CN111973812B - 可降解镁基骨内植物表面具有生物活性、分级结构的羟基磷灰石涂层及制备方法 - Google Patents
可降解镁基骨内植物表面具有生物活性、分级结构的羟基磷灰石涂层及制备方法 Download PDFInfo
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Abstract
本发明提供了一种可降解镁基骨内植物表面具有生物活性、分级结构的羟基磷灰石涂层及制备方法,所述涂层包括内层氟化膜和外层羟基磷灰石转化涂层。该方法通过先对镁及镁合金进行氢氟酸浸泡生成化学转化膜MgF2,之后置于含磷酸钙盐溶液浸泡,化学沉积法生成透钙磷石涂层;最后使用水热转化法,高温加压下将透钙磷石涂层原位转化为较厚的、具有微纳分级结构的复合表面形貌的羟基磷灰石涂层。该涂层与镁及镁合金基体结合强度高,同时显著改善了镁基体的耐腐蚀性和生物活性。制备方法简便易行,成本低廉,并可适用于任意复杂形状的镁基骨内植物器件。
Description
技术领域
本发明属于生物医用材料技术领域,涉及一种具有生物活性的涂层及其制备方法,具体为一种可降解镁基骨内植物表面具有生物活性、分级结构的羟基磷灰石涂层及其制备方法。
背景技术
医用镁合金材料及其骨植入器械因具有良好的生物相容性、强韧性和体内可降解性,被誉为“革命性的金属生物材料”,是近10年来全球各主要国家竞相发展的生物材料领域。这类新型医用金属材料巧妙地利用镁合金在人体环境中易发生腐蚀降解的特性,来实现金属植入物在体内逐渐降解直至消失的医学临床目的。
目前常见的用于临床的骨植入材料多为不可降解的不锈钢、钛合金、钴基合金材料,植入后作为异物长期留存在体内,会不同程度地刺激周边肌体组织。患者在病愈后通常需经二次手术将金属植入物取出,这又会给患者带来了更多的痛苦和经济负担。与以上几种传统骨修复用植入材料相比,镁合金具有如下优势:1)可降解性。镁合金具有较低的腐蚀电位,在含有氯离子的体内环境下易发生腐蚀,并以缓慢腐蚀的方式在体内完全降解。2)生物安全性高。Mg作为人体必需的营养元素,参与体内几乎所有能量代谢,对神经运动机能、生理机能及预防循环系统疾病和缺血性心脏病均有重要作用。过量的镁会通过泌尿系统代谢分解后排出体外,具有良好的生物安全性。3)生物力学相容性好。镁是目前所有金属材料中生物力学性能与人体骨最接近的金属材料,可有效缓解传统医用金属材料临床上的“应力遮挡”效应。4)成本低。
但目前镁及镁合金应用到临床上作为骨科内植入物材料尚存在一些问题,镁的标准电极电位低,在体内降解速率过快,在组织修复再生恢复功能前难以保持足够的力学强度。镁及镁合金释放出的镁离子可以刺激骨膜中的感觉神经末端释放更多的神经递质,进一步促进骨膜内干细胞的成骨分化,但是镁合金的初期降解速度过快导致局部镁离子过量释放,这不仅会引起氢气聚集,还会影响周围成骨细胞粘附和增殖。表面改性是一种行之有效的技术手段,其中生物活性钙-磷涂层拥有与骨组织相近的成分,可提高骨内植物的耐蚀性和生物相容性。目前报道常用于镁基材料表面改性的钙-磷涂层是一种透钙磷石(DCPD),与其他钙磷涂层相比,DCPD最易在镁及镁合金上沉积。但其溶解产物呈弱酸性,易在人体组织中引发炎症反应。申请人前期申请公开的专利(申请号为201110086203.3)中曾对镁及镁合金植入材料进行表面改性,构筑透钙磷石(CaHPO4·H2O)涂层,降低环境对镁及镁合金基材的腐蚀和降解速率,并且提高植入物的生物相容性。尽管透钙磷石涂层对镁及镁合金材料的抗腐蚀降解性能有所改善,但尚不能满足不同类型、不同结构形状等各种可降解镁基骨内植入物器械的多种要求,尤其是对于比表面积大、镁基体降解较快的多孔类植入器件,透钙磷石涂层延缓镁基体降解速率还不能满足临床使用要求。
