CN107385419B - 一种提高医用镁合金表面耐腐蚀及亲水性能的涂层及其制备方法 - Google Patents
一种提高医用镁合金表面耐腐蚀及亲水性能的涂层及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种提高医用镁合金表面耐腐蚀及亲水性能的涂层,为Mg‑MOF‑74/MgF2复合涂层。同时提供了该复合涂层的制备方法,即先通过氢氟酸酸蚀使得镁合金表面生成MgF2膜层,然后再通过水热合成法在其表面原位生成Mg‑MOF‑74涂层,含有Mg‑MOF‑74/MgF2复合涂层的镁合金的表面耐腐蚀性能有很大程度的提高,同时亲水性能也大幅度改善。
Description
技术领域
本发明属于生物医用镁合金表面处理技术领域,具体涉及一种在镁合金表面构筑Mg-MOF-74/MgF2复合涂层的方法,从而提高医用镁合金表面的耐蚀性和亲水性,实现该类复合材料在生物医学工程方面的应用。
背景技术
镁合金密度低,比强度、比刚度高,与人体自身骨组织力学性能接近且具有生物可降解性,因此被认为是一种极具潜力的可降解医用骨植入材料。但是镁合金的耐腐蚀性极差,在人体内的降解速度与组织愈合速度不匹配,进而限制了镁合金在临床中的应用,因此,改善其腐蚀速率过高的问题是医用镁合金研究的重点。表面改性技术是针对镁合金降解过快问题的有效解决途径之一,除此之外,表面改性技术还能够在一定程度上改善镁合金的生物相容性。常见提高镁合金耐腐蚀性的表面涂层材料包括:生物活性玻璃、羟基磷灰石、金属氧化物、高分子聚合物及MgF2化学转化膜等,上述研究成果为医用镁合金的表面处理奠定了一定的基础。但是,大多数耐腐蚀材料表面同时具有疏水性,而疏水性的表面不利于人体细胞的吸附与增殖,尤其是在镁合金作为人体骨组织替代物的时候,耐腐蚀且亲水的表面对骨组织的再生尤其重要。因此开发一种在医用镁合金表面制备耐腐蚀且具优异亲水性能的涂层的技术极为重要。
金属有机骨架材料(MOFs)是近十几年发展起来的一种无机多孔材料,是通过有机配体与金属离子(簇)相互作用构筑的一类具有周期性网络结构的晶态多孔材料,具有超大比表面积和孔体积、密度小、通过修饰手段可使其携带多种功能基团等特点,且部分MOFs材料具有良好的生物相容性及水热稳定性。MOFs材料上述的诸多优点使其具备成为医用镁合金表面优异涂层的潜力。Mg-MOF-74是由二价镁离子与配体2,5-二羟基对苯二甲酸自组装构成的一种具有较好生物相容性的金属有机骨架材料,其表面及孔道中的羟基使这种材料具备了优异的亲水性能。然而目前尚没有将Mg-MOF-74用于制备医用镁合金表面涂层的报道。
发明内容
为解决现有技术中医用镁合金降解过快及亲水性差的问题,本发明提供了一种提高医用镁合金表面耐腐蚀及亲水性能的涂层,为Mg-MOF-74/MgF2复合涂层,及在医用镁合金表面制备该复合涂层的方法,即先通过氢氟酸酸蚀使得镁合金表面生成MgF2膜层,然后再通过水热合成法在其表面原位生成Mg-MOF-74涂层,这样Mg-MOF-74/MgF2复合涂层使得镁合金表面耐腐蚀性能进一步得到提高,同时亲水性能也大幅度改善。
为实现上述目的,本发明采用如下技术方案:
一种提高医用镁合金表面耐腐蚀及亲水性能的涂层,为Mg-MOF-74/MgF2复合涂层。
一种所述提高医用镁合金表面耐腐蚀及亲水性能的涂层的制备方法,包括以下步骤:
(1)医用镁合金的表面预处理:以镁合金AZ31B作为基体材料,用砂纸打磨,用丙酮、乙醇及去离子水清洗,备用;
(2)MgF2膜层的制备:将上述预处理后的镁合金片放入氢氟酸中酸蚀,使其表面产生MgF2化学转化膜,然后取出用去离子水冲洗干净,备用;
(3)反应溶液的配制:将六水合硝酸镁、2,5二羟基对苯二甲酸置于N-N二甲基甲酰胺、去离子水以及乙醇的混合溶液中,于磁力搅拌器上充分搅拌,过滤后制得反应溶液,注入聚四氟乙烯反应釜中;
(4)Mg-MOF-74/MgF2复合涂层的制备:将步骤(2)制得的具有MgF2转化膜的镁合金片垂直置于反应釜且完全没入步骤(3)制得的反应溶液中,密封后将反应釜置于鼓风干燥箱中,升温,反应;
(5)Mg-MOF-74/MgF2复合涂层的后处理:将步骤(4)反应后的镁合金片用无水甲醇冲洗,然后置于无水甲醇中浸泡,而后再取出置于真空干燥箱干燥,即获得具有Mg-MOF-74/MgF2复合涂层的镁合金复合材料。
