CN114984324B - 一种金属表面耐腐蚀性自修复涂层及其制备方法 - Google Patents
一种金属表面耐腐蚀性自修复涂层及其制备方法 Download PDFInfo
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- CN114984324B CN114984324B CN202210625080.4A CN202210625080A CN114984324B CN 114984324 B CN114984324 B CN 114984324B CN 202210625080 A CN202210625080 A CN 202210625080A CN 114984324 B CN114984324 B CN 114984324B
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Abstract
本发明公开了一种金属表面耐腐蚀性自修复涂层及其制备方法，属于生物医用材料技术领域。该制备方法首先通过微弧氧化技术制备MAO‑nHA涂层作为无机涂层，然后采用硅烷偶联剂对MAO‑nHA涂层表面进行改性处理；再与氧化海藻酸镁通过席夫碱反应得到复合涂层；使得该涂层具备良好的生物性能及粘结强度，且对成骨细胞增殖活性及成骨细胞诱导骨化活性具有显著的促进作用。
Description
技术领域
本发明属于生物医用材料技术领域，具体涉及一种金属表面耐腐蚀性自修复涂层及其制备方法。
背景技术
在骨科修复领域，镁扮演着重要的角色。相比于惰性金属，其可降解性避免了二次手术以及长期植入导致的炎症、过敏等潜在风险，尤其是对于老年患者，这是不可多得的福音。而在生物性能方面，首先镁离子是人体必需元素，吸收后多余的镁可通过肾脏排出体外，有动物实验表明即使是肾衰竭亦能维持体内的镁平衡。其次镁离子能够促进钙磷沉积，加速体内矿化过程。镁离子还能通过PI3K/Akt、Wnt等信号通路激活下游蛋白从而促进成骨细胞增殖。力学性能方面，金属镁弹性模量相比于钛合金更接近人体骨，可有效降低由应力遮挡引起的骨质疏松、假体周围骨折等并发症。而且其密度值相比钛也最接近人体骨密度。更可观的是镁储备丰富，价格仅为钛的1/4，作为植入物可大幅减轻患者及社会的经济负担。但镁化学性质活泼易降解，尤其是体内富含氯离子的环境下，并呈现明显的点腐。腐蚀后的镁会出现失重、氢气释放和PH上升等问题。过早失重将削弱其力学性能，不足以提供足够的支撑。而过量的氢气释放会引发肌肉、皮下积气，螺钉置入骨髓部分降解会出现比软组织更严重的氢气积蓄，其生物安全性有待进一步研究。而PH值虽然一定范围内上升可促成骨生产、促血管化和抗菌作用，但过大的pH值会影响成骨细胞在植入物表面的粘附和增殖，甚至会出现溶骨现象。故而迫切需要一种耐腐蚀性好，生物相容性可，又具备一定生物功能的涂层，来进一步推动镁在生物领域的应用。
现有涂层材料主要有无机、有机、无机-有机结合三种模式。涂层制备方法主要有微弧氧化、阳极氧化、化学转化、化学沉积和溶胶凝胶、逐层添加、浸涂、喷涂、旋涂等。现有涂层单一材料或者单一方法都存在着不足，也就是说多种材料或者方法结合的方式是未来涂层研究的方法。
发明内容
本发明的目的在于提供一种金属表面耐腐蚀性自修复涂层及其制备方法。该涂层具有良好的生物相容性及粘结强度，且对成骨细胞增殖活性及成骨细胞诱导骨化活性具有显著的促进作用。
