CN112899606B - 一种钛酸盐载药涂层的制备方法 - Google Patents
一种钛酸盐载药涂层的制备方法 Download PDFInfo
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- CN112899606B CN112899606B CN202110054447.7A CN202110054447A CN112899606B CN 112899606 B CN112899606 B CN 112899606B CN 202110054447 A CN202110054447 A CN 202110054447A CN 112899606 B CN112899606 B CN 112899606B
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Abstract
本发明属于表面改性技术领域，具体涉及一种钛酸盐载药涂层的制备方法。首先制备出混合均匀的适合等离子喷涂工艺过程的复合粉末，然后利用等离子喷涂技术和水热处理结合实现微纳米结构涂层的制备。本发明制备的钛酸盐微纳米结构涂层具有高比表面积、利于细胞粘附等优点，并极大地提高了载药性能，赋予植入体表面的药物装载、药物缓释、原位释放的能力。
Description
技术领域
本发明属于表面改性技术领域，具体涉及一种钛酸盐载药涂层的制备方法。
背景技术
钛及钛合金由于其良好的力学性能、抗腐蚀性能和优良的生物相容性，被广泛地用做骨科植入体物。但此类植入材料不具有诱导周围组织再生的能力，导致其与周围组织的结合力不足，这是目前植入体临床失效率高的一个重要原因。通过在种植体载药已成为一种常用的促进种植体生物学性能的方法，因此如何在钛或钛合金植入体表面构建载药涂层至关重要。TiO2具有良好的化学稳定性、生物相容性以及和钛合金基体结合强等优点被广泛用于钛合金种植体的表面改性。但是由于植入人体后会引发多种炎症的表达，以及对于一些特殊病症条件下如糖尿病、牙周炎患者，因其本身具有较强的炎症，细胞呈现较高的氧化应激程度，胞内ROS(活性氧)水平较正常细胞高，进而组织的愈合能力差，植入体和组织的界面结合不足，最终影响种植体植入的成功率。为了减轻植入体植入后的炎症等问题，有必要赋予种植体一定的载药性能，同时兼具良好的生物相容性，保证种植体的长期稳定性。
目前，常用的植入体表面载药涂层有二氧化钛纳米管、钙磷涂层等，较少有在种植体表面采用钛酸盐作为药物载体。钛酸盐作为一种层状结构的材料，具有大的比表面积、合适的孔径和丰富的内表面羟基官能团，可以有效地吸附和缓释药物。CN102106804A公开了以含有孔结构的纳米线构成的一种新型经皮给药制剂，制备方法如下：将TiF4的盐酸溶液和一定量的KOH加入不锈钢高压反应釜的特富龙内胆中，在一定的温度下反应一定时间，得到浅蓝色的产品，离心分离；将H2Ti3O7纳米带加入到含有十八烷基三甲基溴化铵(CTAB)和NaOH的水溶液中，上述混合物在一定的温度下反应一定的时间，然后在剧烈搅拌的条件下，加入正硅酸乙酯(TEOS)，进行反应；根据不同药物性质，进行介孔表面化学改性以增进药物的吸附和释放；增加适当的介质和辅料，形成可供使用的纳米皮肤给药制剂。
现有技术中通过钛酸盐前驱体溶液制备钛酸盐粉体，粉体材料在骨植入体的应用中，与基底材料之间的结合强度无法保证，或者是在基底材料中制备钛酸盐前躯体存在着不同材料化学性质会产生不同化学反应的技术问题。因此，开发出一种钛酸盐涂层不易从基体表面脱落且具有优异的载药性能的生物医用材料是非常有意义的。
发明内容
