CN111991623B - 一种镍钛形状记忆合金复合涂料及其应用 - Google Patents
一种镍钛形状记忆合金复合涂料及其应用 Download PDFInfo
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Abstract
本发明公开了一种镍钛形状记忆合金复合涂料,属于医学领域。该复合涂料由纳米银、聚乳酸、PVP和溶剂组成,所述纳米银的浓度为0.01‑1g/100ml,所述聚乳酸的浓度为5‑30wt%,所述PVP的浓度是纳米银的1‑5倍。本发明还公开了所述复合涂料在制备镍钛形状记忆合金涂层中的应用以及一种镍钛形状记忆合金涂层的制备方法。该涂料有效地降低了镍钛形状记忆合金因镍离子过量而产生的生物毒性,此外还具有抗菌和隔热效果,能降低镍钛形状记忆合金热驱动引起的热损伤。所制备的复合涂层具有很高的生物相容性,本发明为镍钛形状记忆合金提供了更好的应用前景。
Description
技术领域
本发明涉及一种镍钛形状记忆合金复合涂料,属于医学领域。
背景技术
自20世纪60年代发现镍钛形状记忆合金以来,该材料已广泛应用于航空航天、冶金、制造等诸多领域。Ni-Ti形状记忆合金由于具有良好的形状记忆效应、超弹性、低磁性、耐磨性、抗疲劳性和良好的生物相容性,在医学领域也有着广泛的应用。例如,各种体内固定装置,如正畸弓丝、U形钉、肋骨爪、腓骨环抱器、腕三角融合器、椎间融合器等,广泛应用于血管支架、血管栓塞器、血管吻合器、肠吻合器等以及制造各种新型智能假肢和矫形器等医疗器械。再如,由内置于胶囊内窥镜中的镍钛形状记忆合金驱动的注射系统可以控制其在体内和体外的标记和定位。还有一种膀胱驱动器,通过镍钛形状记忆合金的变形挤压膀胱,代替失控的膀胱小便,排出尿液。经电磁感应加热激活的Ni-Ti-SMA可植入阴茎假体内,取代常用的液压驱动假体,以及用于治疗脊柱侧凸的Ni-Ti-SMA脊柱矫形杆。
Ni-Ti形状记忆合金的形状记忆是由温度驱动的。因此,当反向马氏体相变的终温高于人体最高耐受温度时,Ni-Ti-SMA器件需要在体内稳定工作,否则,装置会在体内自动变形,不再受外界控制。众所周知,在正常情况下,人体产生的最高温度为42℃,但当局部温度达到45℃时,会对周围组织造成明显的热损伤。此外,Ni-Ti形状记忆合金本身也存在镍离子释放过多的问题,可能导致长期植入人体的潜在危险。对于所有的医学植入物来说,细菌感染一直是一个不可避免的问题,异物植入人体是微生物污染的优先场所,导致假体感染,最终导致植入失败。因此目前已有大量的研究集中在减少镍离子释放和控制植入物的细菌感染上,例如通过微弧氧化制备的氧化铝涂层和用于隔离镍离子释放的化学沉积羟基磷灰石涂层,但是减少植入物感染仍然是一个巨大的医学挑战,迫切需要一种能够在防止镍离子释放和控制细菌感染的同时,大大降低镍钛形状记忆合金热损伤的复合隔热涂层。
发明内容
本发明的一个目的是提供一种镍钛形状记忆合金复合涂料,本发明的另一个目的是提供一种镍钛形状记忆合金涂层的制备方法。
为实现上述第一个目的,本发明的技术方案如下:
一种镍钛形状记忆合金复合涂料,它由纳米银、聚乳酸、PVP和溶剂组成,所述纳米银的浓度为0.01-1g/100ml,所述聚乳酸的浓度为5-30wt%,所述PVP的浓度是纳米银的1-5倍。