与现有技术相比,本发明的有益效果为:
(1)本发明是首次在医用镁合金表面原位生成耐腐蚀且亲水的Mg-MOF-74/MgF2复合涂层,本发明的制备方法可以在三维曲面形状的镁合金基底表面制备致密连续的Mg-MOF-74/MgF2复合涂层,且该复合涂层具有良好的抗腐蚀能力,能够有效减缓医用镁合金的腐蚀速率。
(2)本发明制备的Mg-MOF-74/MgF2涂层中Mg-MOF-74骨架材料上的羟基赋予涂层良好的亲水性能,有利于人体细胞的吸附与增殖。
(3)在本发明涂层的制备过程中,镁合金基底表面的镁金属与混合溶液中的镁离子共同参与反应构成复合涂层,因此,涂层与镁合金基底具有较好的结合力。
(4)本发明制备的Mg-MOF-74/MgF2涂层中Mg-MOF-74骨架材料赋予涂层具有良好的生物相容性,使Mg-MOF-74/MgF2复合涂层的镁合金复合材料在生物医学工程方面具有广阔的应用前景。
附图说明
图1为实施例1所得Mg-MOF-74/MgF2复合涂层的扫描电镜(SEM)图片;
图2为将实施例1所得表面涂层材料刮下后测得的X-射线衍射(XRD)谱图;
图3为镁合金空白样及实施例1中制备了Mg-MOF-74/MgF2复合涂层的镁合金片分别浸泡在模拟体液(组成:8.035g/L NaCl,0.355 g/L NaHCO3,0.225 g/L KCl,0.231 g/LK2HPO4·3H2O,0.311 g/L MgCl2·6H2O,0.292 g/L CaCl2,0.072 g/L Na2SO4,6.118 g/LTris,39 ml 1.0M-HCl,(pH=7.4))中时,单位表面积的析氢量随时间的变化曲线;
图4为水滴在镁合金空白样及实施例1中制备的Mg-MOF-74/MgF2复合涂层上的接触角照片。
具体实施方式
下面结合实施例及附图对本发明作进一步的详细说明。
本发明提供一种提高医用镁合金表面耐腐蚀及亲水性能的涂层,为Mg-MOF-74/MgF2复合涂层。
在制备Mg-MOF-74/MgF2复合涂层过程中,所用试剂均为市售,分析纯。
实施例1
一种医用镁合金表面金属有机骨架Mg-MOF-74/MgF2涂层的制备步骤如下:
步骤1:将厚度为1mm的镁合金AZ31B切割成2cm×2cm的长方形,依次用240目、500目、800目水磨砂纸打磨去除表面氧化层,然后将镁合金片置于丙酮、乙醇中分别超声清洗5分钟,再用去离子水超声清洗1分钟,吹干备用;
步骤2:将步骤1中预处理后的镁合金片放入装有适量质量分数为40%氢氟酸的聚乙烯烧杯中,酸蚀2.5小时后取出,用去离子水清洗,备用;
步骤3:称取六水合硝酸镁0.6500g、2,5二羟基对苯二甲酸0.1650g置于烧杯中,然后向其中加入61.0mLN-N二甲基甲酰胺、4.0mL去离子水以及4.0mL乙醇的混合溶液,于磁力搅拌器上充分搅拌1h,过滤后得到澄清反应溶液并注入聚四氟乙烯反应釜中;
步骤4:将经过步骤2后具有MgF2转化膜的镁合金片垂直并完全浸入步骤3所制得的反应溶液,密封反应釜,然后将其放入恒温鼓风干燥箱中,升温至125℃,24h后自然冷却至室温;
步骤5:取出长有涂层的镁合金片,用无水甲醇冲洗数次后置于无水甲醇中浸泡12h,然后将镁合金片置于真空干燥箱中,100℃保持3h,即获得具有Mg-MOF-74/MgF2复合涂层的镁合金复合材料。
制备有Mg-MOF-74/MgF2复合涂层的镁合金片表面的SEM形貌如图1所示。从图1中可以看出,涂层晶体在试样表面紧密排列,晶体呈柱状,且此涂层具备一定的厚度。
图2为镁合金片表面被刮下涂层材料的XRD图谱,与文献Caskey S R, Wong-Foy AG, Matzger A J. Dramatic tuning of carbon dioxide uptake via metalsubstitution in a coordination polymer with cylindrical pores. J Am Chem Soc,2008,130: 10870-10871中得到的Mg-MOF-74单晶结构数据模拟的粉末X-射线谱图对比,衍射峰的位置非常吻合,证明在镁合金片MgF2转化膜上制备出Mg-MOF-74涂层。
在模拟体液(SBF)中测试涂层试样的腐蚀性能,结果如图3所示,可以看出,与镁合金空白样相比,表面制备有Mg-MOF-74/MgF2复合涂层的试样所测得的析氢量明显降低,说明Mg-MOF-74/MgF2复合涂层能够有效减缓基体的腐蚀速率。