本发明为实现上述目的所采取的技术方案为：
一种金属表面耐腐蚀性自修复涂层，包括：无机涂层和有机涂层；上述无机涂层包括微弧氧化MAO涂层，其组分包括纳米羟基磷灰石nano-HA；上述有机涂层至少包括氧化海藻酸镁OMA；上述无机涂层和有机涂层之间通过硅烷偶联剂连接；上述硅烷偶联剂结构中至少包括硅氧烷基团和氨基基团。
本发明采用化学接枝保证了复合涂层间的界面结合强度，能更好的发挥复合涂层的功能。其中本发明以金属为基材，以无机微弧氧化MAO涂层为内层保障耐腐蚀性，中间以硅烷偶联剂连接无机和有机涂层组分，最外层有机成分氧化海藻酸镁利用席弗碱反应接枝到硅烷偶联剂(如APTES等)上，即使在镁降解局部碱性微环境下，席弗碱反应构建的化学结合依旧能保持稳定性。也就是说本涂层同时保障了初始耐腐蚀性以及远期耐腐蚀性，能更好的提升金属镁的耐腐蚀性，延长金属镁在体内的服役时长。
优选地，上述硅烷偶联剂包括3-氨丙基三乙氧基硅烷。
优选地，上述硅烷偶联剂包括改性3-氨丙基三乙氧基硅烷；上述改性3-氨丙基三乙氧基硅烷所用改性剂包括3-氨基吡咯烷-3-羧酸。本发明采用3-氨基吡咯烷-3-羧酸对3-氨丙基三乙氧基硅烷进行改性，3-氨丙基三乙氧基硅烷结构中的氨基与3-氨基吡咯烷-3-羧酸结构中的羧基通过脱水缩合反应得到改性3-氨丙基三乙氧基硅烷，再将其作为“媒介”，将无机涂层和有机涂层紧密连接，进一步提升了复合涂层的界面粘结强度、耐腐蚀性能，且具有良好的生物相容性。
优选地，上述改性3-氨丙基三乙氧基硅烷的制备方法，包括：3-氨丙基三乙氧基硅烷结构中的氨基与3-氨基吡咯烷-3-羧酸结构中的羧基通过缩合反应制备得到改性3-氨丙基三乙氧基硅烷。
具体地，上述改性3-氨丙基三乙氧基硅烷的制备方法为：在3-氨丙基三乙氧基硅烷中加入蒸馏水，配制浓度为0.1-0.3g/mL的溶液，然后加入3-氨基吡咯烷-3-羧酸，混合搅拌，在140-160℃条件下，加热90-120min，用蒸馏水洗涤烘干，得到改性3-氨丙基三乙氧基硅烷。
对本发明而言，3-氨丙基三乙氧基硅烷与3-氨基吡咯烷-3-羧酸的摩尔比为1:0.5-0.7。
对本发明而言，改性3-氨丙基三乙氧基硅烷的化学结构如式I所示：
本发明还提供了一种金属表面耐腐蚀性自修复涂层的制备方法，包括以下步骤：
通过微弧氧化技术将nano-HA涂覆在处理后的基材表面形成MAO-nHA涂层；然后采用硅烷偶联剂对MAO-nHA涂层表面进行改性处理；接着与氧化海藻酸镁通过席夫碱反应得到复合涂层，即为耐腐蚀性自修复涂层。
具体地，上述金属表面耐腐蚀性自修复涂层的制备方法，包括：
氧化海藻酸镁的制备方法，包括：将海藻酸镁MA溶于去离子水，充分搅拌，获得浓度为0.015-0.025g/mL的MA溶液；加入高碘酸钠，在室温避光条件下搅拌反应12-15h，加入乙二醇继续反应2-3h以终止氧化反应；去离子水透析72-84h，将透析后的溶液在-80--85℃条件下冷冻并干燥，获得氧化海藻酸镁OMA；
MAO-nHA涂层的制备方法，包括：金属基材表面预处理后，由包含nano-HA的电解液通过微弧氧化在金属基材表面形成MAO-nHA涂层；微弧氧化过程实验参数为：电压350-370V，电源频率1000-1200Hz，占空比35-45％，时间4-8min；
