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CN108842119A - 一种表面镀有纳米碳晶膜的人体植入材料及其制备方法 - Google Patents

一种表面镀有纳米碳晶膜的人体植入材料及其制备方法 Download PDF

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CN108842119A
CN108842119A CN201810763459.5A CN201810763459A CN108842119A CN 108842119 A CN108842119 A CN 108842119A CN 201810763459 A CN201810763459 A CN 201810763459A CN 108842119 A CN108842119 A CN 108842119A
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magnesium alloy
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CN108842119B (zh
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文炯
张建华
刘永奇
郭留希
杨晋中
刘创勋
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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Abstract

本发明公开了一种表面镀有纳米碳晶膜的人体植入材料及制备方法，所述人体植入材料通过采用梯度过渡层技术，以钛为过渡层元素，在硬质的纳米碳晶膜与软质金属镁之间引入梯度过渡层得到。本发明通过淬火热处理技术，改变镁合金内部的金相结构，从而提高了镁合金的硬度，通过淬火热处理，镁合金内部晶粒细化且分布更加均匀，耐腐性有一定提高，碳化钛作为过渡层具有良好的抗磨损性能、高的硬度、高的强度和刚度，还具有优良的抗裂纹形成能力，不易产生应力集中。同时，引入钛元素在促使应力释放的同时，还能够提高非晶碳膜的稳定性。

