CN106282975B - 在镁合金表面制备的羟基磷灰石超疏水膜层及方法与应用 - Google Patents
在镁合金表面制备的羟基磷灰石超疏水膜层及方法与应用 Download PDFInfo
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Abstract
本发明属于金属材料表面处理技术领域,公开了在镁合金表面制备的羟基磷灰石超疏水膜层及方法与应用。所述方法为(1)预处理:将镁合金进行表面预处理;(2)混合溶液的配制:采用乙醇和水将乙酸钙、磷酸二氢钠和脂肪酸配制成溶液,得到混合溶液;(3)将镁合金与混合溶液同时置于水热反应釜中,在100~230℃下反应1~3h,得到羟基磷灰石超疏水膜层。本发明在镁合金表面水热法一步制备羟基磷灰石超疏水膜层,该方法简单;超疏水表面羟基磷灰石分布均匀,能显著提高镁合金的耐腐蚀性能;该膜层用于医用镁合金领域。
Description
技术领域
本发明属于金属材料表面处理技术领域,涉及一种在镁合金表面制备羟基磷灰石超疏水膜层的方法以及采用该方法制备得到的羟基磷灰石超疏水膜层和该膜层的应用。
背景技术
近年来,随着人们生活质量的提高,生物医疗器械的需求逐年增加。镁及其合金作为一种新型的生物可降解材料,由于其良好的组织相容性,无毒副作用,与人体骨骼相近的密度、弹性模量和良好的力学性能,受到了企业和研究者的广泛关注。然而,镁标准电极电位(-2.37V)较低,腐蚀速率过快。这会导致镁合金植入材料在组织尚未完全愈合前就已被严重腐蚀而失去支撑作用,进而影响机体生理功能。
针对镁合金耐腐蚀性能差的问题,科研工作者们展开了大量的研究,其中在镁合金表面制备一层耐腐蚀性能优异的防护膜层是最快捷和实用的方法。镁合金表面的防腐蚀膜层能有效防止基体镁合金的腐蚀,使其在材料植入人体的初期保持完整的几何结构和力学性能。在众多防腐蚀膜层中,羟基磷灰石膜层由于其优异的生物相容性和骨传导性而备受关注。例如专利号为ZL201410118521.7、名称为“一种直接制备含有羟基磷灰石的微弧氧化陶瓷膜的方法”的专利中公开了一种采用微弧氧化工艺制备羟基磷灰石膜层的方法。Dunne等(C.F.Dunne,G.K.Levy,O.Hakimi,E.Aghion,B.Twomey,K.T.Stanton.Corrosionbehaviour of biodegradable magnesium alloys with hydroxyapatite coatings[J].Surface&Coatings Technology,2016,289:37–44)采用爆炸喷涂技术在不同镁合金表面制备羟基磷灰石膜层,其耐腐蚀性能较未喷镀镁合金提高了1倍。虽然经表面羟基磷灰石处理后的镁合金耐腐蚀性能普遍升高,但由于表面致密性和钙磷膜层性能的影响,仍然不能满足生物医用植入材料对腐蚀性能的要求。
自然界中以荷叶为代表的超疏水表面由于不沾水、自清洁等众多独特的功能引起了广大学者的极大兴趣。在镁合金表面制备不沾水的超疏水表面能有效地阻碍水及水溶液在固体表面的润湿面积,使镁合金表面的腐蚀速率大大降低。因此在镁合金表面制备羟基磷灰石超疏水膜层能在获得羟基磷灰石高生物相容性的基础上,显著提高镁合金耐腐蚀性能,达到生物医用植入材料的腐蚀要求。
发明内容
为了解决现有技术中制备羟基磷灰石超疏水膜层制备工艺复杂和设备要求高的问题,同时为了提高镁合金耐腐蚀性能,本发明的首要目的在于提供一种在镁合金表面制备羟基磷灰石超疏水膜层的方法,该法为一步水热法。利用该方法对镁合金表面处理后,得到的镁合金具备超疏水性能,且耐腐蚀性能优异,可作为生物医用植入镁合金表面的处理技术。