金属表面耐腐蚀性自修复涂层的制备方法，包括：将3-氨丙基三乙氧基硅烷或改性3-氨丙基三乙氧基硅烷加入90-98wt％乙醇溶液中，在隔绝空气的条件下加入MAO-nHA，摇床100-150r/min，20-24h后取出，超声5-10min，获得硅烷偶联剂处理后的MAO-nHA备用；将氧化海藻酸镁溶于去离子水，得到浓度为5-7mg/mL的溶液，然后加入硅烷偶联剂处理后的MAO-nHA，摇床100-150r/min，10-12h后取出，超声5-10min，获得金属表面耐腐蚀性自修复涂层。
优选地，氧化海藻酸镁的制备方法中，MA与高碘酸钠的质量比为1:1-1.5；MA与乙二醇的质量体积比为1g:4-6mL。
优选地，MAO-nHA涂层的制备方法中，电解液成分包括：六偏磷酸钠2-3g/L、KF 8-10g/L、乙二醇7-10mL/L、nano-HA1-3g/L、去离子水4-6L。
优选地，MAO-nHA涂层的制备方法中，金属基材表面预处理包括：将金属基材经300，500，1000，1500，2000#SiC砂纸逐级打磨，乙醇、去离子水超声清洗10-15min，干燥。
优选地，金属表面耐腐蚀性自修复涂层的制备方法中，乙醇溶液与硅烷偶联剂的质量比为2-2.5:1；MAO-nHA涂层与硅烷偶联剂(3-氨丙基三乙氧基硅烷或改性3-氨丙基三乙氧基硅烷)的质量比为1.2-1.5:1；氧化海藻酸镁与硅烷偶联剂的质量比为1.2-1.5:1。
本发明还公开了一种上述制备方法得到的改性3-氨丙基三乙氧基硅烷在增强自修复涂层粘结强度性能中的用途。
更优选地，在上述制备方法制备的金属表面耐腐蚀性自修复涂层中加入牛蒡子苷元，牛蒡子苷元用量为自修复涂层质量的1-2wt％。
具体地，上述加入牛蒡子苷元的金属表面耐腐蚀性自修复涂层制备方法，包括：
以乙醇为溶剂，配制0.01-0.03g/mL的牛蒡子苷元溶液，将金属表面耐腐蚀性自修复涂层在牛蒡子苷元溶液中提拉浸泡200-300s，悬挂式甩干，得到复配牛蒡子苷元的复合涂层。
将本发明制备的自修复涂层与牛蒡子苷元复配使用，自修复涂层在牛蒡子苷元溶液中提拉浸泡甩干后得到最终涂层；所得涂层的粘结强度显著增强，对骨细胞增殖，成骨细胞分化具有促进作用，且具有良好的生物相容性。
本发明有益效果：
本发明采用无机-有机化学结合的复合涂层，充分利用了无机涂层的纯物理耐腐蚀以及有机涂层的功能性防腐，同时有机涂层成分中的镁离子与基体纯镁为同成分，可以减少第二相腐蚀，其次有机涂层中的镁离子还能保障早期促骨生成。后期主要依靠内部基体纯镁释放镁离子，继续促骨生成，也就保障了耐腐蚀的同时还保障了镁离子的促骨生成功能。此外，本发明采用3-氨基吡咯烷-3-羧酸对3-氨丙基三乙氧基硅烷进行改性，将无机涂层和有机涂层紧密连接，进一步提升了复合涂层的界面粘结强度、耐腐蚀性能，且具有良好的生物相容性。同时将涂层浸渍于牛蒡子苷元溶液中处理后，能够进一步增强自修复涂层间的界面粘结强度，耐腐蚀性，且对骨细胞增殖、成骨细胞分化具有更佳的促进效果。
本发明是一种金属表面耐腐蚀性自修复涂层及其制备方法，该涂层具有良好的生物相容性，且对骨细胞增殖、成骨细胞分化具有显著的促进作用。
附图说明
图1为实施例1制备MAO-nHA涂层的扫描电镜图；
图2为实施例1制备MAO-nHA/APTES-OMA涂层的扫描电镜图；
图3为涂层的体外降解PH值变化情况；
图4为涂层的体外降解腐蚀速率图；
图5为涂层的血液相容性测试结果；
图6为涂层对细胞增殖的影响情况；
图7为涂层对成骨细胞诱导骨化的影响情况。
具体实施方式
以下结合具体实施方式和附图对本发明的技术方案作进一步详细描述：