羟基磷灰石是另一类常见骨内植物生物材料及涂层材料。其结晶性好,与骨成分最为接近,能够提高骨整合能力,加速骨组织愈合作用。并且其溶解度在各类钙-磷涂层中最低,降解产物微碱性,有利于从腐蚀化学反应平衡角度进一步抑制镁基体降解。目前常用化学沉积、电沉积、溶胶凝胶法等在镁合金表面制备羟基磷灰石涂层。然而,大多存在制备工艺复杂,厚度较低或涂层结构不致密,结合强度不足等技术问题。专利CN106544714B公开了一种Mg-Zn-Ca镁合金骨螺钉表面涂层的制备方法,将材料微弧电泳处理后再进行水热合成处理,制备羟基磷灰石涂层。存在的问题在于微弧电泳涂层表面存在大量的微孔和裂纹,为腐蚀介质的渗入提供了离子通道,直接影响膜层对镁基体腐蚀降解的保护性能,同时水热处理封孔的制备温度为90-150℃高温条件,易因为类似时效处理的原因导致镁合金基体本身力学特性的改变,从而最终影响器件植入后的功效。专利CN103484845B公开一种ZK60镁合金钙磷涂层复合材料,使用水热法一步合成钙磷涂层。但存在问题和不足是:1)这一方法使用的钙源为Ca(NO3)2,体系中没有络合剂存在,不易调节溶液pH值;2)水热温度(100-200℃)过高易影响金属基体力学性能;3)由于羟基磷灰石不易直接在镁及镁合金表面形核沉积,因此涂层厚度、覆盖率和界面结合强度会有明显欠缺;4)涂层表面无法形成具有更高生物活性的微纳尺度分级结构的复合形貌。
发明内容
本发明针对现有技术存在的不足,提供了一种用于可降解镁合金内植物表层的生物活性、分级结构羟基磷灰石涂层及其制备方法。涂层组成为内层氟化膜和外层较厚的羟基磷灰石转化涂层。制备方法具体是先在氟化的镁及镁合金表面通过化学反应沉积法制备透钙磷石涂层,然后进一步采用水热法将透钙磷石前驱体涂层在碱性环境下转化为羟基磷灰石涂层。本发明解决了目前透钙磷石涂层提高镁及镁合金材料,尤其是高比较面积器件抗腐蚀能力不足并且降解产物呈弱酸性易致炎症的问题,也解决了在镁及镁合金表面直接沉积羟基磷灰石涂层结合强度差、涂层厚度较薄或不致密、抗腐蚀保护效果不足的问题。该发明工艺简便易行,不需特殊大型设备,制备的羟基磷灰石涂层覆盖完整,与基体结合力强,HA沉积颗粒细小,涂层粗糙度小,厚度可控。
本发明的目的是通过以下技术方案实现的:
本发明提供了一种可降解镁及镁合金骨内植物的羟基磷灰石涂层,包括内层氟化膜和外层羟基磷灰石转化涂层。所述羟基磷灰石涂层为表面具有生物活性、分级结构的羟基磷灰石涂层。
优选地,所述氟化膜厚度为150nm-3μm,所述羟基磷灰石转化涂层厚度为10μm-100μm,表面具有微纳尺度复合的粗糙形貌;
所述羟基磷灰石转化涂层与氟化膜的结合力在30MPa以上,所述羟基磷灰石转化涂层Ca/P原子比为1.5-1.67。所得涂层的成骨细胞毒性在0-1级。若Ca/P过低,会生成缺钙型HA,在体外实验中,会优先吸收培养基中的Ca离子补足涂层中的空位,对细胞造成不利影响;若Ca/P过高,溶液浓度过高导致的沉降现象会使涂层不均匀。