优选地,所述纳米银的浓度为0.1-0.5g/100ml,最佳为0.3g/100ml。
优选地,所述聚乳酸的浓度为8-15wt%,最佳为10wt%。
优选地,所述纳米银的粒径为20-100nm,最佳为20nm。
优选地,所述PVP的浓度是纳米银的3.6倍。
优选地,所述溶剂为二氯甲烷。
为实现上述第二个目的,本发明进一步提供一种镍钛形状记忆合金涂层的制备方法,该方法包括在镍钛形状记忆合金表面涂覆以上所述复合涂料的的步骤。
优选地,还包括在涂覆复合涂料前使用微弧氧化的方法在镍钛形状记忆合金表面形成氧化铝镀层的步骤。所述氧化铝镀层能改变镍钛形状记忆合金的表面结构,从而提高复合涂料的粘附性,同时氧化铝镀层还能提高复合涂料的隔热效果。
进一步优选地,所述微弧氧化的电解液含有0.15M NaAlO2和0.03M NaH2PO2·H2O。
进一步优选地,所述微弧氧化的阳极为镍钛形状记忆合金,阴极是螺旋钢管,通电占空比30%,恒定正向电流12A,恒定反向电流4A,恒定正向电压420V,恒定反向电压75V,通电时间30分钟,并且电解液的温度保持在20℃。
本发明的有益效果是:
本发明提供了一种新型复合涂料,该涂料主要由银纳米和聚乳酸组成,具有抗菌、隔热等多种功能,尤其适合用于镍钛形状记忆合金,研究发现,该涂料有效地降低了镍钛形状记忆合金因镍离子过量而产生的生物毒性。多孔结构使复合涂料能够牢固地覆盖在镍钛形状记忆合金表面,所制备的纳米银/PLA/氧化铝复合涂层不仅提高了镍钛形状记忆合金的抗菌效果,而且由于其高红外辐射反射和低导热性降低了镍钛形状记忆合金热驱动引起的热损伤。此外,通过动物实验和免疫组织化学方法,探讨了纳米银/PLA/氧化铝复合涂层的生物相容性。本研究为镍钛形状记忆合金提供了更好的应用前景。
附图说明
图1是镍钛记忆合金棒与复合涂层镍钛记忆合金棒在兔子体内的加热温度曲线。图中:NiTi是镍钛记忆合金棒;PLA@Ag@NiTi是设有纳米银/PLA/氧化铝复合涂层的镍钛记忆合金棒。
图2是不同时间点测得的不同样品对L929细胞活力的影响。图中:NiTi是镍钛记忆合金棒;PLA@Ag@NiTi是设有纳米银/PLA/氧化铝复合涂层的镍钛记忆合金棒;PLA@Ag是Ag/PLA复合薄膜;Pla是聚乳酸薄膜;Ctrl是空白对照。
图3是在不同样品上孵育的L929细胞形态和增殖显微图。
图4是镍钛记忆合金棒和复合涂层镍钛记忆合金棒分别植入兔体内后测得的温度变化情况和镍离子含量。
图5是镍钛记忆合金棒和复合涂层镍钛记忆合金棒分别植入兔体内后的周围组织HE染色图。
具体实施方式
下面通过具体实施例对本发明进行详细说明。
实施例1
1.氧化铝镀层的制备
使用镍钛形状记忆合金作为基体,对镍钛合金进行微弧氧化层的制备,步骤如下:
(1)以镍钛合金作为基体材料,对其进行清洗去污,使用2000#SiC砂纸打磨,去离子水清洗多次。
(2)配制由0.15M NaAlO2和0.03M NaH2PO2·H2O组成的电解液。
(3)镍钛合金样品用作阳极,螺旋钢管用作阴极,接通电源,占空比30%,恒定正向电流12A,恒定反向电流4A,恒定正向电压420V,恒定反向电压75V。该过程持续30分钟,并且电解质溶液的温度保持在20℃。
(4)反应完毕,取出带有氧化铝镀层的镍钛合金,用去离子水清洗干净。
2.不同粒径纳米银粒子的制备
使用硝酸银作为含银化合物,PVP(聚乙烯吡咯烷酮,平均分子量58000)作为保护剂,乙二醇作为还原剂来制备纳米银颗粒。
