钛及钛合金外科植入物阳极氧化表面形貌及元素含量分布研究

Study on Surface Morphology&Elements Distribution of Anodized Surface forTitanium and Titanium Alloys Surgical Implants

目的探讨外科植入物产品阳极氧化表面元素含量分布及表面形貌分析,以促进产业优化,服务企业发展。方法采用扫描电镜及能谱仪对试样阳极氧化膜形貌和表面元素含量进行分析,并对各元素分布情况进行统计分析。结果着色阳极氧化产品表面形貌为不规则的凹凸不平状且均匀分布在氧化膜表面,其表面所含元素除基体元素外,有11.07%的产品表面包含Na、Si、P、S、Al等其他元素中一种或多种,且含量(质量分数)几乎全部落在小于1.00%这个区间。与着色阳极氧化产品相比,微弧阳极氧化产品表面形貌为均匀分布的火山口状突起,内部出现很多孔洞,直径为100~300 nm且出现交联,在整体上呈现立体孔隙结构,且表面所包含其他元素均匀分布在阳极氧化产品表面,其表面所包含元素除基体元素外,均还包含Na、Si、P、S、Ca、Mg、Fe等其他元素中一种或多种,且含量(质量分数)基本落在小于10.00%这个区间,其中Si、P含量落在1.00%~10.00%区间的批次占比均高于80%。结论研究结果显示不同企业、不同生产工艺的阳极氧化表面所含元素的种类和含量差异较大,但对优化改进企业生产工艺而言具有指导性意义,如企业应严格控制电解液的配方,且定期更换;电解池和清洗池的材料应与植入物产品基体材料相同;不同材料的产品应分开进行清洗;对于有意添加的元素(如Si、P、Ca等),其含量应尽量落在同一区间内,以确保作用最大化;而对于工艺引入的杂质元素,其含量应尽可能低,以降低不良反应发生的可能性。此结果对表面元素定量分析、生物安全性评价及临床应用也具有一定的参考意义。

As an important method of surface modification,surface anodic oxidation was widely used in surgical implants.In order to promote industrial optimization as well as service enterprise development,the distribution of surface elements and the surface morphology of anodic oxidation surgical implants were studied in this work.The anodic oxidation products of surgical implants provided by different enterprises were selected as research samples,and the precision cutting machine was used to cut the large-sized sample into a typical sample with suitable-sized.Firstly,the morphology of anodic oxidation film on the sample surface was analyzed by the scanning electron microscopy(Hitachi,S-4800 or Thermo Fisher Scientific,Scios 2),and the pore size of micro-arc anodic oxidation film was measured at the same time.Finally,the element content on the surface of the sample was analyzed by the energy dispersive spectrometer(Bruker,XFlash detector 630M)which was matched with the scanning electron microscopy,and then the distribution of each element was analyzed statistically.The surface morphology of the colored anodic oxidation film was irregular and uneven,but uniformly distributed on the surface.Other than the matrix elements,the surface of 11.07%colored anodic oxidation products contained one or more elements such as Na,Si,P,S,Al and so on.The content(mass fraction)of other elements was almost all in the range of less than 1.00%.Compared with the colored anodic oxidation,the crater-like protrusion which were well-distributed were observed on the surface of micro-arc anodic oxidation film,then many pores with diameters of about 100—300 nm appeared and cross-linked with each other,the three-dimensional pore structure was formed.Except the matrix elements,the surface of micro-arc anodic oxidation film contained one or more kinds of other elements such as Na,Si,P,S,Ca,Mg,Fe and so on.The content(mass fraction)of other elements mostly fell in the range of less than 10.00%,and the proportion of products whose content of Si,P elements fell in the range of 1.00%—10.00%were higher than 80%.The surface elements were analyzed by surface scanning showed that the elements were uniformly distributed on the surface of anodic oxidation film.As well the stability of anodic oxidation process and the uniformity of related products were supported by this result indirectly.The results show that the anodic oxidation film of the products by different enterprises and different production processes have different kinds and contents of the elements.But it’s instructive for the enterprises to optimize and improve their production processes,such as control the composition of electrolyte strictly and renew regularly;keep the electrolytic cell and cleaning cell materials consistent with the implant products;clean the different materials products separately;make the content of intentionally add elements(Si,P,Ca)fall in the same range to ensure the effect maximum,decrease the content of impurity elements as low as possible to reduce the possibility of adverse reactions.This also has certain reference significance for quantitative analysis of surface element,biological evaluation and clinical application.