Chinese Journal of Tissue Engineering Research ›› 2024, Vol. 28 ›› Issue (5): 717-723.doi: 10.12307/2024.263
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Lan Weiwei1, 2, Yu Yaodong1, Huang Di1, 2, Chen Weiyi1, 2
Received:
2023-03-06
Accepted:
2023-04-23
Online:
2024-02-18
Published:
2023-08-16
Contact:
Huang Di, PhD, Professor, Master’s supervisor, Research Center for Nano-Biomaterials and Regenerative Medicine, College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi Province, China; Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030032, Shanxi Province, China
About author:
Lan Weiwei, PhD, Lecturer, Research Center for Nano-Biomaterials and Regenerative Medicine, College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi Province, China; Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030032, Shanxi Province, China
Supported by:
CLC Number:
Lan Weiwei, Yu Yaodong, Huang Di, Chen Weiyi. In vitro degradation behavior of Mg-Zn-Ca alloys[J]. Chinese Journal of Tissue Engineering Research, 2024, 28(5): 717-723.
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2.1 各种Mg合金结构和成分分析 电感耦合等离子体发射光谱表征结果如表1所示,该结果证实,实际所制备合金成分参数基本符合前期设计参数。图1-4中,左下角所示为上述4种合金初始状态和在3种降解环境下不同时间节点的试样降解整体形貌变化,随着降解时间的推移,Mg合金表面有大量的白色沉积物质生成,并且不同Ca含量的Mg合金在不同降解液体中整体的降解形貌和速率也有所不同,整体来看,试样在生理盐水中降解速度最快,其次为PBS,在Hank’s液中降解速率最慢;在生理盐水中的降解速率快慢为:Mg-Zn < Mg-Zn-0.2Ca < Mg-Zn-0.5Ca < Mg-Zn-1Ca,在PBS和Hank’s液中的降解速率快慢为:Mg-Zn < Mg-Zn-0.2Ca≈Mg-Zn-0.5Ca < Mg-Zn-1Ca。"
为了进一步明确试样在不同降解节点内的微观结构变化,进行了扫描电镜分析,如图1-4所示,所有样品表面都观察到不规则的纳米级结晶片状结构,但形貌不同,有呈现疏松、多孔相交叉成团簇状,片层卷曲相交连成网状,还有的片层堆叠在一起。 为了阐明这些新生片层物质的成分,对降解3周的各组试样进行了X射线能谱元素分析,从图5,6中可以看到,主要是以O和Mg元素为主,根据Mg合金在体外降解过程中可能发生化学反应推测可能存在MgO和Mg(OH)2。X射线衍射的测试数据也验证了试样降解后的主要物质是Mg(OH)2,见图7所示。另外值得关注的是,在PBS和Hank’s液中检测到了P和Ca元素的生成,其中在Hank’s液中的含量要较高,从中可以推测出样品在降解的同时也有一定的矿化沉积出现。"
2.2 各种Mg合金在模拟体液中的失重测试结果 为了精确测定4种Mg合金的降解状况,对其质量变化进行了测试和记录(图8A)。整体来看,4种Mg合金随着降解时间的延长整体都有一定的质量损失,其中在生理盐水中降解最快,并且随着时间流逝腐蚀速度加快;在Hank’s液和PBS中降解后试样的质量变化不大,说明在Mg合金基体被腐蚀的同时产生的新物质,也就是发生了矿化。另外,随着Mg合金中钙含量的增加,其腐蚀速率明显加快。 2.3 各种Mg合金在模拟体液中的pH值测试结果 Mg合金作为一种活泼可降解的金属,在复杂人体环境中随着降解的发生会改变其周围环境pH值。根据图8B所示,在短期内(1 d)所有Mg合金样所处的液体环境pH值都在急剧上升,然后趋于平缓,最高pH值介于10.0-11.0之间;整体来看,Mg-Zn合金的pH值改变相较其他有Ca添加合金组略低,随着Ca含量的增加,液体环境pH值上升显著,这种变化与降解速度相对应,试样降解越快释放产物也越多,对周围环境的pH值改变也明显。值得注意的是,相较于其他两种降解环境,Mg合金在PBS中液体环境pH值上升幅度更大,最高为Mg-Zn-1Ca为11.0-12.0。 2.4 各种Mg合金的力学性能表征结果 模如图8C所示,在初始状态下,Mg-Zn合金弹性模量为(1 161±10) MPa,Ca的添加显著增强了Mg合金的力学性能,Mg-Zn-0.2Ca合金弹性模量增加至(1 546±33) MPa,随着钙含量进一步增加,Mg合金的弹性模量有所降低但无显著变化,Mg-Zn-0.5Ca和Mg-Zn-1Ca合金的弹性模量分别为(1 518±28),(1 516±9) MPa,添加Ca元素Mg合金的弹性模量高于Mg-Zn合金(P < 0.05)。随着降解时间的推移,4种Mg合金的力学性能在3种降解环境下均有所降低,其中在生理盐水溶液中的下降最低,Mg-Zn、Mg-Zn-0.2Ca、Mg-Zn-0.5Ca合金降解第3周的弹性模量分别为(882±59),(1 163±7),(602±106) MPa,Mg-Zn-1Ca合金在第3周已经几乎降解完全,降解2周的弹性模量为(268±35) MPa;在PBS和Hank’s液中4种Mg合金的力学性能也均有所降低,但组间比较无明显差异且弹性模量均能保持在初始状态的2/3左右。"
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