CN107119260B - 一种骨植入用镁-铜涂层及其制备方法 - Google Patents
一种骨植入用镁-铜涂层及其制备方法 Download PDFInfo
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- CN107119260B CN107119260B CN201610099989.5A CN201610099989A CN107119260B CN 107119260 B CN107119260 B CN 107119260B CN 201610099989 A CN201610099989 A CN 201610099989A CN 107119260 B CN107119260 B CN 107119260B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 239000007943 implant Substances 0.000 title claims abstract description 28
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 title claims abstract description 27
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- 239000011777 magnesium Substances 0.000 claims abstract description 53
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 22
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 239000000956 alloy Substances 0.000 claims abstract description 5
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- 239000010936 titanium Substances 0.000 claims abstract description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 241000588724 Escherichia coli Species 0.000 description 1
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- 229910004353 Ti-Cu Inorganic materials 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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Abstract
为了解决植入材料的骨结合及感染问题,本发明提供了一种骨植入用镁‑铜涂层及其制备方法,采用化学气相沉积技术及蒸镀技术,在钛及钛合金、钴基合金、不锈钢、高分子材料或网状玻璃碳上制备金属镁‑铜涂层,该涂层的厚度为0.1‑200μm,涂层中铜元素的质量比例为:0%<Cu≤10%。本发明能够解决现有植入材料骨相容性及感染问题,该方法所得永久植入材料适合多种植入部位力学性能要求,且具极佳的生物相容性,同时具备杀菌功能。
Description
技术领域
本发明属于医用材料领域,特别涉及齿科植入物、关节置换和人体组织缺损的填充材料及植入材料抗菌技术领域;具体为在植入物表面的镁-铜涂层材料及其制备方法。
背景技术
由于植入假体松动和磨蚀引发的不良细胞反应使人工关节等植入体只有10-15年的寿命,不能满足长期使用要求。同时,感染仍然是骨科植入物灾难性的术后并发症之一。植入体内的金属异物是导致此类感染发生的危险因素,所引发的一系列体内反应包括巨噬细胞功能的减弱,局部免疫系统的钝化等都为病原体的增殖创造了便利的条件。此外,植入物表面吸附的蛋白还能促进细菌黏附到植入物表面引发感染。过去人们大多关注对环境和个人污染的清除及手术期全身抗生素的应用,而新的方法是针对该类感染发病的特殊机制通过植入物表面修饰改性来降低感染的风险。
