CN112281199B - 基于溶液体系的超声辅助微弧氧化复合膜层的制备与应用 - Google Patents
基于溶液体系的超声辅助微弧氧化复合膜层的制备与应用 Download PDFInfo
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Abstract
本发明涉及一种基于溶液体系的超声辅助微弧氧化复合膜层的制备与应用,属于材料表面处理和医用生物材料工程领域。方法以阳离子钙源、阴离子钙源和磷源形成的溶液体系作为微弧氧化电解液,以钛或钛合金作为微弧氧化阳极,以惰性电极作为微弧氧化阴极进行微弧氧化,微弧氧化的同时对所述电解液进行超声处理;最终在阳极表面原位生成羟基磷灰石膜层,即得到羟基磷灰石与二氧化钛的复合膜层。本发明制备的复合膜层具有优异的生物相容性和成骨活性,可作为人体骨骼植入体的表面修饰陶瓷膜层。
Description
技术领域
本发明属于材料表面处理和医用生物材料工程领域,更具体地,涉及基于溶液体系的超声辅助微弧氧化复合膜层的制备与应用,特别涉及一种采用溶液体系的一步法超声辅助微弧氧化方法,可在钛及其合金表面制备羟基磷灰石/二氧化钛复合膜层。
背景技术
当前,世界人口老龄化和事故致伤致残率的上升所导致的人体骨骼病变促使对人体骨骼植入体需求的急剧上升。钛及其合金由于具有与人体骨骼相似的机械性能与生物相容性,现已被广泛应用于人体骨骼植入体的加工制备过程中。然后,钛及其合金表面存在着一层钝化膜,导致其生物活性不足,无法有效促使骨骼生长与骨质增生,并可能诱发纤维组织包覆,减弱与人体骨组织的结合力,致使发炎、病变并最终导致其失效,造成患者的巨大痛苦与社会资源的极大浪费。因此,增强钛基骨骼植入体的生物活性一直以来是学术界与工业界关注的重点。
羟基磷灰石(HAP)是人体骨骼的主要无机成分,它能与机体组织在界面上实现化学键性结合,其在体内有一定的溶解度,能释放对机体无害的离子,能参与体内代谢,对骨质增生有刺激或诱导作用,能促进缺损组织的修复,显示出优异的生物活性。当前,主流工业采用的等离子体喷涂方法将羟基磷灰石涂覆到钛及其合金的表面,但这种方法具有明显的局限性。首先,等离子体喷涂易导致巨大的残余应力,使得喷涂的羟基磷灰石易脱落,不仅难以发挥作用,还易导致发炎、磨损等一系列问题;其次,对于具有复杂几何结构的骨骼植入体,采用等离子体喷涂方法,将难以获得均匀羟基磷灰石膜层。
基于此,学术界与工业就将目光投向了基于湿法电化学的微弧氧化方法。不同于等离子体喷涂,微弧氧化所产生的陶瓷膜,以冶金结合的方式与基体连接,具有很高的结合力,不易脱落;由于湿法化学的特性,微弧氧化对于复杂几何结构具有更强的处理能力。与此同时,微弧氧化还具有周期短、工艺简洁、环境友好、产品廉价等一系列优势。因此,在钛及其合金上,采用微弧氧化制备具有生物活性的羟基磷灰石/二氧化钛复合膜层,是一种有效的解决钛合金低生物活性的方法。
然而,目前采用微弧氧化制备具有生物活性的羟基磷灰石/二氧化钛复合膜层,均采用了含水溶性较低阳离子钙盐(如:醋酸钙、葡萄糖酸钙等)的悬浊液。不同于稳定的溶液体系,悬浊液并不稳定,极易沉降,不易维护,且对溶液组分的利用率极低,严重限制了微弧氧化在钛基植入体上的应用。因此,设计一种稳定的溶液体系,克服悬浊液的不稳定性,有利于微弧氧化在钛基植入体上的大规模工业应用。
发明内容
本发明解决了现有技术中制备的羟基磷灰石易脱落,膜层不均匀,且利用悬浊液进行微弧氧化利用率低的技术问题。为了克服现有制备羟基磷灰石/二氧化钛复合膜层过程中存在的技术问题,提供了一种采用稳定溶液体系的一步法超声辅助微弧氧化方法,其目的在于利用一步法超声辅助微弧氧化方法,在稳定的溶液体系中,在钛及其合金表面,制备羟基磷灰石/二氧化钛复合膜层。通过采用稳定的溶液体系,克服了传统悬浊液导致的不稳定性问题,从而有助于该方法的工业化应用。