Description

一种表面镀有纳米碳晶膜的人体植入材料及其制备方法
技术领域
本发明属于生物医用材料技术领域，具体涉及一种表面镀有纳米碳晶膜的人体植入材料及其制备方法。
背景技术
镁合金，作为第三代生物医用人体植入材料，具有生物活性且人体自身可降解吸收，由于其降解产物是人体必须元素，可被人体吸收而排除体外，不会引起不良反应，可将其作为心血管支架材料，具有良好的力学性能和生物相容性。因此，镁作为生物医学材料不但具有可行性，而且具有经济意义和发展前景。
但是，镁的耐蚀性能较差，在氯离子存在或所在介质的pH值低于11.5时，镁的腐蚀速率更快。镁的腐蚀会导致氢气的产生，使周围环境碱化，恶化植入材料周围的环境，降低镁植入人体后的使用寿命，这些均不利于镁合金在人体内的应用。因此要将镁合金真正应用到生物医学材料当中，需要控制其腐蚀速度及析氢过程。
纳米碳晶具有硬度高、良好的耐磨损性能、化学惰性以及良好的生物相容性。将纳米碳晶与镁基体相结合，利用纳米碳晶的耐腐蚀性能，可减缓镁合金在体液中的腐蚀速率，并利用其良好的生物相容性，提高镁基体植入材料与人体的相容性。同时，纳米碳晶表面具有超疏水性，可以抑制血小板的粘附和血栓的形成。
发明内容
本发明的目的是提供一种表面镀有纳米碳晶膜的人体植入材料，同时提供其制备方法是本发明的又一发明目的。
为实现上述发明目的，本发明采取的技术方案为：
一种表面镀有纳米碳晶膜的人体植入材料，所述人体植入材料通过采用梯度过渡层技术，以钛为过渡层元素，在硬质的纳米碳晶膜与软质金属镁之间引入梯度过渡层得到。
所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，包括以下步骤：
1)淬火热处理：镁合金试样依次经过酒精浸泡、无水乙醇清洗、氮气吹干后，将其放入马弗炉中快速升温至250℃保温1h后取出，放入水中，待试样达到室温后将其从水中取出，氮气吹干；其中，马弗炉升温速率为4-5℃/min。本申请中控制升温速率则直接影响形成的晶粒大小并最终影响镁合金质量，如升温速度过慢，淬火升温时间延长，会造成加热时形成的初始奥氏体晶核较大，后续保温过程中则会继续长大，导致淬火后的晶粒粗大；但是升温速度过快，奥氏体初始晶粒则会越细，在随后的保温过程中，其长大的倾向就越大，而更容易形成粗晶，造成金相结构不合格，从而影响镁合金质量。
2)碳化钛薄膜的制备：先将经过步骤1)热处理的镁合金试样依次用2000#、3000#的砂纸水磨至表面光亮无痕状态，酒精超声清洗，氮气吹干；
3)碳化钛溶液的制备：称取聚乙烯吡咯烷酮K30和聚乙二醇-1500各0.01-0.02g，加入9-10mL的去离子水混合，用氨水调节溶液的pH值为10，之后加入碳化钛纳米粉末0.25-0.35g，再用氨水调节溶液的pH值为10，将上述配好的溶液以20000-30000HZ的频率超声30-40min，再搅拌1-2h，搅拌采用磁力搅拌，搅拌的速度为1000-1500rpm；
4)碳化钛薄膜样片的制备：把镁合金片和石墨片浸入碳化钛溶液中，分别作为阴极和阳极，施加2.0V电压通电电泳3min后，将阴极镁合金片带电极取出，自然风干后在500-600℃焙烧1h即制得碳化钛薄膜样片；
4)将2-10g的纳米碳晶、30-40mL的乙醇和4-5mL的钛酸四丁酯混合，再加入10mL浓度为20mg/mL的乙酸纤维素混合形成溶胶，旋凃到经步骤4)处理的碳化钛薄膜样片上，于450-500℃下煅烧2-3h，即得。本发明中，加入纳米碳晶过少时，最终得到的产品耐腐蚀性不高，也减缓不了镁合金在体液中的腐蚀速率，同时不能提高镁基体植入材料与人体的生物相容性；加入量过多时，不利于膜的形成，膜表面容易出现空洞，膜的完整性不好，机械性能差，不能有效阻止溶液进入镁合金材料的内部，对基体提供不了良好的保护。
步骤1)中，镁合金试样的尺寸为1cm×1cm×0.5cm，酒精浸泡的时间为30-40min，无水乙醇清洗3-4次。
步骤4)中，镁合金片和石墨片的表面积相同，镁合金片和石墨片二者的距离为7-9cm。
步骤5)中，先称取纳米碳晶2-10g，加入到30-40mL的乙醇中，再向其中加入4-5mL的钛酸四丁酯。
步骤5)中，旋凃采用的旋涂仪参数设置：转速为300-400r/min-60s，加速度为2500-3000r/min-30s。
本发明通过淬火热处理技术，改变镁合金内部的金相结构，从而提高了镁合金的硬度，通过淬火热处理，镁合金内部晶粒细化且分布更加均匀，耐腐性有一定提高，碳化钛作为过渡层具有良好的抗磨损性能、高的硬度、高的强度和刚度，还具有优良的抗裂纹形成能力，不易产生应力集中。同时，引入钛元素在促使应力释放的同时，还能够提高非晶碳膜的稳定性。
与现有技术相比，本发明具有以下优点：
1、在镁合金表面沉积纳米碳晶膜，有效的缓解模拟体液对镁合金的腐蚀，由于硬质膜与软质金属之间膨胀系数的不同导致两者的结合力非常小，在膜与基体之间引入过渡层，可有效的提高两者之间的结合力；
2、以钛为过渡层元素，在镁合金表面沉积纳米碳晶膜，通过静态接触角表明，膜具有超疏水性，有效的阻止了模拟体液进入膜的内部，减少了镁合金的腐蚀；
3、溶血率实验表明，所得纳米碳晶膜溶血率＜5％，材料复合生物医用材料溶血率要求，具有生物相容性。
附图说明
图1不同处理的镁合金腐蚀速率。
具体实施方式
以下采用具体实施方式对本发明做进一步说明。
实施例1
一种表面镀有纳米碳晶膜的人体植入材料，所述人体植入材料通过采用梯度过渡层技术，以钛为过渡层元素，在硬质的纳米碳晶膜与软质金属镁之间引入梯度过渡层得到。
所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，包括以下步骤：
1)淬火热处理：镁合金试样(本实施例中选用挤压态AZ31B镁合金为材料，尺寸为1cm×1cm×0.5cm)依次经过酒精浸泡30min、无水乙醇清洗3次(浸泡清洗的目的是除去表面的油垢)、氮气吹干后，先放入恒温真空室中待用；将其放入马弗炉中快速升温至250℃保温1h后取出，放入水中，待试样达到室温后将其从水中取出，氮气吹干，(放在恒温真空室中待用；其中，马弗炉升温速率为4℃/min；