本发明还提供了一种可降解镁及镁合金骨内植物的羟基磷灰石涂层的制备方法,包括如下步骤:
S1:将镁及镁合金骨内植物置于氢氟酸溶液中恒温浸泡,在镁及镁合金骨内植物表面形成氟化膜;
S2:将步骤S1处理后的镁及镁合金骨内植物转至含磷酸钙盐的溶液中恒温浸泡,在镁及镁合金骨内植物的氟化膜表面形成生物活性透钙磷石涂层;
S3:将步骤S2处理后的镁及镁合金骨内植物进行高温高压浸泡反应,浸泡溶液为Ca-EDTA、磷酸盐和无机碱的混合溶液,将S2所述的生物活性透钙磷石涂层转化为羟基磷灰石涂层。Ca-EDTA(乙二胺四乙酸二钠钙)是钙的螯合物,可以在碱性水溶液环境中提供足够高的钙离子浓度,防止碱性环境下溶液优先生成Ca(OH)2沉淀,并且减弱镁离子进入羟基磷灰石晶格的现象。
优选地,步骤S1中所述氢氟酸溶液的浓度为20%-40%,浸泡温度为10-30℃,浸泡时间为6h-48h。
优选地,步骤S2中所述含磷酸钙盐的溶液包括NaNO3、磷酸钙盐和H2O2,其中所述磷酸钙盐选自磷酸钙、磷酸一氢钙和磷酸二氢钙中的至少一种。
优选地,所述NaNO3、磷酸钙盐和H2O2的质量比为4-7:3-4:1-2。
优选地,步骤S2中所述恒温浸泡的温度为室温,浸泡时间为6-36h。
优选地,步骤S3中所述的磷酸盐选自磷酸钠、磷酸二氢钠和磷酸氢二钠中至少一种;
所述无机碱选自氢氧化钠、氢氧化钾和氨水中至少一种;
所述Ca-EDTA与磷酸盐的物质的量比值为1-2:1,浸泡溶液的pH为6-11;浸泡溶液的pH过高会导致原偏酸性的透钙磷石涂层溶解过快,羟基磷灰石涂层无法生成;pH过低会抑制羟基磷灰石形核生长,生成磷酸八钙第二相甚至导致涂层无法生成。
所述反应温度在50-90℃,反应压力12KPa-100KPa,反应时间为6h-48h。
优选地,所述镁为纯镁,所述镁合金为Mg-Zn系、Mg-Ca系、Mg-Mn系或Mg-Re系等未经任何处理的裸金属镁合金系列。
本发明通过先对镁及镁合金进行氢氟酸浸泡生成化学转化膜MgF2,之后置于含磷酸钙盐溶液浸泡,化学沉积法生成透钙磷石涂层;最后使用水热转化法,高温加压下将透钙磷石涂层原位转化为较厚的、具有微纳复合表面形貌的羟基磷灰石涂层。该涂层与镁及镁合金基体结合强度高,同时显著改善了镁基体的耐腐蚀性和生物活性。制备方法简便易行,成本低廉,并可适用于任意复杂形状的镁基骨内植物器件。
与现有技术相比,本发明具有如下有益效果:
(1)该双层涂层中内层化学转化MgF2膜具有保护基体的作用,可降低其腐蚀速率,同时调控之后透钙磷石涂层的形核和生长。
(2)该双层涂层中外表面的羟基磷灰石涂层由透钙磷石涂层水热转化而得,既具备了透钙磷石易于在镁及镁合金上沉积从而形成结合强度优异、较厚涂层的优势;又具有致密羟基磷灰石涂层显著降低镁及镁合金腐蚀速率的功能;此外,生成的表面微纳分级结构的复合形貌具有更高的生物活性。
(3)本发明得到的涂层具备良好的细胞相容性和生物活性,有利于成骨细胞和骨髓间充质干细胞的粘附增殖和新骨的生成。
(4)本发明工艺流程简便、易于操作,无需大型设备,成本较低。