图4为水滴在镁合金空白样及实施例1中制备的Mg-MOF-74/MgF2复合涂层上的接触角照片,其中,图4a为镁合金空白样,图4b为实施例1中制备的有Mg-MOF-74/MgF2复合涂层的试样。由图4可以看出,水滴在Mg-MOF-74/MgF2复合涂层表面的接触角为零,表现出完全的亲水性能。
实施例2
一种医用镁合金表面金属有机骨架Mg-MOF-74/MgF2涂层的制备步骤如下:
步骤1:将厚度为1mm的镁合金AZ31B切割成2cm×2cm的长方形,依次用240目、500目、800目水磨砂纸打磨去除表面氧化层,然后将镁合金片置于丙酮、乙醇中分别超声清洗10分钟,再用去离子水超声清洗3分钟,吹干备用;
步骤2:将步骤1中预处理后的镁合金片放入装有适量质量分数为40%氢氟酸的聚乙烯烧杯中,酸蚀3小时后取出,用去离子水清洗备用;
步骤3:称取六水合硝酸镁0.6550g、2,5二羟基对苯二甲酸0.1650g置于烧杯中,然后向其中加入61.5mLN-N二甲基甲酰胺、4.1mL去离子水以及4.1mL乙醇的混合溶液,于磁力搅拌器上充分搅拌0.5h,过滤后得到澄清反应溶液并注入聚四氟乙烯反应釜中;
步骤4;将经过步骤2后的镁合金片垂直并完全浸入步骤3所制得的反应溶液,密封反应釜,然后将其放入恒温鼓风干燥箱中,升温至120℃,26h后自然冷却至室温;
步骤5:取出长有涂层的镁合金片,用无水甲醇冲洗数次后置于无水甲醇中浸泡10h,然后将镁合金片置于真空干燥箱中,100℃保持6h,即获得具有Mg-MOF-74/MgF2复合涂层的镁合金复合材料。
实施例3
一种医用镁合金表面金属有机骨架Mg-MOF-74/MgF2涂层的制备步骤如下:
步骤1:将厚度为1mm的镁合金AZ31B切割成2cm×2cm的长方形,依次用240目、500目、800目水磨砂纸打磨去除表面氧化层,然后将镁合金片置于丙酮、乙醇中分别超声清洗15分钟,再用去离子水超声清洗5分钟,吹干备用;
步骤2:将步骤1中预处理后的镁合金片放入装有适量质量分数为40%氢氟酸的聚乙烯烧杯中,酸蚀3.5小时后取出,用去离子水清洗备用;
步骤3:称取六水合硝酸镁0.6450g、2,5二羟基对苯二甲酸0.1600g置于烧杯中,然后向其中加入60.5mLN-N二甲基甲酰胺、3.9mL去离子水以及3.9mL乙醇的混合溶液,于磁力搅拌器上充分搅拌0.5h,过滤后得到澄清反应溶液并注入聚四氟乙烯反应釜中;
步骤4:将经过步骤2后的镁合金片垂直并完全浸入步骤3所制得的反应溶液,密封反应釜,然后将其放入恒温鼓风干燥箱中,升温至115℃,28h后自然冷却至室温;
步骤5:取出长有涂层的镁合金片,用无水甲醇冲洗数次后置于无水甲醇中浸泡8h,然后将镁合金片置于真空干燥箱中,100℃保持9h,即获得具有Mg-MOF-74/MgF2复合涂层的镁合金复合材料。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (1)
1.一种提高医用镁合金表面耐腐蚀及亲水性能的涂层,其特征在于,该涂层为Mg-MOF-74/MgF2复合涂层;
所述提高医用镁合金表面耐腐蚀及亲水性能的涂层的制备方法,包括以下步骤:
(1)医用镁合金的表面预处理:以镁合金AZ31B作为基体材料,用砂纸打磨,用丙酮、乙醇及去离子水清洗,备用;
(2)MgF2膜层的制备:将上述预处理后的镁合金片放入质量分数为40%的氢氟酸中酸蚀2.5h,使其表面产生MgF2化学转化膜,然后取出用去离子水冲洗干净,备用;
(3)反应溶液的配制:将六水合硝酸镁、2,5二羟基对苯二甲酸置于N-N二甲基甲酰胺、去离子水以及乙醇的混合溶液中,于磁力搅拌器上充分搅拌,过滤后制得反应溶液,注入聚四氟乙烯反应釜中;
(4)Mg-MOF-74/MgF2复合涂层的制备:将步骤(2)制得的具有MgF2转化膜的镁合金片垂直置于反应釜且完全没入步骤(3)制得的反应溶液中,密封后将反应釜置于鼓风干燥箱中,升温,反应;
(5)Mg-MOF-74/MgF2复合涂层的后处理:将步骤(4)反应后的镁合金片用无水甲醇冲洗,然后置于无水甲醇中浸泡,而后再取出置于真空干燥箱干燥,即获得具有Mg-MOF-74/MgF2复合涂层的镁合金复合材料。
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