2)碳化钛薄膜的制备：先将经过步骤1)热处理的镁合金试样依次用2000#、3000#的砂纸水磨至表面光亮无痕状态，酒精超声清洗(去除表面污垢)，氮气吹干(将试样表面的酒精吹干)，放在干燥的恒温干燥室中备用；
3)碳化钛溶液的制备：称取聚乙烯吡咯烷酮K30和聚乙二醇-1500各0.01g，加入9mL的去离子水混合，用氨水调节溶液的pH值为10，之后加入碳化钛纳米粉末0.25g，再用氨水调节溶液的pH值为10，将上述配好的溶液以20000HZ的频率超声40min，再搅拌1h，搅拌采用磁力搅拌，搅拌速度为1500rpm；超声和搅拌的目的是使粉末充分分散；
4)碳化钛薄膜样片的制备：把镁合金片和石墨片浸入碳化钛溶液中，分别作为阴极和阳极，其中，镁合金片和石墨片的表面积相同，镁合金片和石墨片二者的距离为7-9cm，施加2.0V电压通电电泳3min后，将阴极镁合金片带电极取出，自然风干后在500-600℃焙烧1h即制得碳化钛薄膜样片；
5)先称取纳米碳晶2g，加入到30mL的乙醇中，再向其中加入4mL的钛酸四丁酯，再加入10mL浓度为20mg/mL的乙酸纤维素混合形成溶胶，旋凃到经步骤4)处理的碳化钛薄膜样片上，于500℃下煅烧2h，即得；旋凃采用的旋涂仪参数设置为转速为300-400r/min-60s，加速度为2500-3000r/min-30s。
实施例2
一种表面镀有纳米碳晶膜的人体植入材料，所述人体植入材料通过采用梯度过渡层技术，以钛为过渡层元素，在硬质的纳米碳晶膜与软质金属镁之间引入梯度过渡层得到。
所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，包括以下步骤：
1)淬火热处理：镁合金试样(本实施例中选用挤压态AZ31B镁合金为材料，尺寸为1cm×1cm×0.5cm)依次经过酒精浸泡40min、无水乙醇清洗4次(浸泡清洗的目的是除去表面的油垢)、氮气吹干后，先放入恒温真空室中待用；将其放入马弗炉中快速升温至250℃保温1h后取出，放入水中，待试样达到室温后将其从水中取出，氮气吹干，(放在恒温真空室中待用；其中，马弗炉升温速率为5℃/min；
2)碳化钛薄膜的制备：先将经过步骤1)热处理的镁合金试样依次用2000#、3000#的砂纸水磨至表面光亮无痕状态，酒精超声清洗(去除表面污垢)，氮气吹干(将试样表面的酒精吹干)，放在干燥的恒温干燥室中备用；
3)碳化钛溶液的制备：称取聚乙烯吡咯烷酮K30和聚乙二醇-1500各0.02g，加入10mL的去离子水混合，用氨水调节溶液的pH值为10，之后加入碳化钛纳米粉末0.35g，再用氨水调节溶液的pH值为10，将上述配好的溶液以30000HZ的频率超声30min，再搅拌2h，采用磁力搅拌，搅拌速度为1000rpm，超声和搅拌的目的是使粉末充分分散；
4)碳化钛薄膜样片的制备：把镁合金片和石墨片浸入碳化钛溶液中，分别作为阴极和阳极，其中，镁合金片和石墨片的表面积相同，镁合金片和石墨片二者的距离为9cm，施加2.0V电压通电电泳3min后，将阴极镁合金片带电极取出，自然风干后在600℃焙烧1h即制得碳化钛薄膜样片；
5)先称取纳米碳晶10g，加入到40mL的乙醇中，再向其中加入5mL的钛酸四丁酯，再加入10mL浓度为20mg/mL的乙酸纤维素混合形成溶胶，旋凃到经步骤4)处理的碳化钛薄膜样片上，于500℃下煅烧2h，即得；旋凃采用的旋涂仪参数设置为转速为300-400r/min-60s，加速度为2500-3000r/min-30s。
实施例3
一种表面镀有纳米碳晶膜的人体植入材料及其制备方法，与实施例1不同之处在于，
步骤5)中纳米碳晶6g。其余同实施例1。
性能测试：
为说明发明效果，本发明以实施例1所制得的人体植入材料为例对其进行了腐蚀速率、接触角及溶血性进行了相关测试。
1、腐蚀速率比较
本实验数据是通过失重实验所得到的，因为镁合金腐蚀过程中会有氢气产生，每天对反应体系称重，记录体系损失的重量，通过析出氢气体系的减少量来评价镁合金的腐蚀速率。结果如图1所示。
由图1的结果可知，与表面沉积纳米碳晶膜的镁合金相比较，没有沉积纳米碳晶膜的镁合金腐蚀速率明显的比沉积了纳米碳晶膜的镁合金腐蚀速率要大，其变化趋势波动比较大。沉积了纳米碳晶膜的镁合金，腐蚀速率明显非常小，变化趋势比较稳定，始终维持在一个相对比较低的水平。通过比较可知，镁合金表面沉积纳米碳晶膜之后腐蚀速率明显减小。
2、接触角
当静态接触角大于90°小于120°时，材料具有疏水性，当接触角大于120°时，材料具有超疏水性。从静态接触角的测试结果表1来看，在沉积纳米碳晶之后镁合金的疏水性明显提高，其接触角为132°，具有超疏水性，而未经处理的镁合金的接触角为76°。由此可见，以碳化钛为过渡层得到的纳米碳晶膜对基体的保护效果较好，此实验结果与其腐蚀速率结果是一致的，这可使溶液更难进入到镁合金表面，更能进一步提高镁合金的耐腐蚀性。
表1不同样品接触角的比较
3、溶血实验
对人体植入材料而言，当异种材料植入人体后，人体会发生排异反应，所以在植入之前应该对材料的生物活性进行表征。其中最重要的就是溶血实验，当材料在模拟体液中发生一定量的溶血，则材料不能植入人体当中。具体标准为：当材料的溶血率＜5％，则说明材料符合生物医用材料的溶血率要求。如果材料的溶血率＞5％，则预示材料有溶血作用，材料不能植入到人体当中，此材料部具有生物相容性。
本实验选用未经任何处理的镁合金(阴性对照组)、空白对照组和经过制备以钛为过渡层元素沉积纳米碳晶膜(实验组)作为实验所用的材料。首先阴性对照试管3支，各加入6mL模拟体液；空白对照试管3支，各加入6mL蒸馏水；待测样品装入3支试管。然后将全部试管放入37±0.5℃恒温培养箱保温60min；取新鲜兔血3mL，加入20g/L草酸钾0.1mL，摇晃均匀后加入3mL的模拟体液稀释待用；将空白组各试管中加入稀释后的兔血200μL，轻轻摇匀。最后将全部试管放入37±0.5℃恒温培养箱保温60min。取出试管，将试管内的溶液以4000r/min的速度离心10min，取上层清液，用分管光度计测量，在波长545nm处读数计算溶血率。
表2溶血率测试结果
从表2可以明显看出，未经任何处理的阴性对照组溶血率达到了63.18％，显然材料不符合植入人体的标准。在镁基体的表面沉积纳米碳晶膜后实验组样品的溶血率＜5％，符合植入人体的条件，说明纳米碳晶具有生物相容性。