(5)本发明适用范围广,适用于目前所有镁及镁合金材料及任意复杂形状的骨内植物等硬组织类修复植入器件。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为实施例1制备的镁合金表面生物活性羟基磷灰石涂层的扫描电镜图,右上角为放大图;图中显示涂层表面具有微米尺度的板状形貌复合纳米尺度的针状形貌;
图2为实施例2制备的镁合金表面生物活性羟基磷灰石涂层的XRD衍射图谱;
图3为实施例3制备的镁合金多孔骨组织工程支架孔内羟基磷灰石涂层的扫描电镜图;
图4为实施例1制备的覆盖透钙磷石DCPD涂层和覆盖羟基磷灰石涂层的镁及镁合金在细胞培养液中的Mg离子释放曲线对比;结果表明,在14天内,覆盖本发明技术制备的羟基磷灰石涂层的镁及镁合金其降解释放的Mg离子浓度是透钙磷石涂层的约50%,即降解速率降低了一半;
图5为实施例1、对比例1、对比例2制备的镁合金表面生物活性羟基磷灰石涂层宏观光学照片;其中图5a为实施例1制备的涂层;图5b为对比例1制备的涂层;图5c为对比例2制备的涂层。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变化和改进。这些都属于本发明的保护范围。
实施例1
在Mg-Nd-Zn-Zr合金骨钉表面制备具有生物活性的羟基磷灰石涂层。具体步骤如下:
1)首先将Mg-Nd-Zn-Zr合金制成Φ14×3mm试样,依次用320#,1200#,3000#水砂纸打磨,无水乙醇超声清洗5min×2次,吹干。
2)将样品置于40%氢氟酸中在30℃下浸泡6h,同时使用摇床震荡。去离子水和无水乙醇依次清洗,吹干。
3)氟化后的样品在NaNO3:Ca(H2PO4)2:H2O2=4:3:1(wt%)的钙磷溶液中室温静置浸泡6h。制得前驱体透钙磷石DCPD涂层。
4)配制水热反应液:取Ca-EDTA:NaH2PO4=1:1(物质的量比值),加入去离子水溶解,再加入1mol/L NaOH溶液调节pH=9。将上述覆盖有DCPD涂层的氟化后的Mg-Nd-Zn-Zr合金浸泡于水热釜内的水热反应液中,调节温度至90℃,反应12h。反应结束后,取出降温,用超纯水和酒精依次清洗后吹干,干燥保存。
扫描电镜(如图1所示)观察到羟基磷灰石涂层总厚度约为11-25μm(其中氟化膜涂层厚度约为1μm),Ca/P原子比约为1.5:1,HA粒径约为10μm,涂层与氟化膜结合力超过30MPa。本实施例制备的羟基磷灰石涂层在α-MEM培养液中浸泡14d的Mg离子释放较步骤1)-3)的方法制得的DCPD涂层低1/2(图4)。采用MC3T3-E1成骨细胞评价本实施例制备的羟基磷灰石涂层的生物相容性,结果显示在羟基磷灰石涂层表面粘附有大量铺展的成骨细胞,说明羟基磷灰石涂层对成骨细胞的铺展、粘附和增殖具有促进作用。本实施例制备的镁合金表面生物活性羟基磷灰石涂层宏观光学照片如图5a所示。
实施例2
在ZK60(Mg-Zn系)合金骨板表面制备具有生物活性的羟基磷灰石涂层。具体步骤如下:
1)首先将ZK60合金制成Φ14×3mm试样,依次用320#,1200#,3000#水砂纸打磨,无水乙醇超声清洗5min×2次,吹干。
2)将样品置于30%氢氟酸中在20℃下浸泡12h,同时使用摇床震荡。去离子水和无水乙醇依次清洗,吹干。
3)氟化后的样品在NaNO3:Ca3(PO4)2:H2O2=7:3:2(wt%)的钙磷溶液中室温静置浸泡36h。制得前驱体透钙磷石DCPD涂层。
