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骨科镁基植入物表面涂层改性技术的研究进展
柳伯韬
胡晓东
郝明明
彭兆祥
作者及单位信息
·
DOI： 10.3760/cma.j.cn121113-20230823-00119
Research progress of surface coating modification techniques for magnesium-based implants in orthopaedics
Liu Botao
Hu Xiaodong
Hao Mingming
Peng Zhaoxiang
Authors Info & Affiliations
Liu Botao
Department of Joint and Sports Medicine, the Affiliated Lihuili Hospital, Ningbo University, Ningbo 315040, China
Hu Xiaodong
Department of Joint and Sports Medicine, the Affiliated Lihuili Hospital, Ningbo University, Ningbo 315040, China
Hao Mingming
Department of Joint and Sports Medicine, the Affiliated Lihuili Hospital, Ningbo University, Ningbo 315040, China
Peng Zhaoxiang
Department of Joint and Sports Medicine, the Affiliated Lihuili Hospital, Ningbo University, Ningbo 315040, China
·
DOI： 10.3760/cma.j.cn121113-20230823-00119
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摘要

镁及镁合金具有优异的机械性能、可降解性和生物相容性，这使其在骨科领域得到广泛关注与研究。但镁及镁合金过快的降解速度无法匹配骨骼自身愈合速度，并可能对周围细胞定植生长与分化产生不利影响，引起植入物早期松动，从而限制其在临床上的广泛应用。在解决镁植入物腐蚀速率不可控问题方面，表面涂层改性是一种可行且极具应用前景的抗腐蚀方案。表面涂层改性技术可以通过改善植入物表面骨诱导能力（如以磷酸盐陶瓷为基础的仿生涂层）或改善抗腐蚀性能（如耐磨损耐腐蚀的微弧氧化涂层、具有自修复潜力的植酸涂层）来优化骨-植入物界面的整合。在调控镁植入物降解速率的同时，还可通过复合成分改性实现促骨整合、药物传递、光热治疗等多功能应用。通过列举骨科镁植入物表面不同的涂层改性方案的优缺点、总结各种制备工艺中的关键技术以及对其复合改性方案进行探讨，可为制备满足骨科临床应用需求的多功能镁植入物提供参考。

镁;假体和植入物;表面改性;涂层
ABSTRACT

Magnesium and its alloys have been widely studied in the field of orthopaedics for their desirable mechanical properties, biodegradability and biocompatibility. However, the rapid degradation rate of magnesium and its alloys cannot match the healing process of bone itself, and may adversely affect the adhesion, growth and differentiation of surrounding cells, resulting in early loosening of implants, thus limiting their wide clinical application. Surface coating modification is a feasible and promising anti-corrosion solution to solve the problem of uncontrollable corrosion rate of magnesium implants. The surface coating modification technology can optimize the integration of the bone-implant interface by improving the bone induction ability of the implant surface (such as the bio-mimetic coating based on phosphate ceramics) or improving the corrosion resistance (such as the micro-arc oxidation coating with wear resistance and corrosion resistance, and the phytic acid coating with self-healing potential). While optimizing the degradation rate of magnesium implant, it can also realize multiple functions such as promoting osseointegration, drug delivery and photothermal therapy through composite component modification. In this paper, the advantages and disadvantages of different coating modification method on the surface of orthopaedic magnesium implants are comprehensively illustrated, and the key technologies in each preparation process are summarized and the composite modification methods are further discussed, so as to provide references for the preparation of multifunctional magnesium implants that meet the requirements of orthopaedic applications.

Magnesium;Prostheses and implants;Surface modification;Coatings
Peng Zhaoxiang, Email: mocdef.labiamtohoaxzp
Copyright by Chinese Medical Association
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All articles published represent the opinions of the authors, and do not reflect the official policy of the Chinese Medical Association or the Editorial Board, unless this is clearly specified.
引用本文

柳伯韬,胡晓东,郝明明,等. 骨科镁基植入物表面涂层改性技术的研究进展[J]. 中华骨科杂志,2024,44(01)：58-64.

