CN106583213A - 一种应用溶胶凝胶法在az31表面制备甲基纤维素/羟基磷灰石复合涂层 - Google Patents
一种应用溶胶凝胶法在az31表面制备甲基纤维素/羟基磷灰石复合涂层 Download PDFInfo
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Abstract
本发明涉及一种应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层。一种应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，以甲基纤维素为添加剂，Ca(OH)2和Ca(H2PO4)2·H2O为原料，通过溶胶凝胶法在AZ31镁合金表面制备了厚度约60μm的甲基纤维素‑羟基磷灰石(MC‑HAP)复合涂层。通过溶胶凝胶法在AZ31镁合金表面制备出的MC‑HAP复合涂层不仅提高了膜层与基体的结合力，降低孔隙率，而且使膜层对基体的保护作用得到增强，是一种较好的制备羟基磷灰石涂层的方法。
Description
技术领域
本发明涉及一种应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层。
背景技术
AZ31镁合金是一种最轻的工程结构金属材料，具有密度小、比强度高、良好的导电能力和电磁屏蔽性能、减振和阻尼性能好且容易回收利用等特点，因此在汽车、航空航天以及3C产品(家用电器、计算机、通信电子器件)等领域已经有了广泛的应用。镁又是人体必需的元素，研究证实镁对人体无毒性且能够促进骨组织愈合，使其成为最具研究价值的生物医用材料。但是镁合金的耐蚀性差，在生物体内降解速率快，不能满足其作为骨植入材料的要求。
羟基磷灰石耐蚀性高，化学性能好，有良好的生物相容性，是人体骨骼组织的主要成分，如果将羟基磷灰石覆盖在镁合金表面，不仅可以提高镁合金的耐蚀性能，延缓其降解速率，而且还使羟基磷灰石具有优良的力学性能。
金属基表面制备羟基磷灰石涂层的方法很多，有激光熔覆法、等离子喷涂法、电化学沉积法、仿生溶液法、溶胶凝胶法等。与其他方法相比，溶胶凝胶法操作简单，成本低廉，但目前利用溶胶凝胶法在AZ31表面制备羟基磷灰石涂层的应用还较少，而且由
于陶瓷与金属的膨胀系数及化学键型的差别较大，导致该方法制备的涂层裂纹较多、厚度较薄。甲基纤维素是一种由纤维素和NaOHCH3Cl制得的纤维素，本身具有一定的热凝胶性及较好的成膜性，制备HAP涂层时添加适量的MC可增加凝胶的粘度，减少它的流动性，有利于涂层均匀成膜并能增加涂层的强度。
因此，需要提供一种既可以提高镁合金的耐蚀性能，延缓其降解速率，又可以使得涂层均匀成膜并能增加涂层的厚度的复合涂层，以用于提高对基体的保护作用。
发明内容
本发明所要解决的技术问题是：如何提高镁合金的耐蚀性能，延缓其降解速率。
本发明所采用的技术方案是：一种应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，按照如下步骤进行：
步骤一、基体预处理：把AZ31镁合金轧板通过打磨去除表面的氧化物后依次进行无水乙醇、去离子水超声清洗，然后用稀磷酸溶液活化，最后再次依次进行去离子水、无水乙醇、去离子水超声清洗；
步骤二、甲基纤维素-羟基磷灰石混合凝胶的制备：将Ca(OH)2过饱和溶液在水浴中加热，然后缓慢滴加Ca(H2PO4)2溶液，搅拌、静置，使其成为凝胶，随后向该凝胶中加入甲基纤维素MC水溶液搅拌均匀，制得甲基纤维素-羟基磷灰石混合凝胶；
步骤三、甲基纤维素-羟基磷灰石复合涂层的制备：将步骤一种
经过预处理的AZ31镁合金放入步骤二中制得的甲基纤维素-羟基磷灰石混合凝胶浸泡，浸泡过程提拉AZ31镁合金，浸泡完成后把AZ31镁合金进行低温干燥和高温热处理，然后再次放入步骤二中制得的甲基纤维素-羟基磷灰石混合凝胶浸泡，浸泡过程提拉AZ31镁合金，浸泡完成后把AZ31镁合金进行低温干燥和高温热处理，重复2-3次，制得MC-HAP复合涂层。