金属材料一直以来被认为具有生物稳定性,虽然人们对其表面进行了各种表面改性的工作,骨细胞的粘附生长仍不理想。而金属材料中的镁(Mg),因为其具有较高的负电极电位,与水发生化学反应而降解,被人体吸收及代谢。同时,镁具有生物活性,可诱导细胞分化、生长和血管的长入,其作为植入器件植入生物体后,骨细胞向镁降解而减少的空间增殖、繁殖,随着镁逐步降解,形成新的具有原来特殊功能和形态的相应组织和器官,达到修复创伤和重建功能的目的。此外,由于镁降解而形成的碱性环境能达到抑制细菌生长的目的。利用铜(Cu)离子来杀菌的历史十分悠久,自1761年Schulthees采用硫酸铜防治小麦腥黑病起至今已有二百多年的历史。有研究报道通过在纯钛中加入1%或5%的Cu元素,形成的Ti-Cu合金有明显的杀菌功能,并在动物体内植入实验中表现出了较强的抗炎症作用及一定的促进成骨的生物医学功能。
发明内容
为了解决植入材料的骨结合及感染问题,本发明提供了一种骨植入用镁-铜涂层及其制备方法,采用化学气相沉积技术及蒸镀技术,在钛及钛合金、钴基合金、不锈钢、高分子材料或网状玻璃碳上制备金属镁-铜涂层,以解决现有植入材料骨相容性及感染问题,该方法所得永久植入材料适合多种植入部位力学性能要求,且具极佳的生物相容性,同时具备杀菌功能。
本发明的技术方案如下:
一种骨植入用镁-铜涂层,其特征在于:镁-铜涂层的厚度为0.1-200μm,涂层中铜元素的质量比例为:0%<Cu≤10%(优选2%≤Cu≤7%)。
本发明所述骨植入用镁-铜涂层的制备方法,其特征在于:对于镁涂层,采用蒸镀法将纯镁蒸发,并用载气将镁蒸气输运到基体表面而获得镁涂层;对于铜涂层,采用化学气相沉积法,使用氢气将金属铜的卤化物还原为金属铜并沉积在基体表面而获得铜涂层。
其中,所用基体为实体或多孔结构,采用钛及钛合金、钴基合金、不锈钢、高分子材料或网状玻璃碳制成。
本发明所述骨植入用镁-铜涂层的制备方法,其特征在于:所用实体基体为医用材料及器件,所用多孔结构基体的孔隙率≧80%,孔径为200μm-5mm。
本发明所述骨植入用镁-铜涂层的制备方法,其特征在于:所述卤化物为纯度≧99.99%的氯化铜粉末;还原气体氢气为纯度≧99.99%的高纯氢气;镁原料为纯度≧99.99%纯镁颗粒。
本发明所述骨植入用镁-铜涂层的制备方法,其特征在于:氢气的流量为50-300SCCM,沉积真空度为5-200Pa,纯镁蒸发温度为500-800℃,氯化铜的蒸发温度为200-350℃,沉积温度为150-300℃。
本发明采用化学气相沉积技术在多孔支架基体表面沉积金属铜的基本原理为:还原性气体(氢气)将气化的无水氯化铜还原为金属铜,并沉积到基体孔隙表面,沉积过程中的化学反应方程式如下:
本发明制备镁-铜涂层的具体步骤如下:
(1)、将多孔支架基体依次用去离子水、无水乙醇超声清洗10分钟后,干燥氮气吹干送入沉积室;
(2)、氯化铜粉末和纯镁颗粒分别放入蒸发室目标位置,抽极限真空至10-4Pa,用高纯氩气反复清洗最少3次,以除去空气,保证无氧环境;
(3)、沉积室升温至沉积温度,蒸发室加热使氯化物汽化,氢气作为还原性气体及载气将氯化铜蒸气送入沉积室并还原为金属铜,镁颗粒蒸发为镁蒸气沉积在基体表面,反应一定时间后随炉冷却至室温。
本发明的有益效果是:
1、本发明提出一种骨植入用镁-铜涂层多孔支架,该多孔支架可模拟人骨的结构和力学性能,满足各个部位对力学性能和结构的不同要求,为骨细胞的粘附和骨组织的长入提供有利的三维空间,利用镁降解后的碱性环境及铜离起到双重杀菌作用。
2、本发明所述金属镁具有良好的生物相容性。金属镁将多孔支架基体包覆其中,利用镁的骨传导优势,骨组织逐步填充降解后的镁的空缺,镁的降解引导骨组织及血管长入多孔基体内部,从而提高多孔支架的组织结合能力;金属铜具有杀菌作用,减少了术后感染的可能,大大提高手术的成功率。
3、本发明提出的制备涂层的方法,可在多种骨科植入材料表面涂覆一定厚度的镁-铜涂层,适用于多种表面,不需要对材料表面进行特殊处理,适用范围广。