DOI:10.3760/cma.j.cn121113-20230823-00119

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人口老龄化是全球面临的重要社会问题之一。随着老龄化趋势的加剧，临床上对骨科植入物的需求增大，推动了植入器械的创新发展 [ 1 ]。镁金属作为一种新兴的可生物降解材料，凭借其良好的生物相容性、优异的机械性能和机体可吸收性被认为是一种具有发展前景的骨科植入材料。作为骨科植入物的备选材料，镁金属能起到调节成骨分化、促进分离段骨质矿化的作用 [ 2 , 3 , 4 ]。已有研究证明镁离子的补充能够有效促进骨质沉积，提高骨密度 [ 5 ]。在机械性能上，镁是目前工程应用中最轻的金属材料，具有密度低、比强度高、比刚度高的性能优点，其屈服强度和抗拉伸能力与人体骨组织接近，可达到与皮质骨相似的弹性模量（15~20 GPa），能有效避免应力集中引起的成骨障碍和骨结合不良 [ 6 ]。相较于传统的惰性材料，可生物降解的镁植入物随着机体的代谢吸收能被新生骨组织完全替代，从而避免了骨愈合后二次手术取出植入物，减少了患者创伤、降低了医疗卫生成本。另外，镁植入物的降解颗粒可被机体吸收，避免了术后不可吸收的磨损颗粒对植入物周围组织产生持续的机械刺激，降低无菌性松动发生的风险 [ 7 ]。
虽然镁具备优良的生物活性和机械性能，使用镁基合金作为植入材料的成功临床案例已有报道，但镁是一种化学性质活跃的金属元素，其在人体内不受调控的降解行为是限制镁植入物无法在临床广泛应用的重要原因之一。快速的降解常伴随植入部位的氢气积累，并可能加速植入物力学性能的衰减，导致机械性能不稳定，影响内固定效果 [ 5 ]。Noviana等 [ 8 ]的研究表明裸镁在体内降解产生的气肿会影响机体的气体交换并干扰细胞免疫的平衡，使机体处于高应激状态。此外，降解产生的局部气腔还会影响成骨细胞的黏附并对骨折端末梢血供造成负面影响，甚至可能引发气体栓塞而影响术后安全。
为提高镁金属在人体植入的安全性与可靠性，目前关于调控镁降解速率的方案已得到研究人员的广泛探索，主要的方向包括新型合金体系的开发和表面涂层改性技术的研发。合金化通过在镁基体中添加Ca、Zn、Al等第二相合金成分可以在一定程度上起到延缓降解、改善机械强度的作用 [ 9 , 10 , 11 ]。但是目前关于合金成分的生物安全性与合适配比尚无定论，并且有学者认为降解过程中杂质元素的不均匀析出会加速植入物后期的腐蚀进展，产生负面的降解效应。因此，单纯的合金化在镁植入物的抗腐蚀应用仍需进一步研究 [ 12 ]。目标是在保证植入物可控降解速率的同时兼顾植入物的生物相容性，在这个层面涂层改性技术被认为是一种可行的抗腐蚀方案 [ 13 , 14 ]。
涂层改性技术是通过物理涂覆、化学沉积等手段在镁植入物表面形成一层合适的抗腐蚀层以改善腐蚀介质与镁基植入物的接触，从而在不干扰镁合金晶粒形貌的前提下起到调控降解速率的作用 [ 15 , 16 ]。表面涂层的存在防止了镁金属腐蚀产物的迅速堆积，降低了因快速降解而对骨-植入物界面的有害影响 [ 17 ]。虽然涂层改性技术并不能直接改善植入物整体的机械强度，但是通过降低植入物在体液环境下的腐蚀速率能对镁金属的力学衰减起到有力的保护，从而使镁金属腐蚀速率与骨折的再生速率相匹配，为受损的骨组织恢复机械强度提供了时间 [ 5 ]；同时，在临床植入过程中，涂层在一定程度上也能降低应力作用对镁金属基体的损伤。
与未涂覆的镁植入物相比，涂层改性技术有两个主要优势。首先，防止了镁金属在植入初始阶段释放过量氢气和产生对成骨细胞有不利影响的极端碱性环境；其次，能调控镁离子的释放，从而稳定诱导新骨组织的形成，促进骨折断端的矿化愈合。通过优化表面微观形状，涂层还能提供更适宜的黏附界面，促进成骨细胞的增殖和铺展，提高镁植入物的骨整合性能 [ 18 ]。此外，涂层还具有丰富的改性位点，为复合涂层的制备提供了基础。通过复合涂层改性的方法可以引入药物递送系统、光热治疗系统等，针对特定临床场景进行优化设计，弥补镁植入物在临床应用中的不足 [ 19 ]。现有研究表明这种复合涂层改性技术改善了镁金属的生物相容性并丰富了植入物的生物学功能，具有较为广泛的应用前景。本综述集中举例了近年来应用于镁基植入物的涂层制备工艺以及基于不同涂层技术的复合改性方案，为镁基植入物在骨科领域的进一步研究与应用提供参考。
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彭兆祥，Email: mocdef.labiamtohoaxzp
B
浙江省医药卫生科技计划项目 (2022KY1083)
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