.50g,同时降温至720℃,15min后加入烘干的高纯锌锭3.3g,等到熔体完全融化保温10min,在720℃时浇入金属型模具中;将铸态样品切割成ϕ30的圆柱样品在400℃条件下进行挤压,挤压比为14。得到样品屈服强度为242MPa,抗拉强度为309MPa,延伸率为23%,在模拟体液中的电化学腐蚀测试结果可得,该合金的自腐蚀电位为-1.401V,腐蚀电流密度为0.78×10-4A/cm2。
对挤压态的Mg-1Nd-0.5Zn-2Sc合金的组织及性能进行测试分析:
图1是挤压态Mg-1Nd-0.5Zn-2Sc合金的显微组织,从图中可以看出该合金的组织均匀,晶粒细小,平均晶粒尺寸达到2-3μm;
图2是挤压态Mg-1Nd-0.5Zn-2Sc合金的SEM和EDS分析图片,图4挤压态Mg-3Nd-0.5Zn、Mg-1Nd-0.5Zn-2Sc合金的XRD图。从图中可以看出,该合金中均匀分布着颗粒状第二相,其主要为Mg12Nd相;
图3是挤压态Mg-1Nd-0.5Zn和Mg-1Nd-0.5Zn-2Sc合金XRD图,从图中可以看出,合金中主要形成的第二相是Mg12Nd相,加入Sc元素之后合金的第二相没有改变,Mg12Nd相与镁基体有相近的电位,不会引起强烈的电偶腐蚀。
图4和图5分别是挤压态Mg-1Nd-0.5Zn-2Sc合金的拉伸断口宏观和微观形貌,从图中可以看出,该合金断口中含有大量韧窝,属于韧性断裂;
图6是挤压态Mg-1Nd-0.5Zn-2Sc合金在模拟体液中的电化学腐蚀测试结果,从图中拟合可得,该合金的自腐蚀电位为-1.512V,腐蚀电流密度为0.89×10-4A/cm2,其腐蚀性能满足生物医用镁合金要求。
图7为挤压态Mg-1Nd-0.5Zn/Mg-1Nd-0.5Zn-2Sc合金做过电化学之后的表面腐蚀形貌,a为Mg-1Nd-0.5Zn,b为Mg-1Nd-0.5Zn-2Sc,可以看出在加入Sc元素之后合金表面的氧化层更加致密,有利于使合金均匀化降解,使其降解速率减少,降解更加均匀,能够使合金在使用过程中减少因为不均匀腐蚀造成的应力集中现象,延长合金使用寿命。
Claims (2)
1.一种可降解的Mg-Nd-Zn-Sc生物医用镁合金,其特征在于:其化学成分按质量百分比计为:Nd:1.0%,Zn:0.5%,Sc:2.0%,其余为Mg和不可避免的杂质元素;所述的可降解的Mg-Nd-Zn-Sc生物医用镁合金的制备方法,包括以下步骤:
第一步 铸态Mg-Nd-Zn-Sc合金的制备
(1)将坩埚、扒渣工具、搅拌棒以及模具加热到200~250℃,然后取出,刷上铸造用涂料,然后放入烘箱烘干,同时预热烘干炉料;
(2)将清理干净的坩埚放入电阻炉中,设定温度为450℃,待炉温达到时,通入二氧化碳和六氟化硫的混合气体,其中,二氧化碳和六氟化硫的体积比为97:3;
(3)通入混合保护气20min后加入烘干的高纯镁锭,同时升温至720℃;待炉料高纯镁锭完全熔化后,向坩埚中加入烘干的Mg-Sc中间合金,加热10-15min后,将温度升至800℃,开始计时保温,保温时间为90min;保温结束后,加入烘干的Mg-Nd中间合金,同时降温至720℃,加热10-15min后加入烘干的高纯锌锭,加热10-15min后进行搅拌,搅拌速度均匀,方向逆时针且不要碰触坩埚内壁和底部,搅拌时间为3min,静置10min后扒渣并再次静置15min;
(4)取出预热烘干后的模具并向其中通入保护气1min;
(5)取出坩埚,进行浇铸,脱模后即制得普通凝固态Mg-Nd-Zn-Sc合金;
第二步 挤压合金试样的制备
(1)将铸造好的合金坯料使用线切割机切下一个圆柱体,使用砂轮机打磨干净;
(2)将清理干净的坯料置于氧化铝粉末中放入保温炉中,在350-450℃条件下进行均匀化退火24h;
(3)将退火完成的坯料的氧化层再次打磨干净;
(4)将坯料涂上润滑剂放入模具中,将温度调到400℃,进行预热;待温度到达400℃之后,保温20min进行挤压,挤压比为14,挤压速率为1~4m/min,挤压过程中挤压筒、垫片、模具、坯料的温度分别为250℃,300℃,350℃,400℃;
(5)挤压结束后将挤压得到的棒材进行水冷得到目标产品;
所述Mg-Nd-Zn-Sc生物医用镁合金在半连续铸造后,其组织特征为等轴晶;经过400℃、挤压比为14的挤压,其基体中均匀分布大量MgNd相;
所述Mg-Nd中间合金为Mg-30wt%Nd中间合金,Mg-Sc中间合金为Mg-30%Sc中间合金。
2.如权利要求1所述的可降解的Mg-Nd-Zn-Sc生物医用镁合金,其特征在于:按所制Mg-Nd-Zn-Sc生物医用镁合金的组成且Nd、Zn、Sc的重量百分含量过量10~20%准备炉料,然后熔炼制成普通凝固态Mg-Nd-Zn-Sc镁合金;其中Mg、Zn、Nd、Sc的炉料分别为高纯镁锭、高纯锌锭、Mg-Nd中间合金和Mg-Sc中间合金。
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