本发明利用等离子体喷涂技术在钛合金表面制备TiO2/CaCO3复合涂层，然后对其水热处理二次改性并载入药物，该方法制备的涂层具有微米、亚微米及纳米级别的粗糙度，有利于细胞的增殖、粘附，此外高比表面积的微纳米结构有良好的载药能力，能更好地实现植入体植入后的生物学性能增强。本发明选择氨硼烷(AB)和亚甲基蓝(MB)作为模型药物，验证材料载药与缓释能力。氨硼烷常用于储氢材料中，具有较高的储氢量，用于验证材料载药后的药物释放情况。亚甲基蓝在化学实验中，是化学试剂中常见的吸附指示剂。
本发明通过以下技术方案，经过三个步骤实现：
(1)制备复合粉末：
按照质量比为CaCO3:TiO2＝57.3:70或TiO2:CaO的质量比为70:30制备CaCO3-TiO2或CaO-TiO2喷涂原料，将复合粉体称取置于球磨罐中，按料球比为1：1.5的比例称取氧化锆球磨珠，大中小球磨珠(直径分别为5mm、3mm和1mm)的比例为1：2：4，即每50g粉体放大中小球磨珠分别为10.8g、21.4g、42.9g，共75g。加入适量无水乙醇，于行星式球磨机球磨180min，转速380r/min，直至复合粉料混合均匀。取出混合均匀的复合粉料置于80℃的干燥箱中烘干。将干燥好复合粉料研磨过80目筛，在过完筛的粉料中加入适量5％PVA溶液，充分研磨造粒，烘干后继续研磨过80目筛，最后制备出流动性好的复合粉料备用。
所述的纳米氧化钛尺寸：100nm-500nm；
(2)等离子喷涂制备涂层；
将喷涂粉体倒入送粉器中，调节设备送粉率，无水乙醇擦洗过的基体装在金属圆筒并固定于转台上，用无水乙醇对固定好的基体表面进行擦拭以去除基体表面上的油脂、浮尘等并用气枪吹干后进行喷涂实验。使用设置的等离子喷涂制备工艺参数完成涂层喷涂实验，将制备好的涂层自然冷却后从金属圆筒上取下，然后用无水乙醇超声清洗干净，去除表面灰尘，烘箱中干燥后备用。
其中，等离子喷涂技术使用的基体包括但不限于钛合金、不锈钢、碳钢或铜合金；优选为钛合金；
所述涂层的等离子喷涂制备工艺参数为：功率35～45kw；Ar流量35～45NLPM；H2流量5～12NLPM；送粉率20～40g/min；喷涂距离80～120mm。优选地，功率40kw；Ar流量40NLPM；H2流量12NLPM；送粉率30g/min；喷涂距离100mm。
(3)水热处理制备钛酸盐微纳结构涂层：
将通过步骤(2)制备的材料清洗后，放置于100mL聚四氟内衬(PTFE)水热反应釜中，加入40mL氢氧化钠溶液，经过120-180℃、6-12小时的水热反应，制备得到微纳结构涂层。
其中，所述的清洗采用无水乙醇、水浸泡涂层，进行超声波清洗，清洗至液体清澈无沉淀为止；
所述氢氧化钠溶液为氢氧化钠的水溶液；所述氢氧化钠溶液的浓度为1-5mol/L，优选为，3mol/L。所述水热反应温度优选为180℃，所述水热反应时间优选为6小时。
(4)涂层载药：
将通过步骤(3)制备的材料清洗后，置于装有模型药物溶液的容器中，浸泡加载，制备得到钛酸盐载药涂层。
所述模型药物为氨硼烷或亚甲基蓝；
所述浸泡加载时间为1小时；优选地，所述浸泡加载环境为真空干燥箱。
本发明的植入体涂层制备操作简单，易于控制，适应性广，经济效益高。
本发明的优点：
(1)利用等离子喷涂技术制备钛酸钙涂层用于装载模型药物，使其应用于植入体表面改性中。
(2)对等离子喷涂技术制备的涂层，再进行水热处理，显著增加了粗糙度，具有微米、亚微米及纳米级别的结构，有利于细胞粘附，同时这种微纳米级的表面能够成为装载药物的有效结构，实现既能促进细胞粘附又能缓慢释放药物的双功能。
(3)本发明制备的载药涂层应用于骨植入体，提高骨整合能力、降低术中/术后感染风险，采用骨骼相近杨氏模量的钛合金基底，可满足新型植入体对骨整合性和长期稳定性的要求，在骨植入体领域具有很好的应用前景。
下面结合附图说明和具体实施案例对本发明作进一步详细说明。
附图说明
图1为实施例1、3、5涂层的XRD图；
图2为实施例1涂层的表面SEM图；
