Publicado

2017-01-01

Titanium dioxide coatings on magnesium alloys for biomaterials: A review

Recubrimientos de dioxido de titanio sobre aleaciones de magnesio para biomateriales: Una revisión

Palabras clave:

Magnesium alloys, titanium dioxide, surface modification, coatings, biomedical (en)
Aleaciones de magnesio, dióxido de titanio, modificación superficial, recubrimientos, biomédico (es)

Autores/as

Magnesium and its alloys are used for biomaterials in orthopedic applications. Such alloys are still under development, and they are used due to their biocompatibility and mechanical (bone-like) properties that make them suitable to be used as biomaterials. Magnesium has potential to be used in biodegradable implants because of its capacity to support tissue regeneration processes. Therefore, multiple strategies have been developed to enhance magnesium properties. Coatings on magnesium alloys have been used to improve the cytocompatibility and corrosion resistance of magnesium. Particularly, titanium dioxide can be used as coating on magnesium to help regulating degradation rate and overcome some issues when magnesium is inserted into the human body. Accordingly, this paper is a critical review to consolidate the available literature about titanium dioxide coatings on magnesium alloys for potential use as biomaterials. The work focuses on coatings obtained by the sol-gel route as a promising technique for biomedical applications.
El magnesio y sus aleaciones, que aún se encuentran en desarrollo, se usan en aplicaciones ortopédicas debido a su biocompatibilidad y propiedades mecánicas (similares al hueso), que los hacen adecuados para aplicaciones en biomateriales. El magnesio tiene potencial para ser usado en implantes biodegradables dada su capacidad de soportar los procesos de regeneración de tejidos. En consecuencia, se han desarrollado varias estrategias para mejorar las propiedades del magnesio. Los recubrimientos sobre magnesio se emplean para mejorar su citocompatibilidad y resistencia a la corrosión. Específicamente, el dióxido de titanio se puede usar como recubrimiento protector sobre el magnesio, con el fin de ayudar a regular la velocidad de degradación y superar algunos problemas que se encuentran cuando el magnesio es implantado en el cuerpo. Por tanto, en este artículo se realizó una revisión crítica para consolidar la literatura disponible acerca de recubrimientos de dióxido de titanio sobre aleaciones de magnesio para potenciales aplicaciones en biomateriales. En este documento se hace énfasis en los recubrimientos obtenidos por medio de la de la ruta sol-gel como técnica prometedora para aplicaciones biomédicas.

Descargas

Los datos de descargas todavía no están disponibles.

Citas

Qizhi, C. and Thouas, G., Metallic implant biomaterials. Materials Science and Engineering: R: Reports, 87, pp. 1-57, 2015. DOI: 10.1016/j.mser.2014.10.001

Williams, D.F., On the mechanisms of biocompatibility. Biomaterials 29 (20) pp. 2941-2953, 2008. DOI: 10.1016/j.biomaterials.2008.04.023

Elshahawy, W., Advances in Ceramics - Electric and Magnetic Ceramics, Bioceramics, Ceramics and Environment. Edited by Costas Sikalidis. InTech, 2011. DOI: 10.5772/726

Murugan, R. and Ramakrishna, S., Development of nanocomposites for bone grafting. Composites Science and Technology, 65(15), pp. 2385-2406, 2005. DOI: 10.1016/j.compscitech.2005.07.022

Allo, B., Costa, D., Dixon, S., Mequanint, K. and Rizkalla, A., Bioactive and biodegradable nanocomposites and hybrid biomaterials for bone regeneration. Journal of Functional Biomaterials, 3(2), pp. 432-463, 2012. DOI: 10.3390/jfb3020432

Böstman, O. and Pihlajamäki, H., Clinical biocompatibility of biodegradable orthopaedic implants for internal fixation: A review. Biomaterials, 21(24), pp. 2615-2621, 2000. DOI: 10.1016/S0142- 9612(00)00129-0