制备20nm粒径的纳米银步骤如下:
(1)将约0.472克硝酸银和约1.08克PVP溶解在60毫升乙二醇中并充分混合,然后将溶液在配备有回流冷凝器的反应器中剧烈搅拌30分钟;
(2)将该溶液在7.5℃min-1的恒定速率下加热至120℃,加热持续30分钟。
(3)通过11000rpm离心收集得到粒径约20nm的纳米银颗粒,并用去离子水反复清洗几次。
其它条件不变,通过控制加热速率即可得到不同粒径的纳米银,其中50nm纳米银的加热速率为1℃min-1,100nm纳米银的加热速率为0.8℃min-1。
3.纳米银/PLA复合涂料的制备
使用上述合成的纳米银颗粒,二氯甲烷作为溶剂,PLA(聚乳酸,平均分子量50000)作为基质制备纳米银/PLA复合涂料。制备步骤如下:
将纳米银溶解在二氯甲烷溶液中,加入PVP(为使纳米银颗粒分散均匀并提高涂料的粘附性),纳米银颗粒与PVP质量比为1:3.6,随后在600W超声下混合30分钟得到均匀的纳米银二氯甲烷溶液,最后将PLA加入到纳米银二氯甲烷溶液中,使PLA占溶液总质量的10%,混合均匀,将混合物在冰浴中(0℃)搅拌2小时,避光。
通过调整加入纳米银颗粒的质量,可以得到纳米银颗粒浓度分别为0.1g/100ml,0.2g/100ml,0.3g/100ml,0.4g/100ml的纳米银&PLA复合涂料。其中PLA浓度始终为10%wt,PVP加入量与纳米银颗粒的加入量相关,纳米银颗粒与PVP质量比为1:3.6。
4.纳米银/PLA/氧化铝复合涂层的制备
取出之前通过微弧氧化镀有氧化铝层的镍钛形状记忆合金,将其浸没在纳米银/PLA复合涂料中,浸泡5-10分钟使涂料与氧化铝层充分结合。随后置于70-100℃的烘箱中烘干6小时,最终在镍钛形状记忆合金上得到纳米银/PLA/氧化铝复合涂层。
实施例2复合涂料的抗菌性能
1.纳米银粒径和浓度对涂料抑菌效果的影响
为了探讨纳米银颗粒的不同粒径和浓度对复合涂料抗菌性能的影响,将实施例1步骤3制备的复合涂料采用溶剂浇铸法制备了Ag/PLA薄膜。将复合涂料倒入模具中,置于100℃的干燥箱中蒸发6小时,获得完全干燥的膜并将其切割成所需的形式。
以革兰氏阳性菌金黄色葡萄球菌为实验菌,将细菌在LB肉汤中稀释至107CFU/ml,并将稀释后的400ul细菌溶液加入到含有不同Ag/PLA薄膜的12孔板中。接种的细菌在37℃培养。使用分光光度计酶免疫分析分析仪(美国Perkin Elmer Enspire 2300)在620nm处分析并测量各组在不同时间点的细菌浓度并按下式计算抑菌率:
抑菌率(%)=(A-B)/A×100%
其中A是空白对照的OD值,B是给定样本的OD值。
表1纳米银粒径和浓度对涂料抑菌效果的影响
其中空白对照未加入任何涂料,PLA薄膜是仅用聚乳酸制成的薄膜。
从以上结果可以得出,纳米银粒径越小、浓度越高,薄膜对金黄色葡萄球菌的抑菌率越高,当纳米银粒径为20nm、浓度大于0.3g/100ml时,各时间点测得的抑菌率都较高。
2.环境温度对涂料抑菌效果的影响
探讨复合涂料(20nm,0.2g/100ml)在不同温度下抗菌效果的差异,将稀释后的400ul菌液加入12孔板中,在37℃培养箱中培养4小时,然后在恒温水浴锅中加热30分钟。水浴锅的温度设定为37℃、41℃、45℃、49℃。然后将12孔板放回37℃培养箱中8h,测量各组的细菌浓度并按计算抑菌率,同时以空白组在相同温度下作为对照为对照。