本发明的另一目的在于提供上述方法制备得到的羟基磷灰石超疏水膜层。
本发明的再一目的在于提供上述羟基磷灰石超疏水膜层的应用。所述羟基磷灰石超疏水膜层应用于医用镁合金。
本发明目的通过以下技术方案实现:
一种在镁合金表面制备羟基磷灰石超疏水膜层的方法,包括如下步骤:
(1)预处理:将镁合金进行表面预处理
(2)混合溶液的配制:采用乙醇和水将乙酸钙、磷酸二氢钠和脂肪酸配制成溶液,得到混合溶液;所述脂肪酸为硬脂酸或十四酸中的一种以上;
(3)将镁合金与混合溶液同时置于水热反应釜中,在100~230℃下反应1~3h,得到羟基磷灰石超疏水膜层即在镁合金表面获得具有超疏水特性的羟基磷灰石表面膜层。
所述混合溶液中乙酸钙的浓度为0.01~0.05mol/L;磷酸二氢钠的浓度为0.005~0.03mol/L,脂肪酸的浓度为0.01~0.05mol/L。
所述混合溶液中乙醇和水的体积比为3:7~7:3。
所述混合溶液的具体配制步骤为:将乙酸钙和磷酸二氢钠溶于水中,调节pH至溶液澄清(pH为4~5),得到含钙磷的水溶液;将脂肪酸溶于乙醇中,得到脂肪酸的乙醇溶液;将脂肪酸的乙醇溶液缓慢倒入含钙磷的水溶液中,40~70℃搅拌0.5~2h,获得混合溶液。
所述的预处理为本领域常规的打磨、清洗及去油脂等处理,优选包括以下步骤:将金属表面用砂纸打磨至1500~2000#,室温下酒精超声清洗10min,冷风吹干待用。
本发明提供了一种制备镁合金表面羟基磷灰石超疏水膜层的方法,通过水热法,在镁合金表面一步完成了具有微纳粗糙尺寸的特殊形状羟基磷灰石结构的构筑和低表面自由能物质的修饰。
上述方法得到的羟基磷灰石超疏水膜层,其水滴表面接触角均大于150°。通过电化学测试发现,所制备的羟基磷灰石超疏水膜层耐腐蚀性能较未处理的镁合金降低了4个数量级。
与现有技术相比,本发明具有如下优点及有益效果:
(1)本发明的方法可一步同时完成在金属表面制备超疏水表面所需的粗糙结构和低表面能物质,制备方法简便;
(2)获得的超疏水表面羟基磷灰石分布均匀,能显著提高镁合金的耐腐蚀性能;
(3)本发明设计的溶液配方均对环境和人类身体无害,甚至有益,可用于生物医用镁合金的表面处理。
附图说明
图1为实施例1制备的羟基磷灰石超疏水膜层的SEM图;
图2为实施例1制备的羟基磷灰石超疏水膜层与基体的极化曲线图;
图3为实施例2制备的羟基磷灰石超疏水膜层与基体的XRD图;
图4为实施例2制备的羟基磷灰石超疏水膜层与蒸馏水的接触角。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
尺寸为20×20×2(mm)的Mg-Gd-Nd-Zn-Zr镁合金,经表面预处理后水热处理一步获得结构特征突出的羟基磷灰石超疏水膜层,具体包括以下步骤:
(1)将镁合金表面用砂纸打磨至2000#后放入无水乙醇中,超声波清洗10min,分别用蒸馏水和乙醇冲洗,冷风吹干表面;
(2)将乙酸钙、磷酸二氢钠溶于水中,采用0.5M盐酸溶液调节pH至5,得到含钙磷的水溶液;将硬脂酸溶于无水乙醇中,得到硬脂酸的乙醇溶液;将硬脂酸的乙醇溶液缓慢倒入含钙磷的水溶液中,50℃搅拌1.5h(搅拌的转速为400r/min),获得水热反应溶液;所述水热反应溶液中乙醇与水的体积比为4:6,乙酸钙的浓度为0.01mol/L,磷酸二氢钠的浓度为0.005mol/L,硬脂酸的浓度为0.02mol/L;
(3)取80mL步骤(2)的水热反应溶液置于100mL水热反应釜内胆中,同时放入打磨好的镁合金试样,在220℃条件下水热反应3h,在镁合金表面获得羟基磷灰石超疏水膜层。
本实施例通过水热反应在镁合金表面获得羟基磷灰石超疏水膜层,其结构表征(SEM图)如图1所示。