图3为实施例3材料的表面SEM图；图3中，(A)1M NaOH溶液、120℃、6h；(B)1M NaOH溶液、120℃、12h；(C)1M NaOH溶液、180℃、6h；(D)1M NaOH溶液、180℃、12h；(E)3M NaOH溶液、120℃、6h；(F)3M NaOH溶液、120℃、12h；(G)3M NaOH溶液、180℃、12h；(H)5M NaOH溶液、120℃、6h；(I)5M NaOH溶液、120℃、12h；(J)5M NaOH溶液、180℃、6h；(K)5M NaOH溶液、180℃、12h；
图4为实施例3材料的表面SEM图，(A)为3M NaOH溶液、180℃、6h水热处理的TiO2/CaCO3复合涂层；(B)为钛合金；
图5为实施例5、对比例3涂层载模型药物氨硼烷后循环释放图；
图6为实施例1、3、5，对比例1、3涂层的细胞活性检测图；
图7为MB在638nm下的标准曲线(A)；不同材料对MB的载药率(B)；
图8为1-5M NaOH溶液、120-180℃、6-12h水热处理得到的TiO2/CaCO3微纳结构，即花状、片层、复合多级结构三种结构对MB的载药率；
图9为对比例6CaCO3:TiO2＝15:70得到的微纳结构的表面SEM图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
第一步：制备等离子喷涂所需要的TiO2/CaCO3复合粉末；
用天平按照质量比CaCO3:TiO2＝57.3:70称取粉末，放入洁净的陶瓷球磨罐，每个罐子放入57.3g CaCO3粉末，70g TiO2粉末。选取二氧化锆球磨珠，球料质量比为1.5:1。球磨珠按照大(10mm)中(4mm)小(2mm)的规格，以大中小质量比1:2:4的比例加入，即大球27.3g，中球54.6g，小球109.1g。无水乙醇与粉料的质量比为1:1，称量完毕后，将粉末分3次同无水乙醇一起加入球磨罐，无水乙醇与粉末和球磨珠的总体积不宜超过球磨罐的2/3～4/5，准备完毕后，将球磨罐放上行星球磨机，设置时间3h，转数380r/min。
粉末球磨3小时后，用不锈钢标准筛分离球磨珠和复合粉末，同时用酒精冲洗。将托盘铺上保鲜膜，将分离的粉料倒入，待酒精自然挥发一定时间后，再放入烘箱，设置60℃，8h。待烘干后的复合粉末继续研磨，然后过80目的标准筛。
为增强粉末的流动性，防止等离子喷涂过程中堵塞喷枪，所以需要对复合粉末再处理，加入PVA溶液以增强粉末流动性。将上述的粉末每次取20g倒入研钵，之后用胶头滴管加入5％PVA溶液，再用研磨棒搅拌，目的是使粉料与PVA溶液充分混合。建议此过程研磨的较长时间，以保证充分混合，防止实验中堵塞枪口，并且使用新球磨罐，因为新球磨罐表面粗糙，有利于复合粉末与PVA溶液混合。PVA溶液加入过少会使粉料的尺寸太小，过多反而会降低粉料的流动性，所以5％PVA溶液与粉料应该控制在质量比1:4左右。混合完毕后放入烘箱烘干，设置温度为80℃，时间8h。然后取出，继续研磨过80目筛，就是最终喷涂用的等离子喷涂粉。
第二步：喷涂前对基体进行预处理，包括超声清洗、烘干、表面喷砂；
本次喷涂所使用的基体是Ti-6Al-4V钛合金(本发明所述的基体包括但不限于#45钢、不锈钢、钛合金和铜合金等)。准备了规格为15mm×15mm×0.5mm的Ti-6Al-4V钛合金基体。在喷涂前，对基体进行预处理，首先对基体除油去污，将基体用超声波清洗，清洗介质为无水乙醇，之后烘干。将基材工装到喷涂所使用的夹具上，准备喷涂。
第三步：涂层的制备；
等离子喷涂：喷涂功率40kw；Ar流量40NLPM；H2流量12NLPM；送粉率30g/min；喷涂距离100mm。
喷涂结束后可能会出现一些粉末没有融化残留在基材表面或者高温被氧化形成杂质附着在基材表面，这些因素在之后的表征过程中带来误差，所以须对表面进行再清洗。将喷涂好的喷涂片装在烧杯中放入超声波清洗机中进行清洗，清洗的介质仍为无水乙醇，最后一遍用去离子水进行清洗，之后自然晾干。得到清洁的涂层片后对涂层进行表征。