根据本发明的第一方面,提供了一种采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,所述方法以阳离子钙源、阴离子钙源和磷源形成的溶液体系作为微弧氧化电解液,以钛或钛合金作为微弧氧化阳极,以惰性电极作为微弧氧化阴极进行微弧氧化,微弧氧化的同时对所述电解液进行超声处理;
通过外加超声场的空化效应,电解液中形成细小的Ca和P团簇,并通过微弧氧化的外电场作用,促使阴离子钙源向阳极进行电迁移,使Ca和P团簇生长为羟基磷灰石晶核,然后,在电击穿的热效应和电效应作用下,羟基磷灰石晶核逐渐生长,最终在阳极表面原位生成羟基磷灰石膜层,即得到羟基磷灰石与二氧化钛的复合膜层。
优选地,所述微弧氧化的工作电压为300-700V,工作频率为100-600Hz,电流密度为0.05-0.50A/cm2,占空比为0~50%,处理时间为5~30min,反应温度为0~40℃。
优选地,所述超声处理的功率为100-500W,频率为20-50kHz。
优选地,所述钛合金为TA1、TA2、TA3、Ti-6Al-4V、Ti-Ni、Ti-2Al-2.5Zr、Ti-32Mo或Ti-Mo-Ni。
优选地,所述阳离子钙源为乳酸钙、葡萄糖酸钙、氯化钙或硝酸钙,所述微弧氧化电解液中阳离子钙源的浓度为10-30g/L。
优选地,所述阴离子钙源为乙二胺四乙酸钙钠或乙二胺四乙酸钙钾,所述微弧氧化电解液中阴离子钙源的浓度为0.5-2g/L。
优选地,所述磷源为磷酸二氢钠或磷酸二氢钾,所述微弧氧化电解液中磷源的浓度为5-10g/L。
优选地,所述惰性电极为铂片、石墨或不锈钢;所述阳极和阴极的距离为3cm-20cm。
按照本发明的另一方面,提供了任一所述方法制备得到的羟基磷灰石与二氧化钛复合膜层。
按照本发明的另一方面,提供了所述的羟基磷灰石与二氧化钛复合膜层用于制备骨骼植入体的表面修饰陶瓷膜层的应用。
总体而言,通过本发明所构思的以上技术方案与现有技术相比,主要具备以下的技术优点:
(1)本发明采用复合钙源,在阳离子钙盐的基础上,添加了阴离子钙盐,避免了悬浊液的形成。同时,采用了超声辅助的微弧氧化方法,在钛及其合金表面,一步制备羟基磷灰石/二氧化钛复合膜层。通过外加超声场的空化效应,在溶液中,形成细小的Ca、P团簇;借助外电场,促使阴离子钙盐向钛阳极电迁移,帮助Ca、P团簇生长为羟基磷灰石晶核;随后,在电击穿的热效应和电效应作用下(羟基磷灰石(HA)的生长过程中,电击穿(dielectricbreakdown)所导致的局部放电(plasma discharge)会释放大量的热量,导致局部温度的急剧上升,促进其形成;与此同时,羟基磷灰石的长大过程也依靠离子交换过程,也就是说之前的HA带正电,则将吸引带负电的磷酸根;而之前HA若带负电,那么将吸引钙离子。与此同时,微弧氧化的外电场也会促进相应的传质过程),羟基磷灰石晶核逐渐生长;最终,在二氧化钛表面,形成了羟基磷灰石膜层,极大地提高了钛基植入体的生物活性。该方法操作简单方便、对设备要求较低、简单快捷,有利于工业化的大规模生产。
(2)本发明提供了一种稳定性溶液体系,代替传统悬浊液体系,为微弧氧化方法一步制备成羟基磷灰石/二氧化钛复合膜层提供了稳定反应工艺简单、流程短、无污染、能耗少,适合工业化生产,该复合膜层具有优异的生物相容性和成骨活性,可作为人体骨骼植入体的表面修饰陶瓷膜层。
(3)本发明采用稳定溶液体系,经过一步超声辅助微弧氧化处理,在钛及其合金表面,制备出羟基磷灰石/二氧化钛复合膜层,制备工艺简单可控,电解液体系稳定、可充分利用,原料易得,成本低廉,适合工业大规模生产。