表2不同温度下复合涂料的抑菌率
上述空白对照使用的PLA薄膜,从以上结果可以看出,PLA薄膜和Ag/PLA复合薄膜的抑菌率随温度升高而增加,其中PLA薄膜在49℃的温度下有25.23%的抗菌活性。复合涂料在正常培养温度下即37℃的抑菌效果并不理想仅为60.86%,但在49℃的温度下却提高到了93.42%。说明高温与纳米银在协同作用下使得本身没有较高抗菌活性的低纳米银浓度的复合涂料产生了较高的抗菌效果。
近年来非接触性金属植入感应加热是一种新兴的防止金属植入物感染的方法,即通过电磁加热在体外加热金属植入物到60℃以高温杀死细菌并清除表面生物膜。但因为有效温度过高,受热不均匀,温度不好控制等问题常常产生组织热损伤。而我们的复合涂料可以很好地解决上述问题,因为隔热层的作用,表面温度上升变慢使得可以更好的控制温度,而在加热状态下镀层中的银离子更多的释放到了组织中与高温协同作用起到了非常好的杀菌作用,而且不需要作用温度达到60℃的高温,这极大地减少了对组织的热损伤。因此本发明的复合涂料不仅在使用中有着优秀的抗菌效果,在必要时还可以通过体外电磁加热的方法,进一步提升材料的杀菌能力,大大减少金属植入物感染的发生率。
实施例3复合涂料的隔热性能
1.复合涂料的隔热效果
为评估复合涂料的热绝缘效果以及探究加入纳米银颗粒的浓度和粒径的大小对热绝缘效果的影响。我们设置了8个实验组,包括空白对照组和PLA组,20nm 0.1g/100ml纳米银组,20nm 0.2g/100ml纳米银组,20nm 0.3g/100ml纳米银组,20nm 0.4g/100ml纳米银组,50nm 0.3g/100ml纳米银组,100nm 0.3g/100ml纳米银组。我们将复合涂料采用浇筑法制备成Φ10*0.3的圆形薄膜。把薄膜放在50摄氏度的恒温水浴中。用美国FLIR-X6900sc-SLS热成像仪(FLIR-X6900sc-SLS)拍摄实验组的热图像,记录温度变化。观察不同薄膜在50℃恒温水浴中的升温表现,直观的展现不同薄膜的热绝缘效果。
表3不同复合涂料的隔热性能
从结果来看Ag/PLA复合薄膜确实有着不错的热绝缘效果,在50℃的环境下其表面温度明显低于单纯PLA薄膜,更比空白对照低。而且随着银纳米粒子浓度的升高以及粒径的增大热绝缘能力也显著提升。因此想要复合涂料热绝缘效果更好,就需要引入更多的粒径更大的纳米银粒子。结合之前不同纳米银浓度与粒径的抗菌效果最终为了兼顾抗菌与隔热,纳米银粒子应选用20nm左右的粒径,浓度越大越好。结合经济因素,以及我们的使用目的,我们最终选定了20nm0.3wt%纳米银粒子复合涂料。因为其在升温过程中最大温差已经达到了7.74℃,这已经足够达到我们保护组织免受热损伤的目的。
2.Al2O3镀层与复合涂料的隔热效果
复合涂料均匀涂布在Al2O3镀层表面就形成最终的复合涂层,为验证复合涂层在生物体内的表现,将单纯镍钛记忆合金棒与复合涂层镍钛记忆合金棒分别植入兔子背部组织内,并将光纤测温探头固定在镍钛记忆合金棒上,最后获得在相同的加热条件下的温度曲线。