作为一种优选方式：所述的步骤一中稀磷酸溶液的质量百分比浓度为4%，活化时间为10秒钟。
作为一种优选方式：所述的步骤二中水浴温度为70℃。
作为一种优选方式：所述的步骤二中滴加Ca(H2PO4)2溶液至钙磷物质的量比为1.67，搅拌的时间为1小时。
作为一种优选方式：所述的步骤二中甲基纤维素MC的质量百分比浓度为2%。
作为一种优选方式：所述的步骤三中每次浸泡时间为2分钟，提拉速度为0.1mm/s。
作为一种优选方式：所述的步骤三中干燥温度为80℃，干燥时间为15分钟。
作为一种优选方式：所述的步骤三中热处理温度为200℃，热处理时间为30分钟。
作为一种优选方式：在Ca(OH)2过饱和溶液中添加磷酸铵，磷酸铵的质量百分比浓度为0.2-1%。
本发明的有益效果是：本发明利用溶胶凝胶法在AZ31表面制备的甲基纤维素-羟基磷灰石复合涂层兼具了羟基磷灰石良好的生物活性及生物相容性与甲基纤维素较好的粘合性、成膜性及水分保持性。甲基纤维素-羟基磷灰石复合涂层既可以提高镁合金的耐蚀性能，延缓其降解速率，又可以使得涂层均匀成膜并能增加涂层的厚度，对AZ31镁合金起到很好的保护作用。
附图说明
图1是本发明制备的甲基纤维素-羟基磷灰石复合涂层XRD图。
图2是本发明制备的甲基纤维素-羟基磷灰石复合涂层FTIR图。
图3(a)、(b)分别是本发明制备的甲基纤维素-羟基磷灰石复合涂层SEM和截面图。
图4是本发明制备的甲基纤维素-羟基磷灰石复合涂层的极化曲线图。
具体实施方式
选用尺寸为20mm×20mm×1mm的AZ31镁合金轧板为基体，经过600#、1000#的SiC砂纸打磨，去除表面的氧化物，再分别经去离子水、无水乙醇、去离子水超声清洗10分钟，然后用质量百分比浓度为4%的稀磷酸溶液活化10秒钟，最后再次依次进行去离子水、无水乙醇、去离子水超声清洗10分钟，使用稀磷酸溶液使得AZ31镁合金轧板更易和羟基磷灰石和甲基纤维素的混合凝胶结合；
按钙磷比为1.67分别配制Ca(OH)2过饱和溶液和Ca(H2PO4)2溶液，先将Ca(OH)2过饱和溶液放入70℃水浴中加热，然后加入磷酸铵使得溶液中磷酸铵的质量百分比浓度为0.5%（磷酸铵增加Ca(OH)2的可溶性，由于Ca(OH)2的水溶性很差，如果不使用磷酸铵，后续制得MC-HAP复合涂层厚度非常薄，并且其致密性差，会出现部分腐蚀的现象），然后缓慢滴加Ca(H2PO4)2溶液强力搅拌1小时后，取出溶胶，静置，再对溶胶进行去水处理使其成为凝胶。向上述凝胶中缓慢加入质量百分比浓度为2%的甲基纤维素（MC）水溶液并搅拌均匀，制得羟基磷灰石和甲基纤维素的混合凝胶。
将经过预处理的镁合金放入上述凝胶中浸泡2分钟，并以0.1mm/s的速度提拉，然后在80℃干燥箱中干燥15分钟，最后放入200℃电阻炉中热处理30分钟，重复2-3次，制得MC-HAP复合涂层。
产品分析：
图1是本发明制备的甲基纤维素-羟基磷灰石复合涂层XRD图，从图1可见，除了存在高而尖锐的镁的特征衍射峰外，在25.9°、31.8°、32.2°、32.9°、39.8°、49.5°能明显的看到HAP的特征衍射峰，这些衍射峰与羟基磷灰石粉末标准衍射图谱（JCPDS#09-0432）基本吻合。
图2是本发明制备的甲基纤维素-羟基磷灰石复合涂层FTIR图，从图2可见，图2(a)是纯MC的红外光谱，3455cm-1为-OH的伸缩振动峰，在2981cm-1和2887cm-1有甲氧基CH的伸缩振动峰，1040cm-1为OH的弯曲振动峰。图2(b)为HAP的红外谱图，3462cm-1和610cm-1分别为-OH的伸缩振动峰和弯曲振动峰，1094 cm-1、604 cm-1、1031cm-1和566cm-1处的较强特征峰为PO的峰。图2(c)为从AZ31表面刮落的粉体的红外光谱，图中存在各成分的主要特征峰，但有一些-OH峰发生了偏移，这可能是由于HAP-MC两种材料的分子间或分子内氢键的作用所致。在1457cm-1和875cm-1处有较弱的红外吸收特征峰，这主要是Ca-O的伸缩振动和弯曲振动。所以可以证实通过甲基纤维素辅助凝胶法在AZ31表面制备的羟基磷灰石涂层中存在甲基纤维素。