实施例1：
一种金属表面耐腐蚀性自修复涂层的制备：
氧化海藻酸镁制备：将海藻酸镁MA溶于去离子水，充分搅拌，获得浓度为0.015g/mL的MA溶液；加入高碘酸钠，在室温避光条件下搅拌反应12h，加入乙二醇继续反应2h以终止氧化反应；去离子水透析84h，将透析后的溶液在-80℃条件下冷冻并干燥，获得氧化海藻酸镁OMA；其中，MA与高碘酸钠的质量比为1:1；MA与乙二醇的质量体积比为1g:4mL；
微弧氧化MAO涂层制备：纯镁表面预处理后，由包含nano-HA的电解液通过微弧氧化在金属基材表面形成MAO-nHA涂层；其中，表面预处理包括：300，500，1000，1500，2000#SiC砂纸逐级打磨，乙醇、去离子水超声清洗10min，干燥；电解液组分：六偏磷酸钠3g/L、KF8g/L、乙二醇10mL/L、nano-HA(1g/L)、去离子水5L；微弧氧化过程实验参数为：采用恒定电压360V，电源频率1000Hz，占空比40％，时间5min，获得MAO-nHA涂层；
金属表面耐腐蚀性自修复涂层复合涂层制备：将3-氨丙基三乙氧基硅烷加入95％乙醇溶液中，在隔绝空气的条件下加入MAO-nHA，摇床100r/min，24h后取出，超声5min，获得MAO-nHA/APTES备用；将氧化海藻酸镁溶于去离子水，然后加入MAO-nHA/APTES，摇床100r/min，12h后取出，超声5min，获得MAO-nHA/APTES-OMA复合涂层；其中，乙醇溶液与硅烷偶联剂的质量比为2:1；MAO-nHA涂层与3-氨丙基三乙氧基硅的质量比为1.2:1；氧化海藻酸镁与3-氨丙基三乙氧基硅的质量比为1.2:1。
实施例2：
一种金属表面耐腐蚀性自修复涂层的制备方法与实施例1的区别：
MAO-nHA涂层与3-氨丙基三乙氧基硅的质量比为1.3:1；氧化海藻酸镁与3-氨丙基三乙氧基硅的质量比为1.3:1。
实施例3：
一种金属表面耐腐蚀性自修复涂层的制备方法与实施例1的区别：
MAO-nHA涂层与3-氨丙基三乙氧基硅的质量比为1.5:1；氧化海藻酸镁与3-氨丙基三乙氧基硅的质量比为1.5:1。
实施例4：
一种金属表面耐腐蚀性自修复涂层的制备方法与实施例1的区别：采用改性3-氨丙基三乙氧基硅烷替代3-氨丙基三乙氧基硅烷。
改性3-氨丙基三乙氧基硅烷的制备：在3-氨丙基三乙氧基硅烷中加入蒸馏水，配制成浓度为0.2g/mL的溶液，然后加入3-氨基吡咯烷-3-羧酸，混合搅拌，然后在150℃条件下，加热90min，用蒸馏水洗涤烘干，得到改性3-氨丙基三乙氧基硅烷(其化学结构如下所示)；其中，3-氨丙基三乙氧基硅烷与3-氨基吡咯烷-3-羧酸的摩尔比为1:0.5。
1H NMR(400MHz，D2O)：3.91(m，6H，O-CH 2)，3.40、3.11、2.75～2.84、2.23、2.01(6H，-CH 2)，3.31(t，2H，Si-CH2-CH2-CH 2)，1.69(m，2H，Si-CH2-CH 2)，1.27(t，9H，-CH 3)，0.68(t，2H，Si-CH 2)；HRMS(ESI)：C14H31N3O4Si,m/z[M+H]+,333.21。
实施例5：
一种金属表面耐腐蚀性自修复涂层的制备方法与实施例4的区别：以乙醇为溶剂，配制0.01g/mL的牛蒡子苷元溶液，将复合涂层在牛蒡子苷元溶液中提拉浸泡200s，悬挂式甩干，得到复配牛蒡子苷元的复合涂层；其中，牛蒡子苷元用量为自修复涂层质量的1wt％。
