CN111359014A - 聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法 - Google Patents

聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法 Download PDF

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CN111359014A
CN111359014A CN201811589537.0A CN201811589537A CN111359014A CN 111359014 A CN111359014 A CN 111359014A CN 201811589537 A CN201811589537 A CN 201811589537A CN 111359014 A CN111359014 A CN 111359014A
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hydroxyapatite
coating
ciprofloxacin
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江晓红
周兵兵
何纯
肖金涛
李贝贝
许正巍
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法。所述的复合涂层由基体、喷涂在基体表面的羟基磷灰石涂层和沉积在羟基磷灰石涂层表面的聚乳酸基环丙沙星抗菌薄膜组成，先采用等离子喷涂技术在基体表面喷涂羟基磷灰石，再采用低功率电子束沉积技术在羟基磷灰石涂层表面沉积聚乳酸/环丙沙星复合物。本发明制备过程简单，制得的聚乳酸基环丙沙星/羟基磷灰石复合涂层具有生物活性和生物的稳定性，还具有抗菌功能，消除局部炎症。

Description

聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法
技术领域
本发明属于医用材料人工植入体技术领域，涉及一种聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法。
背景技术
羟基磷灰石[Ca10(PO4)6(OH)2简称HA]，钙磷比1.67，是氢氧化钙和磷酸三钙的复盐，其晶粒的端面是正六边形，晶粒的c轴为柱轴方向，a轴与正六边形的任一边平行。它具有与人体骨和牙齿中主要矿物质相类似的化学组成和晶体结构，是人体骨骼组织的主要无机成分，能与人体骨骼组织形成化合键性结合，是一类典型的生物活性材料。单纯的HA陶瓷力学性能较差，其抗弯强度和断裂韧性指标均低于人体致密骨，难以在生物体承载部位使用，但在生物惰性合金基体上沉积一层HA陶瓷涂层时则能得到具有很好综合性能的生物植入材料，既有利于材料与周围骨组织的结合，也可以阻止金属离子的释放。制备羟基磷灰石陶瓷涂层的方法很多，主要有：等离子喷涂、离子束溅射、溶胶-凝胶法等。其中离子束溅射存在制备的涂层为非晶态，易在体液中分解；溶胶-凝胶法存在制备薄膜所需时间长，涂层与基体的结合强度能力较差。
聚乳酸(PLA)热稳定性好、生产过程无污染、具有良好的生物相容性和可降解性，还具有一定的抗菌性，应用广泛，如用于包装材料、注塑、生物医药等方面，是一种理想的绿色高分子材料。环丙沙星具有广泛的抗菌作用，对大肠杆菌、金黄色葡萄球菌、绿脓杆菌等具有良好的抗菌效果。目前，聚乳酸与羟基磷灰石的复合方法主要有：采用溶液法使用聚乳酸修饰羟基磷灰石，存在两者结合力不足，反应时间过久；采用电沉积法修饰存在会水解产生的氢气影响沉积质量。([1]肖素光,赵婧,翁杰.聚乳酸涂层改善网状羟基磷灰石陶瓷支架力学性能的研究[J].功能材料,2007,38(3):432-434.DOI:10.3321/j.issn:1001-9731.2007.03.027；[2]CN201010540770.7)。
低功率电子束沉积技术的原理是一束电子通过5-10kV的电场后被加速，最后聚集到待蒸发材料的表面。当电子束打到待蒸发材料的表面时，电子会迅速损失自己的能量，将能量传递给待蒸发材料使其熔化并蒸发。电子束蒸发是制备高熔点和高纯度薄膜的主要方法，并且功率调节范围广，使用方便。
发明内容
本发明目的在于提供一种兼具生物活性和抗菌性的聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法，采用等离子喷涂技术和低功率电子束沉积技术制备。
实现本发明目的的技术方案如下：
聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法，所述的复合涂层由基体、喷涂在基体表面的羟基磷灰石涂层和沉积在羟基磷灰石涂层表面的聚乳酸基环丙沙星抗菌薄膜组成，先采用等离子喷涂技术在基体表面喷涂羟基磷灰石，再采用低功率电子束沉积技术在羟基磷灰石涂层表面沉积聚乳酸/环丙沙星复合物，具体步骤如下：
步骤1，将干燥的粒度在50～85μm的高纯羟基磷灰石粉末，采用等离子喷涂技术喷涂在洁净和粗糙化的金属基体表面上，喷涂电流650～710A，喷涂距离9～13cm，氩气流量2600～3000L/H，氢气流量120～180L/H，得到厚度为150～220μm的羟基磷灰石涂层；
步骤2，将环丙沙星粉末与聚乳酸混合均匀，置于反应腔室，调整靶材与羟基磷灰石涂层的距离为20～30cm，抽真空，镀膜，设置工作电流为7～9A，工作电压为0.8～1.8kV，采用低功率电子束沉积技术在羟基磷灰石涂层表面沉积聚乳酸基环丙沙星抗菌薄膜，得到聚乳酸基环丙沙星/羟基磷灰石复合涂层。
优选地，步骤1中，通过对金属基材表面进行预处理，除去表面的残存油污以及氧化膜，并对金属基体表面进行喷砂处理得到洁净并粗糙化的金属基体。
优选地，步骤1中，所述的高纯羟基磷灰石的纯度≥99％。
优选地，步骤2，所述的电子束沉积时间为5分钟。
优选地，步骤2，所述的环丙沙星粉末与聚乳酸的质量比为2:1～1:2。
与现有的技术相比，本发明具有以下优点：