图3(a)、(b)是本发明制备的甲基纤维素-羟基磷灰石复合涂层SEM和截面图，从图3(a)可见，制备的甲基纤维素-羟基磷灰石复合膜层表面的形貌相对平整、更加致密，产生的裂纹较少，这是因为甲基纤维素成膜性较好使表面的涂层相对致密，它可以弥补在加热时失去水分子所形成的裂纹。从图3(b)可见，制备的甲基纤维素-羟基磷灰石复合膜层与基体的连接紧密，说明膜层与基体的结合强度较高，而且膜层厚度大约为60μm，说明MC对提高HAP涂层与基体的结合力起到关键作用，正是由于涂层与基体的结合力提高了，使添加甲基纤维素后膜层的厚度增加。
图4是本发明制备的甲基纤维素-羟基磷灰石复合涂层的极化曲线图，从图4可见，添加甲基纤维素后，材料的腐蚀电位增加，腐蚀电流减小，说明添加MC后涂层的耐蚀性比未添加MC的涂层提高了。这跟添加甲基纤维素后的膜层的较厚的厚度和较低的孔隙率有关。
通过以上试验得出：本发明制备的甲基纤维素-羟基磷灰石复合涂层既可以提高镁合金的耐蚀性能，延缓其降解速率，又可以使得涂层均匀成膜并能增加涂层的厚度，对AZ31镁合金起到很好的保护作用。
Claims (8)
1.一种应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：按照如下步骤进行：
步骤一、基体预处理：把AZ31镁合金轧板通过打磨去除表面的氧化物后依次进行无水乙醇、去离子水超声清洗，然后用稀磷酸溶液活化，最后再次依次进行去离子水、无水乙醇、去离子水超声清洗；
步骤二、甲基纤维素-羟基磷灰石混合凝胶的制备：将Ca(OH)2过饱和溶液在水浴中加热，然后缓慢滴加Ca(H2PO4)2溶液，搅拌、静置，使其成为凝胶，随后向该凝胶中加入甲基纤维素MC水溶液搅拌均匀，制得甲基纤维素-羟基磷灰石混合凝胶；
步骤三、甲基纤维素-羟基磷灰石复合涂层的制备：将步骤一中经过预处理的AZ31镁合金放入步骤二中制得的甲基纤维素-羟基磷灰石混合凝胶浸泡，浸泡过程提拉AZ31镁合金，浸泡完成后把AZ31镁合金进行低温干燥和高温热处理，然后再次放入步骤二中制得的甲基纤维素-羟基磷灰石混合凝胶浸泡，浸泡过程提拉AZ31镁合金，浸泡完成后把AZ31镁合金进行低温干燥和高温热处理，重复2-3次，制得MC-HAP复合涂层。
2.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤一中稀磷酸溶液的质量百分比浓度为4%，活化时间为10秒钟。
3.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基
纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤二中水浴温度为70℃。
4.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤二中滴加Ca(H2PO4)2溶液至钙磷物质的量比为1.67，搅拌的时间为1小时。
5.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤二中甲基纤维素MC的质量百分比浓度为2%。
6.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤三中每次浸泡时间为2分钟，提拉速度为0.1mm/s。
7.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤三中干燥温度为80℃，干燥时间为15分钟。
8.根据权利要求1所述的应用溶胶凝胶法在AZ31表面制备甲基纤维素/羟基磷灰石复合涂层，其特征是：所述的步骤三中热处理温度为200℃，热处理时间为30分钟。
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