实施例6：
一种金属表面耐腐蚀性自修复涂层的制备方法与实施例5的区别：采用3-氨丙基三乙氧基硅烷替代改性3-氨丙基三乙氧基硅烷。
试验例1：
自修复涂层的性能
1.扫描电镜
采用Hitachi公司的S-4800冷场发射扫描隧道显微镜观察，加速电压为15KV。
对实施例1制备的MAO-nHA涂层和MAO-nHA/APTES-OMA涂层进行上述测试，测试结果如图1、图2所示。由图1、图2分析可知，MAO-nHA/APTES-OMA涂层除了在表面覆盖外，一定程度上填充了原本MAO-nHA涂层的多孔，可进一步提升耐腐蚀性。
2.粘结强度测试
涂层与基底间的粘结强度测试，根据ASTM C-633标准，采用万能材料试验机测试，在125℃条件下将涂层用环氧树脂胶粘结，固化2小时，然后进行测试。
表1粘结强度测试结果
对实施例1～6制备的自修复涂层进行上述测试，结果如表1所示。由表1可知，实施例6与实施例1相比，粘结强度明显增加，说明牛蒡子苷元对涂层与基底间的粘结强度具有促进作用；实施例4的粘结强度明显好于实施例1，说明3-氨基吡咯烷-3-羧酸的加入增强了涂层与基底间的粘结强度；且实施例5的粘结强度比实施例4更强，说明牛蒡子苷元与加入3-氨基吡咯烷-3-羧酸的涂层复配使用时，明显增强了涂层与基底间的粘结强度。
3.体外降解实验
采用PBS浸泡研究耐腐蚀性能。按照ASTM G31标准将涂层样品称重后放入含有PBS溶液的锥形瓶中，37℃恒温振荡不同时间后取出，去离子水清洗，干燥，在浸泡过程使用pH计记录pH值变化，将浸泡后的涂层样品用铬酸洗液(200g/L CrO3+10g/L AgNO3)清洗，然后用乙醇清洗、烘干称重，公式如下：
WL＝w/At
CR＝WL/d
WL：失重速率(mg/cm2/d)；A：试样表面积(cm2)；w：失重(mg)；t：浸泡时间(day)；CR：腐蚀速率(mm/y)；d：镁密度(g/cm3)。测试浸泡6天后的腐蚀速率。
对实施例1～6制备的自修复涂层进行上述测试，结果如图3、图4所示。由图3可知，从pH可见涂层明显降低了镁离子的释放，从而减少了Mg(OH)2的生成，降低了pH，降低了早期镁离子大量释放导致的局部毒性。此外复合涂层具备更好的耐腐蚀性，在弱碱性环境下更稳定。由图4可知，实施例4的腐蚀速率明显比实施例1低，说明3-氨基吡咯烷-3-羧酸的加入增强了涂层的耐腐蚀性；实施例6与实施例1相当，说明单独加入牛蒡子苷元对涂层的耐腐蚀速率无消极影响；实施例5相对于实施例4、实施例6的腐蚀速率下降明显，说明牛蒡子苷元与加入3-氨基吡咯烷-3-羧酸的涂层复配使用时，具有更优的耐腐蚀性能。
4.血液相容性-溶血试验
将3mL新鲜小鼠血加入EDTA抗凝管中，离心弃上清液，然后加入3mL 0.9wt％生理盐水离心，重复三次操作。为获得红细胞悬浮液，将0.1M PBS(10×PBS)重悬红细胞稀释50倍。依据GB/T16886.10标准和要求，按表面积/浸提介质为1.25cm2/mL的比例配置浸提液，其中，浸提介质均为0.9wt％生理盐水，浸提物质为实施例1～6制备的自修复涂层样品，温度37℃浸提24小时，得涂层浸提液。将900μL上述制备的红细胞悬浮液加入到100μL样品涂层的浸提液中，对照组加入100μL 0.9wt％生理盐水。在37℃下培养60min后离心，取上清液100μL于96孔板上，测试在541nm处吸光度值。
溶血率＝(样品吸光度-生理盐水吸光度)/Triton-X100的吸光度