其性能测试即极化测试曲线如图2所示,从图2中可知,对比未经处理的镁合金和表面有羟基磷灰石超疏水膜层的镁合金在模拟体液中的腐蚀性能,镁合金基体的腐蚀电流密度为13μA/cm2,而表面有羟基磷灰石超疏水膜层的镁合金腐蚀电流密度降低至2.1nA/cm2。这证明所制备超疏水膜层可以将腐蚀电流密度降低4个数量级。
本实施例通过水热反应在镁合金表面获得羟基磷灰石超疏水膜层与蒸馏水的接触角达到154℃。
实施例2
尺寸为20×20×2(mm)的Mg-Gd-Nd-Zn-Zr镁合金,经表面预处理后水热处理一步获得结构特征突出的超疏水表面,具体包括以下步骤及工艺条件:
(1)将镁合金表面打磨至2000#后放入无水乙醇中,超声波清洗10min,分别用蒸馏水和乙醇冲洗,冷风吹干表面;
(2)将乙酸钙、磷酸二氢钠溶于水中,采用0.1M盐酸溶液调节pH至4.5,得到含钙磷的水溶液;将硬脂酸溶于无水乙醇中,得到硬脂酸的乙醇溶液;将硬脂酸的乙醇溶液缓慢倒入含钙磷的水溶液中,60℃搅拌1h(搅拌的转速为400r/min),获得水热反应溶液;所述水热反应溶液中乙醇与水的体积比为6:4,乙酸钙的浓度为0.026mol/L,磷酸二氢钠的浓度为0.015mol/L,硬脂酸的浓度为0.05mol/L;
(3)取80mL步骤(2)的水热反应溶液置于100mL水热反应釜内胆中,同时放入打磨好的镁合金试样,在200℃条件下水热反应2h,在镁合金表面获得羟基磷灰石超疏水膜层。
本实施例通过水热反应在镁合金表面获得羟基磷灰石超疏水膜层的XRD图如图3所示;从图3中可知,表面生成了羟基磷灰石和硬脂酸钙。本实施例的羟基磷灰石超疏水膜层的表面接触角的表征图如图4所示,其接触角达到155°。在极化测试中,该超疏水膜层在模拟体液中的腐蚀电流密度降低至8.0nA/cm2,相较于Mg-Gd-Nd-Zn-Zr镁合金基体(镁合金基体的腐蚀电流密度为13μA/cm2)降低了4个数量级。
实施例3
尺寸为20×20×2(mm)的Mg-Mn-Ce镁合金,经表面预处理后水热处理一步获得羟基磷灰石超疏水膜层,具体包括以下步骤及工艺条件:
(1)将镁合金表面用砂纸打磨至2000#后放入无水乙醇中,超声波清洗10min,分别用蒸馏水和乙醇冲洗,冷风吹干表面;
(2)将乙酸钙、磷酸二氢钠溶于水中,采用0.1M盐酸溶液调节pH至4,得到含钙磷的水溶液;将硬脂酸溶于无水乙醇中,得到硬脂酸的乙醇溶液;将硬脂酸的乙醇溶液缓慢倒入含钙磷的水溶液中,70℃搅拌1h,获得水热反应溶液,所述水热反应溶液中乙醇与水的体积比为5:5,乙酸钙的浓度为0.05mol/L,磷酸二氢钠的浓度为0.03mol/L,硬脂酸的浓度为0.03mol/L;
(3)取80mL步骤(2)的水热反应溶液置于100mL水热反应釜内胆中,同时放入打磨好的镁合金试样;在100℃条件下水热反应2h,获得具有超疏水特性的羟基磷灰石膜层。
本实施例中通过水热反应获得的羟基磷灰石超疏水膜层与蒸馏水的接触角达到了152°。在极化测试中,该超疏水膜层在模拟体液中的腐蚀电流密度降低至3.0nA/cm2,相较于Mg-Mn-Ce镁合金基体(35μA/cm2)降低了4个数量级。
实施例4
尺寸为20×20×2(mm)的AZ31镁合金,经表面预处理后水热处理一步获得羟基磷灰石超疏水膜层,具体包括以下步骤:
(1)将镁合金表面用砂纸打磨至2000#后放入无水乙醇中,超声波清洗10min,分别用蒸馏水和乙醇冲洗,冷风吹干表面;
(2)将乙酸钙、磷酸二氢钠溶于水中,采用0.1M盐酸溶液调节pH至4.5,得到含钙磷的水溶液;将硬脂酸溶于无水乙醇中,得到硬脂酸的乙醇溶液;将硬脂酸的乙醇溶液缓慢倒入含钙磷的水溶液中,60℃搅拌2h,获得水热反应溶液,所述水热反应溶液中乙醇与水的体积比为3:7,乙酸钙的浓度为0.02mol/L,磷酸二氢钠的浓度为0.011mol/L,硬脂酸的浓度为0.02mol/L;