4)配制水热反应液:取Ca-EDTA:Na2HPO4=1.67:1(物质的量比值),加入去离子水溶解,再加入1mol/L NaOH溶液调节pH=6.5。将上述覆盖有DCPD涂层的氟化后的ZK60合金浸泡于水热釜内的溶液中,调节温度至90℃,反应6h。反应结束后,取出降温,用超纯水和酒精依次清洗后吹干,干燥保存。
扫描电镜观察到羟基磷灰石涂层总厚度约为25-40μm(其中氟化膜涂层厚度约为150nm),Ca/P原子比约为1.6:1,HA粒径约为5μm,涂层与氟化膜结合力超过32MPa,本实施例制备的羟基磷灰石涂层在α-MEM培养液中浸泡14d的Mg离子释放较步骤1)-3)的方法制得的DCPD涂层低1/2。本实施例制备的镁合金表面生物活性羟基磷灰石涂层的XRD衍射图谱如图2所示。采用MC3T3-E1成骨细胞评价本实施例制备的羟基磷灰石涂层的生物相容性和活性,使用涂层浸提液培养成骨细胞,存活率可达90%以上。细胞毒性在0-1级,满足体内植物的基本要求。
实施例3
在组织工程用纯镁多孔骨组织工程支架表面制备具有生物活性的羟基磷灰石涂层。具体步骤如下:
1)首先将多孔纯镁制成Φ10×2mm试样,丙酮和无水乙醇分别超声清洗5min,吹干。
2)将样品置于20%氢氟酸中在10℃下浸泡48h,同时使用摇床震荡。去离子水和无水乙醇依次清洗,吹干。
3)氟化后的样品在NaNO3:Ca3(PO4)2:CaHPO4:H2O2=5:2:1:1(wt%)的钙磷溶液中室温静置浸泡36h。制得多孔纯镁表面透钙磷石DCPD涂层。
4)配制水热反应液:取Ca-EDTA:Na3PO4=2:1(物质的量比值),加入去离子水溶解,再加入1mol/L NaOH溶液调节pH=8.5。将上述覆盖有DCPD涂层的氟化后的多孔纯镁浸泡于水热釜内的溶液中,调节温度至70℃,反应24h。反应结束后,取出降温,用超纯水和酒精依次清洗后吹干,干燥保存。
扫描电镜(如图3所示)观察到羟基磷灰石涂层总厚度约为50μm(其中氟化膜涂层厚度约为2μm),Ca/P原子比约为1.67:1,涂层在多孔内分布均匀。采用骨髓间充质干细胞评价本实施例制备的羟基磷灰石涂层的生物相容性和活性,涂层浸提液培养细胞存活率可达95%以上。细胞毒性在0-1级,满足体内植物的基本要求。培养一周后细胞ALP表达比步骤1)-3)的方法制得的DCPD涂层对照组高约3倍。
实施例4
在组织工程用WE43(Mg-Re系)合金多孔骨组织工程支架表面制备具有生物活性的羟基磷灰石涂层。具体步骤如下:
1)首先将多孔WE43合金制成Φ10×2mm试样,丙酮和无水乙醇分别超声清洗5min,吹干。
2)将样品置于30%氢氟酸中在20℃下浸泡18h,同时使用摇床震荡。去离子水和无水乙醇依次清洗,吹干。
3)氟化后的样品在NaNO3:Ca(H2PO4)2:CaHPO4:H2O2=4:1:3:1(wt%)的钙磷溶液中室温静置浸泡18h。制得多孔AZ31合金表面透钙磷石DCPD涂层。
4)配制水热反应液:取Ca-EDTA:Na2HPO4:NaH2PO4=2:1:1(物质的量比值),加入去离子水溶解,再加入1mol/L NaOH溶液调节pH=10。将上述覆盖有DCPD涂层的氟化后的多孔AZ31合金浸泡于水热釜内的溶液中,调节温度至80℃,反应48h。反应结束后,取出降温,用超纯水和酒精依次清洗后吹干,干燥保存。