(4)本发明仅需一步微弧氧化过程即可制备出羟基磷灰石/二氧化钛复合膜层,具有良好的生物相容性和成骨活性,并提高其耐蚀性能,为钛基骨骼植入体的稳定性和生物功能性提供保障。
附图说明
图1为实施实例1制备的陶瓷膜截面的TEM照片。
图2为图1中虚线框所选区域的TEM照片。
图3为图2对应区域的EDX照片。
图4为图2中片层沉淀物的TEM高分辨照片。
图5为实施实例2制备的陶瓷膜表面的SEM照片。
图6为实施实例2制备的陶瓷膜的XRD谱图。
图7为实施实例3制备的陶瓷膜表面的SEM照片。
图8为实施实例3制备的陶瓷膜的XRD谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
(1)将纯钛进行去油去污处理,然后用砂纸逐级打磨,用丙酮清洗后干燥;试样用绝缘胶带包覆,确保反应面积尺寸为20mm×20mm;
(2)配置微弧氧化溶液,质量浓度如下:0.15mol/L乳酸钙,0.09mol/L磷酸二氢钠、2g/L乙二胺四乙酸钙钠;通过磁力搅拌器充分搅拌,使电解液分散均匀;
(3)以预处理后的纯钛为阳极,不锈钢为阴极,将阳极、阴极接脉冲电源,阴极、阳极板距离为6cm,并置于上述电解液中;采用功率360W,频率40kHz的超声场辅助微弧氧化过程,设定微弧氧化电源参数:电流密度为0.08A/cm2,频率为600Hz,总占空比为20%,温度为30℃,时间为800s。
(4)反应完毕后,取出带有陶瓷膜层的试样用去离子水冲洗,自然晾干,即得到羟基磷灰石/二氧化钛复合膜层。
实施例2
(1)将Ti6Al4V进行去油去污处理,然后用600#、1000#、1500#、2000#SiC砂纸逐级进行打磨,用丙酮清洗后干燥;试样用绝缘胶带包覆,确保反应面积尺寸为10mm×10mm;
(2)配置微弧氧化溶液,质量浓度如下:0.30mol/L乳酸钙,0.18mol/L磷酸二氢钠、1g/L乙二胺四乙酸钙钠;通过磁力搅拌器充分搅拌,使电解液分散均匀;
(3)以预处理后的纯钛为阳极,不锈钢为阴极,将阳极、阴极接脉冲电源,阴极、阳极板距离为12cm,并置于上述电解液中;采用功率400W,频率35kHz的超声场辅助微弧氧化过程,设定微弧氧化电源参数:电流密度为0.12A/cm2,频率为100Hz,总占空比为20%,温度为30℃,时间为600s;
(4)反应完毕后,取出带有陶瓷膜层的试样用去离子水冲洗,自然晾干,即得到羟基磷灰石/二氧化钛复合膜层。
实施例3
(1)将TA2进行去油去污处理,然后逐级进行打磨,用丙酮清洗后干燥;试样用绝缘胶带包覆,确保反应面积尺寸为15mm×15mm;
(2)配置微弧氧化溶液,质量浓度如下:0.05mol/L葡萄糖酸钙,0.03mol/L磷酸二氢钾、0.5g/L乙二胺四乙酸钙钠;通过磁力搅拌器充分搅拌,使电解液分散均匀;
(3)以预处理后的纯钛为阳极,不锈钢为阴极,将阳极、阴极接脉冲电源,阴极、阳极板距离为12cm,并置于上述电解液中;采用功率400W,频率40kHz的超声场辅助微弧氧化过程,设定微弧氧化电源参数:电流密度为0.10A/cm2,频率为1000Hz,总占空比为10%,温度为30℃,时间为1000s;
(4)反应完毕后,取出带有陶瓷膜层的试样用去离子水冲洗,自然晾干,即得到羟基磷灰石/二氧化钛复合膜层。
图1为实施例1合成的陶瓷膜层的截面形貌,可见陶瓷膜由两部分组成,包括:多孔内层和片层状的外层。内层厚度在2~4μm之间。
图2为图1中虚线框所选区域的放大照片,可见内层中具有大量微孔和微裂纹,外层片状沉淀物的厚度在400~500nm之间。
图3为图2对应区域的EDX照片,分析表明:内层为TiO2膜层,而外层则是富Ca、P的磷灰石类似物。