(3)取80mL步骤(2)的水热反应溶液置于100mL水热反应釜内胆中,同时放入打磨好的镁合金试样;在200℃条件下水热反应1h,在镁合金表面获得羟基磷灰石超疏水膜层。
本实施例中通过水热反应获得的羟基磷灰石超疏水膜层与蒸馏水的接触角达到了157°。在极化测试中,该超疏水膜层在模拟体液中的腐蚀电流密度降低至1.6nA/cm2,相较于AZ31镁合金基体(27μA/cm2)降低了4个数量级。
实施例5
尺寸为20×20×2(mm)的ZK60镁合金,经表面预处理后水热处理一步获得羟基磷灰石超疏水膜层,具体包括以下步骤:
(1)将镁合金表面用砂纸打磨至2000#后放入无水乙醇中,超声波清洗10min,分别用蒸馏水和乙醇冲洗,冷风吹干表面;
(2)将乙酸钙、磷酸二氢钠溶于水中,采用0.1M盐酸溶液调节pH至4,得到含钙磷的水溶液;将硬脂酸溶于无水乙醇中,得到硬脂酸的乙醇溶液;将硬脂酸的乙醇溶液缓慢倒入含钙磷的水溶液中,70℃搅拌2h,获得水热反应溶液,所述水热反应溶液中乙醇与水的体积比为7:3,乙酸钙的浓度为0.04mol/L,磷酸二氢钠的浓度为0.023mol/L,硬脂酸的浓度为0.03mol/L;
(3)取80mL步骤(2)的水热反应溶液置于100mL水热反应釜内胆中,同时放入打磨好的镁合金试样;在150℃条件下水热反应2h,在镁合金表面获得羟基磷灰石超疏水膜层。
本实施例中通过水热反应获得的羟基磷灰石超疏水膜层与蒸馏水的接触角达到了157°。在极化测试中,该超疏水膜层在模拟体液中的腐蚀电流密度降低至9.2nA/cm2,相较于ZK60镁合金基体(22μA/cm2)降低了4个数量级。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种在镁合金表面制备羟基磷灰石超疏水膜层的方法,其特征在于包括如下步骤:
(1)预处理:将镁合金进行表面预处理;
(2)混合溶液的配制:采用乙醇和水将乙酸钙、磷酸二氢钠和脂肪酸配制成溶液,得到混合溶液;所述混合溶液中乙酸钙的浓度为0.01~0.05mol/L;磷酸二氢钠的浓度为0.005~0.03mol/L,脂肪酸的浓度为0.01~0.05mol/L;
(3)将镁合金与混合溶液同时置于水热反应釜中,在100~230℃下反应1~3h,得到羟基磷灰石超疏水膜层。
2.根据权利要求1所述在镁合金表面制备羟基磷灰石超疏水膜层的方法,其特征在于:所述脂肪酸为硬脂酸或十四酸中的一种以上。
3.根据权利要求1所述在镁合金表面制备羟基磷灰石超疏水膜层的方法,其特征在于:所述混合溶液中乙醇和水的体积比为3:7~7:3。
4.根据权利要求1所述在镁合金表面制备羟基磷灰石超疏水膜层的方法,其特征在于:所述混合溶液的具体配制步骤为:将乙酸钙和磷酸二氢钠溶于水中,调节pH为4~5,得到含钙磷的水溶液;将脂肪酸溶于乙醇中,得到脂肪酸的乙醇溶液;将脂肪酸的乙醇溶液缓慢倒入含钙磷的水溶液中,40~70℃搅拌0.5~2h,获得混合溶液。
5.根据权利要求1所述在镁合金表面制备羟基磷灰石超疏水膜层的方法,其特征在于:所述的预处理包括以下步骤:将金属表面用砂纸打磨至1500~2000#,室温下酒精超声清洗10min,冷风吹干待用。
6.一种由权利要求1~5任一项所述的方法制备得到的羟基磷灰石超疏水膜层。
7.根据权利要求6所述羟基磷灰石超疏水膜层的应用,其特征在于:所述羟基磷灰石超疏水膜层应用于医用镁合金。
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