4、在器件表面涂覆的金属镁具有良好的生物相容性。镁与水可发生腐蚀电化学反应,生成可溶于水并可被人体吸收的物质。同时,镁在人体内属常量元素,其含量在体内所有元素中占第四位,对人体新陈代谢起到非常重要的作用。
附图说明
图1为实施例1中沉积设备示意图。图中,1沉积室炉体;2蒸发室炉体;3、衬底;4、蒸发源;5、尾气处理装置;6、真空系统;7、流量控制器。
图2a,b,c,d分别是实施例1-4的表面电子显微镜照片。
图3为实施例1用碱性磷酸酶染色判断细胞增值率结果,A和C为涂层组,B和D为基体组。
图4为实施例2沉积前后样品X射线衍射图。图中,横坐标为衍射角2θ(度),纵坐标为强度(A.U.)。
图5为实施例5浸泡后材料表面宏观照片。
具体实施方式
如图1所示,本发明方法所用的沉积设备主要包括:沉积室炉体1、蒸发室炉体2等,在沉积室炉体1中放置基体,在蒸发室炉体2中放置蒸发源4,蒸发源4的一端与流量控制器7的一端连通,流量控制器7的另一端分别连接H2和Ar供应管路,蒸发源4的另一端与基体所在的沉积室相通,基体所在的沉积室分别与尾气处理装置5和真空系统6相通。
本发明采用化学气相沉积系统制备涂层,纯镁颗粒为蒸发源,氯化铜粉末作为反应源,氢气为还原性气体,氩气为载气,设备图如图1所示。多孔钛合金(Ti-6Al-4V)支架基体由3D打印技术中的电子束熔融方法制备,孔隙率≧80%,孔径为200μm-1mm,网状玻璃碳支架基体为浸渍法制备,孔隙率≧80%,孔径为500μm-5mm,支架基体样品需经酸洗,水洗,酒精清洗后,干燥氮气吹干,再置入沉积室炉体1。
实施例1
将多孔钛合金(Ti-6Al-4V)样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=25:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度300℃,氯化铜源蒸发温度为200℃,工作真空度5Pa,氢气流量为50SCCM,沉积时间3h,沉积金属镁-铜层的厚度为200μm,铜质量百分比为2%。为确定涂层的细胞相容性,进行了ALP染色,结果如图3所示,培养4天及7天后,涂层的细胞数量均高于基体,说明涂层提高了基体的细胞相容性。
实施例2
将多孔钛合金(Ti-6Al-4V)样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=20:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度200℃,氯化铜源蒸发温度为300℃,工作真空度5Pa,氢气流量为100SCCM,沉积时间2h,沉积金属镁-铜层的厚度为100μm,铜质量百分比为5%,其X射线衍射图谱如图4所示,由于铜含量比较低,因此只可见金属镁的衍射信息。
实施例3
将多孔钛合金(Ti-6Al-4V)样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=15:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度150℃,氯化铜源蒸发温度为300℃,工作真空度50Pa,氢气流量为100SCCM,沉积时间1.5h,沉积金属镁-铜层的厚度为150μm,铜质量百分比为7%。
实施例4
将多孔钛合金(Ti-6Al-4V)样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=10:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度100℃,氯化铜源蒸发温度为350℃,工作真空度100Pa,氢气流量为200SCCM,沉积时间1h,沉积金属镁-铜层的厚度为120μm,铜质量百分比9%。
实施例5