(1)先采用等离子喷涂制备厚度150～220μm的羟基磷灰石涂层，再采用低功率电子束技术在羟基磷灰石涂层上沉积聚乳酸基环丙沙星抗菌薄膜，将两种涂层叠加复合，与单一的羟基磷灰石的涂层对比，制备的复合涂层不仅具有生物活性和生物的稳定性，还具有抗菌功能，消除局部炎症反应；
(2)选用的材料绿色安全，可由人体自行降解代谢；
(3)羟基磷灰石涂层表面的微米和亚微米的孔，除了提供聚乳酸分子和环丙沙星小分子的附着，也起到药物缓释的作用以及后续植入体进入人体后为细胞提供附着点。
附图说明
图1为不同工艺参数羟基磷灰石涂层复合相同抗菌涂层(PLA:环丙沙星＝1:2)对金黄色葡萄球菌的抗菌效果图；
图2为不同工艺参数羟基磷灰石涂层复合相同抗菌涂层(PLA:环丙沙星＝1:1)对金黄色葡萄球菌的抗菌效果图；
图3为不同工艺参数羟基磷灰石涂层复合相同抗菌涂层(PLA:环丙沙星＝2:1)对金黄色葡萄球菌的抗菌效果图；
图4为复合涂层中羟基磷灰石涂层的截面SEM图；
图5为复合涂层中羟基磷灰石涂层的表面形貌SEM图；
图6为复合涂层中羟基磷灰石涂层的XRD图。
具体实施方式
下述各实施例中所用的羟基磷灰石都是市售医用级别，为纳米团聚球形粉末，粒径在50～85μm，PLA与环丙沙星粉末均为医用级别。喷涂前在真空干燥烘箱120℃烘干3h，金属基材是经过预处理和喷砂的医用钛合金，规格为2*15*15mm，喷涂所用的气体均为纯度99.99％。
实施例1
采用等离子喷涂将羟基磷灰石粉末喷涂在经过预处理和喷砂处理的基体表面上，喷涂工艺参数：喷涂电流650A，喷涂距离13cm，氩气流量2600L/H，氢气流量150L/H，喷涂一次，得到羟基磷灰石涂层。
将喷涂了羟基磷灰石涂层的金属基体放置于电子束沉积的腔室中，用夹子将基底固定，将质量比(PLA：环丙沙星＝1:2)的靶材放入电子束沉积的反应室中，用机械泵和分子泵分别抽真空，使真空度达到6×10-3～8×10-3Pa。打开沉积薄膜的电源，将工作电流调节在7～9A，工作电压控制在0.8～1.8kV，当真空度显示在5×10-2～6×10-2Pa时，可通过观察窗看到在靶材和基底之间有等离子态的物质由靶材向基底转移，通过膜厚仪上膜厚的变化可以判断沉积是否完成，当膜厚不再变化时，即可说明沉积结束，此时将电流和电压缓慢归零，等待10min，使真空室的温度降下来后，关闭仪器电源，镀膜完成。并且重复以上步骤，在上述相同羟基磷灰石涂层基底沉积不同质量比(1:1、2:1)的抗菌涂层。
金黄色葡萄球菌的培养
称取酵母浸粉0.5g，蛋白胨1.0g，NaCl 1.0g，用去离子水溶解在烧杯中，滴加少许的NaOH溶液，直至pH值调节至7，然后用玻璃棒引流，将溶液倒入100mL的锥形瓶中，定容，摇匀，取三支洗净的小试管，在每个小试管中用移液枪取5.00mL的溶液，然后把试管口用锡纸封上，再把小试管放入高压蒸汽灭菌锅中灭菌。
灭菌完成后，将试管，接种环，打火机放入超净工作台中用紫外灯照射20min，照射完成后开风扇吹2min，之后戴上一次性的橡胶手套，取出金黄色葡萄球菌的菌种，点燃酒精灯，用酒精棉擦拭双手及超净工作台，将接种环放在酒精灯外焰上灼烧，直到烧红为止，接种环杆的部分要边旋转边灼烧，再将装有金黄色葡萄球菌的试管口放在酒精灯上烧，然后将接种环伸入到装有金黄色葡萄球菌的试管中，取适量的菌种接种到液体培养基中，然后再用锡纸包好，用橡皮筋扎紧，重复以上步骤三次，直到3个试管都接种完成，熄灭酒精灯，关闭超净工作台，将接种好的金黄色葡萄球菌放入30℃的摇床中，培养12个小时。
聚乳酸基环丙沙星/羟基磷灰石复合涂层抗菌性能的研究
称取酵母浸粉0.5g，蛋白胨1.0g，NaCl 1.0g，琼脂粉1.6g，用去离子水溶解在烧杯中，滴加少许的NaOH溶液，直至pH值调节至7，然后用玻璃棒引流，将溶液倒入100mL的锥形瓶中，定容，摇匀，再用封口膜将锥形瓶口封好，将用报纸包好的培养皿、镊子、移液枪头和液体培养基一同放入高压蒸汽灭菌锅中灭菌。
灭菌完成后将培养皿、移液枪头、移液枪和打火机放入超净工作台中用紫外灯照射20min，用风扇吹2分钟，从培养的三个金黄色葡萄球菌的试管中选择一个效果最好的倒入锥形瓶中，充分震荡，摇匀；将复合涂层材料镀膜的一面朝上，并放置于培养皿的中心位置，用移液枪移取10.0mL的培养基到培养皿中，注意移取过程中尽量避免有气泡，移取过程要迅速，防止培养基凝固。最后接种好的培养基放在30℃的培养箱中培养24h。
实施例2
采用等离子喷涂将羟基磷灰石粉末喷涂在经过预处理和喷砂处理的基体表面上，喷涂工艺参数：喷涂电流680A，喷涂距离11cm，氩气流量2800L/H，氢气流量120L/H，喷涂一次，得到羟基磷灰石涂层。PLA基环丙沙星复合膜的沉积、金黄色葡萄球菌的培养以及抗菌性能的研究，其余步骤与实施例1相同。
实施例3
采用等离子喷涂将羟基磷灰石粉末喷涂在经过预处理和喷砂处理的基体表面上，喷涂工艺参数：喷涂电流710A，喷涂距离9cm，氩气流量3000L/H，氢气流量180L/H，喷涂一次，得到羟基磷灰石涂层。PLA基环丙沙星复合膜的沉积、金黄色葡萄球菌的培养以及抗菌性能的研究，其余步骤与实施例1相同。
对比例1
羟基磷灰石涂层采用低功率电子束制备。由于电子束能量对羟基磷灰石粉末过低，导致不能在金属基体上形成涂层。
对比例2
聚乳酸基环丙沙星抗菌涂层采用等离子喷涂制备。由于喷涂时温度为2000℃甚至更高，聚乳酸和环丙沙星这类高分子材料，会直接分解。
从图1到图3可以得出不同实施例中的羟基磷灰石涂层上都能进行沉积抗菌涂层，并且具有抗菌性能，实施3制备的聚乳酸基环丙沙星/羟基磷灰石复合涂层具有最好的抗菌性能；从图1到图3得出随着抗菌涂层中配比不同，依然可以沉积在羟基磷灰石涂层上，并且出现不同的抗菌能力，环丙沙星的质量上升，抗菌性能上升。
图4与图5体现羟基磷灰石的涂层的厚度与表面形貌，明显看出表面的多孔形貌，截面上的孔形貌一定程度上体现了内部结构，自左向右分别对应实施例1、2、3，厚度分别为182.1μm、190.3μm、186.2μm。
图6中002晶面的出现的体现了涂层中的羟基磷灰石具有c轴择优取向。