从图1结果可以看出,复合涂层镍钛记忆合金棒具有优秀的隔热效果,从开始加热起到120s后加热结束实验组组的温度均小于镍钛记忆合金棒,并且温差越来越大。可以看到各组在加热结束时温度的情况,镍钛记忆合金棒约为54.55±0.71℃,复合涂层镍钛记忆合金棒约为48.39±0.45℃,温差约为6.16℃。因此复合涂层在生物体内可以起到优秀的隔热作用,具有保护机体免受金属植入物产热造成组织损伤的效果。
实施例4复合涂料的生物相容性
1.体外生物相容性
为检测细胞活力,选用从美国细胞库中购得的鼠成纤维细胞(L929),在96孔板上每孔培养24小时(每孔,200uL培养基),然后加入0.2ml新鲜培养基和改良的DMEM培养基、10%胎牛血清(Gibco,美国)、1%青霉素(Gibco,美国)和1%链霉素(Gibco,美国),在95%的空气湿度和5%的CO2中37℃孵育1、3和5天。根据ISO/EN 10993-5标准,将样本以3cm2/ml浸泡在DMEM培养基中,37℃孵育48h,在给定的时间点,用细胞计数试剂盒-8(CCK-8)测定细胞活力,在450nm处用分光光度计酶免疫分析分析仪(Perkin Elmer Enspire 2300,USA)测量每个孔的光密度,以指示细胞活力。所有实验都是一式三份。
纯聚乳酸薄膜,Ag/PLA复合膜、纳米银/PLA/氧化铝复合涂层镍钛记忆合金棒、纯镍钛记忆合金棒对鼠成纤维细胞L929增殖的影响如下图2所示,根据CCK-8分析,与空白对照组相比,纯镍钛记忆合金棒组的L929细胞增殖能力略有下降,这说明镍钛形状记忆合金棒具有微弱的细胞毒性。Ag/PLA复合膜组和复合涂层镍钛记忆合金棒组间有较好的增殖能力,说明复合膜和复合涂层具有良好的生物相容性,可降低镍钛记忆合金棒的细胞毒性。
许多研究表明,生物材料的表面形态与细胞粘附、细胞生长、迁移和分化有关,这对生物材料和组织工程具有重要意义。材料表面的孔隙率和平整度是影响细胞粘附和生长的关键因素,与平坦的表面相比,高孔隙率的表面更有利于细胞形成片状的脂壁和丝状足,以调整其结构以适应摄食和迁移。本发明复合涂层表面嵌入了大量的纳米银,使其表面更有利于细胞的粘附、生长和分化。图3显示了直接在不同样品上孵育的L929细胞的形态和增殖情况,与空白对照组相比,复合薄膜更适合细胞生长。培养2小时后,三组L929细胞开始贴壁;培养1天后,L929细胞在三组样品上的粘附和扩散增强,出现丝状足和片状脂肪细胞;培养3天后,L929细胞在Ag/PLA复合薄膜上的丝状伪足多于正常对照组和PLA组,其粘附和铺展均优于正常对照组和PLA组。
2.动物体内实验
本实验选用新西兰实验兔。所有动物均在控制温度(22-26℃)、光照12小时、黑暗12小时的条件下饲养,并辅以适当的食物和水。家兔随机分为3组:纳米银/PLA/氧化铝复合涂层镍钛记忆合金棒组、镍钛记忆合金棒组及假手术对照组,不经任何处理,暴露创面,用0.4浓度的异氟烷匀速吸入麻醉家兔,并进一步固定和剃毛,手术区用碘消毒,将植入物肌肉内放置在兔脊柱附近,然后用光纤温度计将温度测量固定在镍钛表面,以测量温度变化。伤口用尼龙单丝缝合,并用青霉素预防术后伤口感染,对每只兔子进行手术后均获得X线图像。术后第3天,用电磁加热装置对家兔镍钛形状记忆合金棒进行加热。在光纤温度计的监测下,保证电磁加热装置固定在相同的加热功率和加热距离下,每组开启120s,术后15天取每只兔的全血及植入物周围组织进行组织病理学分析。组织用10%甲醇溶液固定(上海贝奥蒂姆),然后用乙醇脱水,石蜡包埋。取组织切片,苏木精伊红染色。免疫组化也在该组织上进行。组织的组织病理学变化由一位经验丰富的病理学家在光学显微镜下进行了盲法检查(Aperio VERSA 8,德国)。