实施例2
涂层形貌的观察：
对实施例1涂层喷金后，采用场发射扫描电镜(FE-SEM，德国ZEISS，SUPRA55)观察涂层的表面形貌，喷涂后的表面形貌如图2所示，从图中可知，形成的涂层具有表面微纳米结构。
实施例3
水热处理制备TiO2/CaCO3微纳结构涂层：
将实施例1涂层放置于100mL聚四氟内衬(PTFE)水热反应釜中，加入40mL1-5mol/L氢氧化钠溶液，烘箱温度为120-180℃，经过6-12小时的水热反应，制备得到TiO2/CaCO3微纳结构涂层。
实施例4
水热处理后样品形貌的观察：
对实施例3样品喷金后，采用场发射扫描电镜(FE-SEM，德国ZEISS，SUPRA55)观察水热处理后涂层的表面形貌，表面形貌如图3所示，从图中可知，TiO2/CaCO3微纳结构涂层形成的表面具有二级微纳米结构，针状结构(如图3A)、花状结构(如图3B)、立方体结构(如图3F)、片层结构(如图3J)，还有多种结构并存的复合多级微纳结构(如图3G、图4A)。
实施例5
涂层中加载氨硼烷(AB)：
3M NaOH溶液、180℃、6h水热处理的TiO2/CaCO3微纳结构涂层置于装有1mol/L氨硼烷溶液的容器中，再将容器放入真空干燥箱中浸泡12小时加载。清洗去除游离的氨硼烷，采用富氢水测试笔(ENH-2000，日本RUSTLEX)测试样品在超纯水中的氢气释放量，每24小时进行记录释放量的数值以及进行换液，如图5所示，制备的载AB后TiO2/CaCO3微纳结构涂层可循环释放氢气。
实施例6
细胞增殖实验：
将实例1、3(3M NaOH溶液、180℃、6h水热处理的)制备的材料清洗后，75％酒精浸泡30分钟灭菌后，在无菌环境中材料置于24孔板，无菌PBS缓冲溶液冲洗3遍，在材料上以2×104cell/孔的密度接种小鼠骨髓间充质干细胞(BMSC)，在37℃、5％CO2培养箱中分别培养1，3，5和7d后，用CCK-8来测量吸光度值，评价细胞在不同材料上的增殖情况。细胞增殖如图6所示。从图中可知，随着培养时间的延长，TiO2/CaCO3微纳结构涂层和载AB后TiO2/CaCO3微纳结构涂层能促进BMSC细胞的增殖。
其中，所述细胞增殖实验保证了材料接种细胞，细胞培养均在无菌环境中完成。
所述细胞增殖实验每组均为3个平行样对照。
实施例7
亚甲基蓝(MB)吸附测试：
将实施例1、3(3M NaOH溶液、180℃、6h水热处理的)制备的材料清洗后，浸泡于30mg/L亚甲基蓝溶液在黑暗环境中每十分钟取液测试一次。使用酶标仪96孔板638nm下测试得到亚甲基蓝溶液折光率的下降，从而推算载药能力。如图7所示。
其中，所述的推算载药能力是通过MB的标准曲线测算。
实施例8
将实施例3制备的不同结构的TiO2/CaCO3微纳结构涂层，浸泡于30mg/L亚甲基蓝溶液在黑暗环境中每十分钟取液测试一次。使用酶标仪96孔板638nm下测试得到亚甲基蓝溶液折光率的下降，从而推算载药能力。如图8所示，相同条件下，不同的结构中，复合多级微纳结构具有更优的载药效率。
对比例1
未经过等离子喷涂技术的钛合金基底，常规混酸腐蚀去除氧化层后，放置于100mL聚四氟内衬(PTFE)水热反应釜中，加入40mL 3mol/L氢氧化钠溶液，烘箱温度为180℃，经过6小时的水热反应，制备得到水热处理后钛合金基底。
对比例2
对对比例1样品喷金后，采用场发射扫描电镜(FE-SEM，德国ZEISS，SUPRA55)观察水热处理后样品的表面形貌，与实施例3中同一水热条件(3M NaOH溶液、180℃、6h水热处理的)的表面形貌进行对比。
TiO2/CaCO3微纳结构涂层具有复合多级微纳结构(如图4A)。没有TiO2/CaCO3复合涂层的钛合金基底，经过同样的水热处理，显示出明显的结构差异，钛合金基底仅形成单一的花状结构(如图4B)。
对比例3