Claims (6)

1.聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法，其特征在于，具体步骤如下：
步骤1，将干燥的粒度在50～85μm的高纯羟基磷灰石粉末，采用等离子喷涂技术喷涂在洁净和粗糙化的金属基体表面上，喷涂电流650～710A，喷涂距离9～13cm，氩气流量2600～3000L/H，氢气流量120～180L/H，得到厚度为150～220μm的羟基磷灰石涂层；
步骤2，将环丙沙星粉末与聚乳酸混合均匀，置于反应腔室，调整靶材与羟基磷灰石涂层的距离为20～30cm，抽真空，镀膜，设置工作电流为7～9A，工作电压为0.8～1.8kV，采用低功率电子束沉积技术在羟基磷灰石涂层表面沉积聚乳酸基环丙沙星抗菌薄膜，得到聚乳酸基环丙沙星/羟基磷灰石复合涂层。
2.根据权利要求1所述的制备方法，其特征在于，步骤1中，通过对金属基材表面进行预处理，除去表面的残存油污以及氧化膜，并对金属基体表面进行喷砂处理得到洁净并粗糙化的金属基体。
3.根据权利要求1所述的制备方法，其特征在于，步骤1中，所述的高纯羟基磷灰石的纯度≥99％。
4.根据权利要求1所述的制备方法，其特征在于，步骤2，所述的电子束沉积时间为5分钟。
5.根据权利要求1所述的制备方法，其特征在于，步骤2，所述的环丙沙星粉末与聚乳酸的质量比为2:1～1:2。
6.根据权利要求1至5任一所述的制备方法制得的聚乳酸基环丙沙星/羟基磷灰石复合涂层。
CN201811589537.0A 2018-12-25 2018-12-25 聚乳酸基环丙沙星/羟基磷灰石复合涂层的制备方法 Pending CN111359014A (zh)

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