Bergsma, E., Rozema, F., Bos, R. and De Bruijn. W., Foreign body reactions to resorbable Poly (l-Lactide) bone plates and screws used for the fixation of unstable zygomatic fractures. Journal of Oral and Maxillofacial Surgery, 51(6), pp. 666-670, 1993. DOI: 10.1016/S0278-2391(10)80267-8

Farraro, K., Kim, K., Woo, S., Flowers, J. and McCullough, M., Revolutionizing orthopaedic biomaterials: The potential of biodegradable and bioresorbable magnesium-based materials for functional tissue engineering. Journal of Biomechanicsvol, 47(9), pp. 1979-1986, 2014. DOI: 10.1016/j.jbiomech.2013.12.003

Gu, X. and Zheng, Y., A review on magnesium alloys as biodegradable materials. Frontiers of Materials Science in China, 4(2), pp. 111-115, 2010. DOI: 10.1007/s11706-010-0024-1

Witecka, A., Bogucka, A., Yamamoto, A., Máthis, K., Krajňák, T., Jaroszewicz, J. and Święszkowski, W., In vitro degradation of ZM21 magnesium alloy in simulated body fluids. Materials Science and Engineering: C, 65, pp. 59-69, 2016. DOI: 10.1016/j.msec.2016.04.01

Poinern, E., Brundavanam, S. and Fawcett, D., Biomedical magnesium alloys: A review of material properties, surface modifications and potential as a biodegradable orthopaedic implant. American Journal of Biomedical Engineering, 2(6), pp. 218-240, 2013. DOI: 10.5923/j.ajbe.20120206.02

Song G., Control of biodegradation of biocompatable magnesium alloys. Corrosion Science, 49(4), pp. 1696-1701, 2007. DOI: 10.1016/j.corsci.2007.01.001

Peng, W., Tan, L. and Yang, K., Surface modification on biodegradable magnesium alloys as orthopedic implant materials to improve the bio-adaptability: A review. Journal of Materials Science & Technology, 32(9), pp. 827-834. 2016. DOI: 10.1016/j.jmst.2016.05.003

Hornberger, H., Virtanen, S. and Boccaccini, A., Biomedical coatings on magnesium alloys – A review. Acta Biomaterialia, 8(7), pp. 2442- 2455, 2012. DOI: 10.1016/j.actbio.2012.04.012

Agarwal, S., Curtin, J., Duffy, B. and Jaiswal, S., Biodegradable magnesium alloys for orthopaedic applications: A review on corrosion, biocompatibility and surface modifications. Materials Science and Engineering: C, 2016. DOI: 10.1016/j.msec.2016.06.020

Zheng, Y., Gu, X.N. and Witte, F., Biodegradable metals. Materials Science and Engineering: R: Reports, 77, pp. 1-34, 2014. DOI: 10.1016/j.mser.2014.01.001

Sanchez, A., Luthringer, B., Feyerabend, F. and Willumeit, R., Mg and Mg Alloys: How comparable are in vitro and in vivo corrosion rates? A review. Acta Biomaterialia. 13, pp. 16-31, 2015. DOI: 10.1016/j.actbio.2014.11.048

Chen, Y., Zhao, S., Chen, M., Zhang, W., Mao, J., Zhao, Y., Maitz, M., Huang, N. and Wan, G. ,Sandwiched Polydopamine (PDA) layer for titanium dioxide (TiO2) Coating on magnesium to enhance corrosion protection. Corrosion Science, 96, pp. 67-73, 2015. DOI: 10.1016/j.corsci.2015.03.020

Burnat, B., Dercz, G. and Blaszczyk, T., Structural analysis and corrosion studies on an ISO 5832-9 biomedical alloy with TiO2 Sol– gel layers. Journal of Materials Science: Materials in Medicine 25(3), pp. 623-634, 2014. DOI: 10.1007/s10856-013-5099-7

Shan, C.X., Hou, X. and Choy, K., Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition. Surface and Coatings Technology, 202(11), pp. 2399-2402, 2008. DOI: 10.1016/j.surfcoat.2007.08.066