Claims (6)

1.一种表面镀有纳米碳晶膜的人体植入材料，其特征在于，所述人体植入材料通过采用梯度过渡层技术，以钛为过渡层元素，在硬质的纳米碳晶膜与软质金属镁之间引入梯度过渡层得到。
2.权利要求1所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，其特征在于，包括以下步骤：
1）淬火热处理：镁合金试样依次经过酒精浸泡、无水乙醇清洗、氮气吹干后，将其放入马弗炉中快速升温至250℃保温 1h后取出，放入水中，待试样达到室温后将其从水中取出，氮气吹干；
2）碳化钛薄膜的制备：先将经过步骤1）热处理的镁合金试样依次用2000#、3000#的砂纸水磨至表面光亮无痕状态，酒精超声清洗，氮气吹干；
3）碳化钛溶液的制备：称取聚乙烯吡咯烷酮K30和聚乙二醇-1500各0.01-0.02g，加入9-10mL的去离子水混合，用氨水调节溶液的pH值为10，之后加入碳化钛纳米粉末0.25-0.35g，再用氨水调节溶液的pH值为10，将上述配好的溶液以20000-30000HZ的频率超声30-40min，再搅拌1-2h；
4）碳化钛薄膜样片的制备：把镁合金片和石墨片浸入碳化钛溶液中，分别作为阴极和阳极，施加2.0V电压通电电泳3min后，将阴极镁合金片带电极取出，自然风干后在500-600℃焙烧1h即制得碳化钛薄膜样片；
5）将2-10g的纳米碳晶、30-40mL的乙醇和4-5mL的钛酸四丁酯混合，再加入10mL浓度为20mg/mL的乙酸纤维素混合形成溶胶，旋涂到经步骤4）处理的碳化钛薄膜样片，于450-500℃下煅烧2-3h，即得。
3.如权利要求2所述的所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，其特征在于，步骤1）中，镁合金试样的尺寸为1cm×1cm×0.5cm，酒精浸泡的时间为30-40min，无水乙醇清洗3-4次；步骤3）中搅拌采用磁力搅拌，搅拌的速度为1000-1500rpm。
4.如权利要求2所述的所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，其特征在于，步骤4）中，镁合金片和石墨片的表面积相同，镁合金片和石墨片二者的距离为7-9cm。
5.如权利要求2所述的所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，其特征在于，步骤5）中，先称取纳米碳晶2-10g，加入到30-40mL的乙醇中，再向其中加入4-5mL的钛酸四丁酯。
6.如权利要求2所述的所述的表面镀有纳米碳晶膜的人体植入材料的制备方法，其特征在于，步骤5）中，旋凃采用的旋涂仪参数设置为转速为300-400r/min-60s，加速度为2500-3000r/min-30s。
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