图4为外层片状沉淀物的TEM高分辨照片,发现其为羟基磷灰石,这说明了羟基磷灰石/二氧化钛复合膜层的形成。
图5为实施例2制备的陶瓷膜的表面形貌。陶瓷膜表层出现了明显的沉淀物,并覆盖了一部分孔洞。
图6为实施实例2制备的陶瓷膜的XRD谱图,可发现出现了明显的二氧化钛及羟基磷灰石的特征峰,说明了羟基磷灰石/二氧化钛复合膜层的形成。
图7为实施例3制备的陶瓷膜的表面形貌。可明显观察到其表面的多孔结构与沉淀物。
图8为实施实例3制备的陶瓷膜的XRD谱图,可发现出现了明显的二氧化钛及羟基磷灰石的特征峰,说明了羟基磷灰石/二氧化钛复合膜层的形成。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,其特征在于,所述方法以阳离子钙源、阴离子钙源和磷源形成的溶液体系作为微弧氧化电解液,以钛或钛合金作为微弧氧化阳极,以惰性电极作为微弧氧化阴极进行微弧氧化,微弧氧化的同时对所述电解液进行超声处理;所述超声处理的功率为100-500W,频率为20-50kHz;所述阴离子钙源为乙二胺四乙酸钙钠或乙二胺四乙酸钙钾;
所述微弧氧化电解液中阳离子钙源的浓度为10-30g/L;所述微弧氧化电解液中阴离子钙源的浓度为0.5-2g/L;
所述磷源为磷酸二氢钠或磷酸二氢钾,所述微弧氧化电解液中磷源的浓度为5-10g/L;
通过外加超声场的空化效应,电解液中形成细小的Ca和P团簇,并通过微弧氧化的外电场作用,促使阴离子钙源向阳极进行电迁移,使Ca和P团簇生长为羟基磷灰石晶核,然后,在电击穿的热效应和电效应作用下,羟基磷灰石晶核逐渐生长,最终在阳极表面原位生成羟基磷灰石膜层,即得到羟基磷灰石与二氧化钛的复合膜层。
2.如权利要求1所述的采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,其特征在于,所述微弧氧化的工作电压为300-700V,工作频率为100-600Hz,电流密度为0.05-0.50A/cm2,占空比为0~50%,处理时间为5~30min,反应温度为0~40℃。
3.如权利要求1所述的采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,其特征在于,所述钛合金为TA1、TA2、TA3、Ti-6Al-4V、Ti-Ni、Ti-2Al-2.5Zr、Ti-32Mo或Ti-Mo-Ni。
4.如权利要求1所述的采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,其特征在于,所述阳离子钙源为乳酸钙、葡萄糖酸钙、氯化钙或硝酸钙。
5.如权利要求1所述的采用溶液体系制备羟基磷灰石与二氧化钛复合膜层的一步超声辅助微弧氧化方法,其特征在于,所述惰性电极为铂片、石墨或不锈钢;所述阳极和阴极的距离为3cm-20cm。
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CN102747403A (zh) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | 在医用钛合金表面制备掺镁羟基磷灰石/二氧化钛活性膜层的方法 |
CN103451706A (zh) * | 2013-09-02 | 2013-12-18 | 吉林大学 | 一种钛表面直接生成含羟基磷灰石生物陶瓷膜的制备方法 |
CN108103551A (zh) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | 一种促进微弧氧化膜层中羟基磷灰石结晶的方法 |
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