Krishna, D. and Sun, Y., Thermally oxidised rutile-TiO2 coating on stainless steel for tribological properties and corrosion resistance enhancement. Applied Surface Science 252(4), pp. 1107-1116, 2005. DOI: 10.1016/j.apsusc.2005.02.046

Peltola, T., Patsi, M. Rahiala, H., Kangasniemi, I. and Yli-Urpo, A., Calcium phosphate induction by sol-gel-derived titania coatings on titanium substrates in vitro. Journal of Biomedical Materials Research, 41(3), pp. 504-510, 1998. DOI: 10.1002/(SICI)1097- 4636(19980905)41:3<504::AID-JBM22>3.0.CO;2-G

Burnat, B., Robak, J., Batory, D., Leniart, A., Piwoński, I., Skrzypek, S. and Brycht, M., Surface characterization, corrosion properties and bioactivity of Ca-Doped TiO2 coatings for biomedical applications. Surface and Coatings Technology, 280, pp. 291-300, 2015. DOI: 10.1016/j.surfcoat.2015.09.01

Markowska-Szczupak, A., Ulfig, K. and Morawski, A. The Application of Titanium Dioxide for Deactivation of Bioparticulates: An Overview. Catalysis Today, 169 (1), pp. 249–257, 2011. DOI: 10.1016/j.cattod.2010.11.055

Chu, P., Surface engineering and modification of biomaterials. Thin Solid Films, 528, pp. 93-105, 2013. DOI: 10.1016/j.tsf.2012.07.144

Payr, E.. Beitrage zur technik der blutgefass-und nervennaht nebst mittheilungen uber die verwendung eines resorbirbaren metalles in der chirurgie. Arch Klin Chir, 62(1), pp. 67-93, 1900.

Staiger, M., Pietak, A., Huadmai, J. and Dias, G., Magnesium and its alloys as orthopedic biomaterials: A review. Biomaterials, 27(9), pp. 1728-1734, 2006. DOI: 10.1016/j.biomaterials.2005.10.003

Witte, F, Kaese, V., Haferkamp, H., Switzer, E., Meyer-Lindenberg, A., Wirth, C. and Windhagen, H., In vivo corrosion of four magnesium alloys and the associated bone response. Biomaterials, 26(17), pp. 3557-3563, 2005. DOI: 10.1016/j.biomaterials.2004.09.049

Wu, G., Ibrahim, J. and Chu, P., Surface design of biodegradable magnesium alloys — A review. Surface and Coatings Technology, 233, pp. 2-12, 2013. DOI: 10.1016/j.surfcoat.2012.10.009

Pompa, L., Rahman, Z., Munoz, E. and Haider, W., Surface characterization and cytotoxicity response of biodegradable magnesium alloys. Materials Science & Engineering. C, Materials for Biological Applications, 49, pp. 761-768, 2015. DOI: 10.4028/www.scientific.net/JBBTE.12.25

Li, H., Zheng, Y. and Qin, L., Progress of biodegradable metals. Progress in Natural Science: Materials International. 24(5), pp. 414- 422, 2014. DOI: 10.1016/j.pnsc.2014.08.014

Persaud-Sharma, D. and McGoron, A., biodegradable magnesium alloys: a review of material development and applications. Journal of Biomimetics, Biomaterials, and Tissue Engineering, 12, pp. 25-39, 2012. DOI: 10.4028/www.scientific.net/JBBTE.12.25

Mezbahul-Islam, M., Mostafa, A. and Medraj, M., Essential magnesium alloys binary phase diagrams and their thermochemical data. Journal of Materials, 2014, pp. 1–33, 2014. DOI: 10.1155/2014/704283

Esmaily, M., Blücher, D., Svensson, J., Halvarsson, M. and Johansson, L., New insights into the corrosion of magnesium alloys — The role of aluminum. Scripta Materialia, 115, pp. 91-95, 2016. DOI: 10.1016/j.scriptamat.2016.01.008