将多孔钛合金(Ti-6Al-4V)样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=10:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度100℃,氯化铜源蒸发温度为350℃,工作真空度100Pa,氢气流量为100SCCM,首先加热沉积室炉体1高温区,纯镁沉积时间1h,纯镁厚度为100μm,后加热蒸发室炉体2,沉积时间20min,沉积金属镁-铜层的厚度为20μm,获得底部为100μm纯镁层及顶部为20μm镁-铜层的双层结构,铜质量百分比2%。样品经模拟体液浸泡后,由于铜与镁自腐蚀电位的不同而发生电偶腐蚀,在材料表面形成微孔,这些微孔特别有利于细胞的粘附和生长,如图5所示。
实施例6
网状玻璃碳样品置入沉积室炉体1;将氯化铜粉末放入蒸发室炉体2,将纯镁放入沉积室炉体1的高温区,原子比为镁:氯化铜=10:1,然后连接气路,并检查密封状况,抽极限真空(10-4Pa)后,氩气反复清洗整个系统3次,以确保氧气含量降到最低。设定沉积温度100℃,氯化铜源蒸发温度为350℃,工作真空度100Pa,氢气流量为200SCCM,沉积时间10min,沉积金属镁-铜层的厚度为20μm,铜质量百分比9%。将样品按照“JIS Z 2801-2000《抗菌加工制品-抗菌性试验方法和抗菌效果》、GB/T 2591-2003《抗菌塑料抗菌性能实验方法和抗菌效果》”等相关标准规定进行定量的抗菌性能检测。结果得到样品对常见感染菌(大肠杆菌、金黄色葡萄球菌)作用后的杀菌率为99%。
实施例结果表明,本发明选择3D打印多孔钛合金作为基体提供适合骨组织生长和骨缺损重建的多孔几何环境,采用蒸镀法及化学气相沉积技术共同沉积制备高生物相容性及抗菌性的金属镁-铜涂层,利用模拟骨骼外形、表面粗糙度和力学性能的多孔基体,采用蒸镀法和化学气相沉积技术可提供镁-铜涂层的有效覆盖,可在提高医用材料骨长入能力的同时增加材料的抗菌性能。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种骨植入用镁-铜涂层,其特征在于:镁-铜涂层的厚度为0.1-200μm,涂层中铜元素的质量比例为:0%<Cu≤10%,所述涂层的制备方法为:镁采用蒸镀法,铜采用化学气相沉积法,两种物质同时沉积从而获得镁-铜涂层;其中沉积真空度为5-200Pa。
2.一种权利要求1所述骨植入用镁-铜涂层的制备方法,其特征在于:对于镁涂层,采用蒸镀法将纯镁蒸发,并用载气将镁蒸气输运到基体表面而获得镁涂层;对于铜涂层,采用化学气相沉积法,使用氢气将金属铜的卤化物还原为金属铜并沉积在基体表面而获得铜涂层。
3.按照权利要求2所述骨植入用镁-铜涂层的制备方法,其特征在于:所用基体为实体或多孔结构,采用钛及钛合金、钴基合金、不锈钢、高分子材料或网状玻璃碳制成。
4.按照权利要求3所述骨植入用镁-铜涂层的制备方法,其特征在于:所用实体基体为医用材料及器件;所用多孔结构基体的孔隙率≧80%,孔径为200μm-5mm。
5.按照权利要求2所述骨植入用镁-铜涂层的制备方法,其特征在于:所述金属铜的卤化物为纯度≧99.99%的氯化铜粉末;还原气体氢气为纯度≧99.99%的高纯氢气;纯镁原料为纯度≧99.99%纯镁颗粒。
6.按照权利要求2所述骨植入用镁-铜涂层的制备方法,其特征在于:氢气的流量为50-300SCCM。
7.按照权利要求5所述骨植入用镁-铜涂层的制备方法,其特征在于:纯镁蒸发温度为500-800℃,氯化铜的蒸发温度为200-350℃。
8.按照权利要求2所述骨植入用镁-铜涂层的制备方法,其特征在于:沉积温度为150-300℃。
9.按照权利要求2所述骨植入用镁-铜涂层的制备方法,其特征在于,具体制备步骤如下:
(1)、将基体依次用去离子水、无水乙醇超声清洗后,干燥氮气吹干送入沉积室;
(2)、氯化铜粉末和纯镁颗粒分别放入蒸发室目标位置,抽极限真空至10-4Pa,用高纯氩气反复清洗最少3次,以除去空气,保证无氧环境;
(3)、沉积室升温至沉积温度,蒸发室加热使氯化物汽化,氢气作为还原性气体及载气将氯化铜蒸气送入沉积室并还原为金属铜,镁颗粒蒸发为镁蒸气沉积在基体表面,反应完成后随炉冷却至室温。
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