如图4a所示,将镍钛记忆合金棒和复合涂层镍钛记忆合金棒分别植入兔背部组织,并将光纤温度探头固定在合金棒上以假手术组为对照组。如图4b所示,在相同的加热条件下,从加热开始到结束共120秒,两组间的温差越来越大。在图4c中,镍钛记忆合金棒和复合涂层镍钛记忆合金棒在加热结束时分别为54.55±0.71℃和48.39±0.45℃,温差约为6.16℃。然而,值得注意的是,镍钛记忆合金棒的温度在停止加热后迅速下降,而复合涂层镍钛记忆合金棒的温度则在停热后稍有下降,温度下降幅度低于镍钛记忆合金棒组。在图4d中,镍钛记忆合金棒家兔血清中镍离子含量较高,约为63±4mg/ml。但在对照组和复合涂层镍钛记忆合金棒组分别为29±2mg/ml和37±3mg/ml。与纯镍钛记忆合金棒相比,植入复合涂层镍钛记忆合金棒的兔血清中镍离子浓度明显降低。在实际应用中,复合涂层能有效地减少Ni离子的释放,提高镍钛形状记忆合金的生物相容性。
周围组织的HE染色如图5所示。与对照组相比,镍钛记忆合金棒组和复合涂层镍钛记忆合金棒组可见炎性细胞浸润及纤维组织薄层,其中镍钛记忆合金棒组有大量炎性细胞浸润,肌纤维细胞内空泡有细胞溶解迹象。但是复合涂层镍钛记忆合金棒组比镍钛记忆合金棒组弱,仅有少量炎性细胞浸润,肌纤维细胞形态正常。人类组织细胞耐热性差,高温可通过多种机制杀死细胞,包括坏死、凋亡和与核分裂灾难相关的模式。当细胞所处的环境温度高于其所能耐受的最高温度(约43℃)时,细胞发生一系列变化,包括染色体畸变、有丝分裂障碍、细胞骨架损伤、膜流动性受限等,最终死亡。但是,如果人体局部仅略高于临界温度,这个过程相对温和,人体组织也能忍受。当局部温度高于50℃时,即使在较短的时间内也会发生明显的组织热损伤,当局部温度超过56℃的临界温度时,会发生不可逆的组织热损伤。复合涂层具有良好的隔热性能和生物相容性。在交变磁场作用下,镍钛记忆合金棒的温度迅速升高,达到54.6℃,而复合涂层的表面温度保持相对安全。复合涂层的保温效果在组织耐受范围内,虽然也有轻微的组织损伤,但还没有达到人体不能忍受的程度。因此,复合涂层具有良好的耐蚀性、生物活性和良好的隔热性能,在体内金属种植体表面改性中具有广阔的应用前景,也为临床人体种植体的研究提供了新的视角。
Claims (1)
1.一种镍钛形状记忆合金涂层的制备方法,其特征在于包括在镍钛形状记忆合金表面涂覆复合涂料的步骤,以及在涂覆复合涂料前使用微弧氧化的方法在镍钛形状记忆合金表面形成氧化铝镀层的步骤,所述复合涂料由纳米银、聚乳酸、PVP和溶剂组成,所述纳米银的浓度为0.1-0.5g/100ml,所述聚乳酸的浓度为8-15wt%,所述PVP的浓度是纳米银的1-5倍,所述纳米银的粒径为20-100nm,所述溶剂为二氯甲烷,
所述微弧氧化的电解液含有0.15M NaAlO2和0.03M NaH2PO2·H2O;
所述微弧氧化的阳极为镍钛形状记忆合金,阴极是螺旋钢管,通电占空比30%,恒定正向电流12A,恒定反向电流4A,恒定正向电压420V,恒定反向电压75V,通电时间30分钟,并且电解液的温度保持在20℃。
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