对实施例1～6制备的自修复涂层进行上述测试，测试结果如图5所示。由图5可知，无论是纯镁还是附加涂层的镁基均具有较好的血液相容性，满足体内植入要求。
5.促骨细胞增殖CCK-8测试和成骨作用测试
将样品涂层分别置于96孔培养板中，将MC3T3细胞按1×104个/cm2的密度接种于涂层表面，分别培养1、3、5、7天，然后用CCK-8试剂检测细胞增殖。碱性磷酸酶ALP定量检测试剂盒用于在第3，7天检测不同涂层的ALP表达量。
对实施例1、实施例4、实施例5、实施例6制备的自修复涂层进行上述测试，测试结果如图6、图7所示。由图6、图7可知，实施例1和实施例6对骨细胞增殖、成骨骨化的影响效果相当，说明牛蒡子苷元的加入对骨细胞增殖、骨化无消极影响；实施例4相比于实施例1骨细胞增殖速度、成骨骨化明显增加，说明3-氨基吡咯烷-3-羧酸的加入对骨细胞增殖、成骨细胞诱导骨化起到促进效果；而实施例5的骨细胞增殖、骨化速度明显快于实施例4，说明牛蒡子苷元与加入3-氨基吡咯烷-3-羧酸的涂层复配使用后，对骨细胞增殖、成骨细胞诱导骨化具有明显的促进作用。
上述实施例中的常规技术为本领域技术人员所知晓的现有技术，故在此不再详细赘述。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。
Claims (5)
1.一种金属表面耐腐蚀性自修复涂层，包括：无机涂层和有机涂层；所述无机涂层包括微弧氧化MAO涂层，其组分包括纳米羟基磷灰石nano-HA；所述有机涂层至少包括氧化海藻酸镁OMA；所述无机涂层和有机涂层之间通过硅烷偶联剂连接；所述硅烷偶联剂为改性3-氨丙基三乙氧基硅烷，其结构如式I所示：
I；
所述改性3-氨丙基三乙氧基硅烷的制备方法，包括：3-氨丙基三乙氧基硅烷结构中的氨基与3-氨基吡咯烷-3-羧酸结构中的羧基通过缩合反应制备得到改性3-氨丙基三乙氧基硅烷；
所述3-氨丙基三乙氧基硅烷与3-氨基吡咯烷-3-羧酸的摩尔比为1:0.5-0.7。
2.权利要求1所述的金属表面耐腐蚀性自修复涂层的制备方法，包括以下步骤：
通过微弧氧化技术将nano-HA涂覆在处理后的基材表面形成MAO-nHA涂层；然后采用硅烷偶联剂对MAO-nHA涂层表面进行改性处理；接着与氧化海藻酸镁通过席夫碱反应得到复合涂层，即为耐腐蚀性自修复涂层。
3.根据权利要求2所述的金属表面耐腐蚀性自修复涂层的制备方法，其特征在于：所述MAO-nHA涂层与硅烷偶联剂的质量比为1.2-1.5:1；氧化海藻酸镁与硅烷偶联剂的质量比为1.2-1.5:1。
4.根据权利要求2所述的金属表面耐腐蚀性自修复涂层的制备方法，其特征在于：所述氧化海藻酸镁的制备方法，包括：将海藻酸镁MA溶于去离子水，充分搅拌，获得浓度为0.015-0.025g/mL的MA溶液；加入高碘酸钠，在室温避光条件下搅拌反应12-15h，加入乙二醇继续反应2-3h以终止氧化反应；去离子水透析72-84h，将透析后的溶液在-80~-85℃条件下冷冻并干燥，获得氧化海藻酸镁OMA。
5.根据权利要求2所述的金属表面耐腐蚀性自修复涂层的制备方法，其特征在于：所述MAO-nHA涂层的制备方法，包括：金属基材表面预处理后，由包含nano-HA的电解液通过微弧氧化在金属基材表面形成MAO-nHA涂层。
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