扫描电镜观察到羟基磷灰石涂层总厚度约为100μm(其中氟化膜涂层厚度约为3μm),Ca/P原子比约为1.55:1,涂层在多孔内分布均匀。动物体内植入实验发现两周内即有大量新生骨形成,骨密度、骨体积等参数都较步骤1)-3)的方法制得的DCPD涂层对照组有明显提高。
对比例1
本对比例与实施例1的方法基本相同。不同之处仅在于:本对比例不进行氢氟酸浸泡和磷酸钙盐溶液浸泡步骤,直接将打磨完毕的Mg-Nd-Zn-Zr合金裸金属置于反应釜中进行水热反应。所得材料外观呈黑色,观察无钙磷涂层生成。本对比例制备的镁合金表面生物活性羟基磷灰石涂层宏观光学照片如图5b所示。
对比例2
本对比例与实施例1的方法基本相同。不同之处仅在于:本对比例不进行磷酸钙盐溶液浸泡步骤,直接将表面有氟化膜的Mg-Nd-Zn-Zr合金置于反应釜中进行水热反应。所得材料外观呈黄褐色,观察几乎无钙磷涂层生成。本对比例制备的镁合金表面生物活性羟基磷灰石涂层宏观光学照片如图5c所示。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变化或修改,这并不影响本发明的实质内容。在不冲突的情况下,本申请的实施例和实施例中的特征可以任意相互组合。
Claims (6)
1.一种可降解镁或镁合金骨内植物的羟基磷灰石涂层,其特征在于,包括内层氟化膜和外层羟基磷灰石转化涂层;
所述氟化膜厚度为150nm-3μm,所述羟基磷灰石转化涂层厚度为10μm-100μm,表面具有微纳尺度分级结构复合的粗糙形貌;
所述羟基磷灰石转化涂层与氟化膜的结合力在30 MPa以上,所述羟基磷灰石转化涂层Ca/P原子比为1.5-1.67;
所述羟基磷灰石涂层的制备方法,包括如下步骤:
S1: 将镁或镁合金骨内植物置于氢氟酸溶液中恒温浸泡,在镁或镁合金骨内植物表面形成氟化膜;
S2: 将步骤S1处理后的镁或镁合金骨内植物转至含磷酸钙盐的溶液中恒温浸泡,在镁或镁合金骨内植物的氟化膜表面形成生物活性透钙磷石涂层;
S3: 将步骤S2处理后的镁或镁合金骨内植物进行高温高压浸泡反应,浸泡溶液为Ca-EDTA、磷酸盐和无机碱的混合溶液,将S2所述的生物活性透钙磷石涂层转化为羟基磷灰石涂层;
浸泡溶液的pH为6-11;
所述反应温度在50-90℃,反应压力12KPa-100KPa,反应时间为6h-48h。
2.如权利要求1所述的羟基磷灰石涂层,其特征在于,步骤S1中所述氢氟酸溶液的浓度为20%-40%,浸泡温度为10-30℃,浸泡时间为6h-48h。
3.如权利要求1所述的羟基磷灰石涂层,其特征在于,步骤S2中所述含磷酸钙盐的溶液包括NaNO3、磷酸钙盐和H2O2,其中所述磷酸钙盐选自磷酸钙、磷酸一氢钙和磷酸二氢钙中的至少一种。
4.如权利要求3所述的羟基磷灰石涂层,其特征在于,所述NaNO3、磷酸钙盐和H2O2的质量比为4-7:3-4:1-2。
5.如权利要求3所述的羟基磷灰石涂层,其特征在于,步骤S2中所述恒温浸泡的温度为室温,浸泡时间为6-36h。
6.如权利要求3所述的羟基磷灰石涂层,其特征在于,步骤S3中所述的磷酸盐选自磷酸钠、磷酸二氢钠和磷酸氢二钠中至少一种;
所述无机碱选自氢氧化钠、氢氧化钾和氨水中至少一种;
所述Ca-EDTA与磷酸盐的物质的量比值为1-2:1。
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