水热处理后钛合金基底置于装有氨硼烷溶液的容器中，再将容器放入真空干燥箱中浸泡12小时加载。制备得到水热处理钛合金基底载AB。清洗去除游离的氨硼烷，采用富氢水测试笔(ENH-2000，日本RUSTLEX)测试其在超纯水中的氢气释放量，每24小时进行记录释放量的数值以及进行换液，如图5所示，制备的载AB后钛合金基底释放的氢气量和循环释放天数均不如TiO2/CaCO3微纳结构涂层。
对比例4
将对比例1、3制备的材料清洗后，75％酒精浸泡30分钟灭菌后，在无菌环境中材料置于24孔板，无菌PBS缓冲溶液冲洗3遍，在材料上以2×104cell/孔的密度接种小鼠骨髓间充质干细胞(BMSC)，在37℃、5％CO2培养箱中分别培养1，3，5和7d后，用CCK-8来测量吸光度值，评价细胞在不同材料上的增殖情况。细胞增殖如图6所示。细胞在对比例材料上的生物活性明显不如实施例材料。
其中，所述细胞增殖实验保证了材料接种细胞，细胞培养均在无菌环境中完成。
所述细胞增殖实验每组均为3个平行样对照。
对比例5
将对比例1制备的材料清洗后，浸泡于30mg/L亚甲基蓝溶液在黑暗环境中每十分钟取液测试一次。使用酶标仪96孔板638nm下测试得到亚甲基蓝溶液折光率的下降，从而推算载药能力。所述的推算载药能力是通过MB的标准曲线测算。
如图7B所示，同等条件下，水热处理后的钛酸钙涂层优于同样处理后的钛合金基体的载药率。
对比例6
用天平按照质量比CaCO3:TiO2＝15:70称取粉末，按照实施例1的方法制备涂层，并水热处理(3M NaOH溶液、180℃、6h)制备TiO2/CaCO3结构涂层，涂层形貌见图9。碳酸钙太少，无法形成特殊形貌结构，相对平整。如果碳酸钙过多则或导致涂层不坚固。
以上所述仅为本发明的较佳实施案例而已，并不用以限制本发明，凡是在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.钛酸盐载药涂层，其特征在于，所述载药涂层的制备方法步骤如下：
(1)制备适合等离子喷涂的纳米氧化钛和碳酸钙或氧化钙复合粉末；
(2)采用等离子喷涂技术在基体上喷涂复合粉末，制备钛酸盐涂层；
所述的等离子喷涂制备钛酸盐涂层的工艺参数：功率35～45kw；Ar流量35～45NLPM；H2流量5～12NLPM；送粉率20～40g/min；喷涂距离80～120mm；
(3)水热处理实现具有微纳结构钛酸盐涂层的制备；
所述的水热处理是将等离子喷涂技术制备得到的涂层清洗后，与氢氧化钠溶液进行水热反应；
(4)将通过步骤(3)制备的涂层清洗后，置于装有模型药物溶液的容器中，浸泡加载，制备得到钛酸盐载药涂层；
所述模型药物为氨硼烷或亚甲基蓝；所述浸泡加载为真空干燥箱浸泡1小时。
2.如权利要求1所述的钛酸盐载药涂层，其特征在于：步骤(1)所述的纳米氧化钛尺寸：100nm-500nm；纳米氧化钛和碳酸钙的质量比为70:57 .3，纳米氧化钛和氧化钙的质量比为70:30。
3.如权利要求1所述的钛酸盐载药涂层，其特征在于：步骤(2)所述的等离子喷涂技术使用的基体包括但不限于钛合金、不锈钢、碳钢或铜合金。
4.如权利要求1所述的钛酸盐载药涂层，其特征在于：步骤(2)所述的等离子喷涂技术使用的基体为Ti6Al4V钛合金；所述的等离子喷涂制备钛酸盐涂层的工艺参数：功率40kw；Ar流量40NLPM；H2流量12NLPM；送粉率30g/min；喷涂距离100mm。
5.如权利要求1所述的钛酸盐载药涂层，其特征在于：所述的清洗采用无水 乙醇、水浸泡涂层，进行超声波清洗；所述的氢氧化钠溶液浓度为：0 .1-10mol/L，水热反应温度100-230℃，水热反应时间6-12h。
6.如权利要求5所述的钛酸盐载药涂层的制备方法，其特征在于：所述的氢氧化钠溶液浓度为：3mol/L，水热反应温度180℃，水热反应时间6h。
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