Xin, Y., Hu T. and Chu, P., In vitro studies of biomedical magnesium alloys in a simulated physiological environment: A review. Acta Biomaterialia 7(4), pp. 1452-1459, 2011. DOI: 10.1016/j.actbio.2010.12.004

Pardo, A., Merino, M., Coy, A., Arrabal, R., Viejo, F. and Matykina, E., Corrosion behaviour of magnesium/aluminium alloys in 3.5wt.% NaCl. Corrosion Science, 50(3), pp. 823-834, 2008. DOI: 10.1016/j.corsci.2007.11.005

Yun, Y., Dong, Z., Yang, D., Schulz, M., Shanov, V., Yarmolenko, S., Xu, Z., Kumta, P. and Sfeir, C., Biodegradable Mg corrosion and osteoblast cell culture studies. Materials Science and Engineering: C, 29(6), pp. 1814-1821, 2009. DOI: 10.1016/j.msec.2009.02.008

Zhen, Z., Liu, X., Huang, T., Xi, T. and Zheng, Y., Hemolysis and cytotoxicity mechanisms of biodegradable magnesium and its alloys. Materials Science & Engineering. C, Materials for Biological Applications, 46, pp. 202-206, 2015. DOI: 10.1016/j.msec.2014.08.038

Wang, L., Fang, G., Qian, L., Leeflang, S., Duszczyk, J. and Zhou, J., Forming of magnesium alloy microtubes in the fabrication of biodegradable stents. Progress in Natural Science: Materials International, 24(5), pp. 500-506, 2014. DOI: 10.1016/j.pnsc.2014.08.006

Heublein, B, Rohde, R., Kaese, V., Niemeyer, M., Hartung, W. and Haverich, A., Biocorrosion of magnesium alloys: A new principle in cardiovascular implant technology?. Heart (British Cardiac Society).

[online]. 89(6), pp. 651-656, 2003. Available at: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1767674/

Haude, M., Erbel, R., Erne, P., Verheye, S., Degen, H., Böse, D., Vermeersch, P., et al., Safety and performance of the drug-eluting absorbable metal scaffold (DREAMS) in patients with de-Novo coronary lesions: 12 month results of the prospective, Multicentre, First-in-Man BIOSOLVE-I Trial. Lancet (London, England), 381(9869), pp. 836844, 2013. DOI: 10.1016/S0140-6736(12)61765- 6

Tang, J., Wang, J., Xie, X., Zhang, P., Lai, Y., Li, Y. and Qin, L., Surface coating reduces degradation rate of magnesium alloy developed for orthopaedic applications. Journal of Orthopaedic Translation, 1(1), pp. 41-48, 2013. DOI: 10.1016/j.jot.2013.06.003

Cao, G., Wang, L., Fu, Z., Hu, J., Guan, S., Zhang, C., Wang, L. and Zhu, S., Chemically anchoring of TiO2 coating on OH-terminated Mg3 (PO3)2 surface and its influence on the in vitro degradation resistance of Mg–Zn–Ca Alloy. Applied Surface Science, 308, pp. 38- 42, 2014. DOI: 10.1016/j.apsusc.2014.04.080

Witecka, A., Yamamoto, A., Idaszek, J., Chlanda, A. and Święszkowski, W., Influence of biodegradable polymer coatings on corrosion, cytocompatibility and cell functionality of Mg-2.0Zn- 0.98Mn magnesium alloy. Colloids and Surfaces B: Biointerfaces, 144, pp. 284-292, 2016. DOI: 10.1016/j.colsurfb.2016.04.021

Ma, J., Thompson, M., Zhao, N. and Zhu, D., Similarities and differences in coatings for magnesium-based stents and orthopaedic implants. Journal of Orthopaedic Translation, 2(3), pp. 118-130, 2014. DOI: 10.1016/j.jot.2014.03.004

Ren, Y., Zhou, H., Nabiyouni, M. and Bhaduri, S., Rapid coating of AZ31 magnesium alloy with calcium deficient hydroxyapatite using microwave energy, Materials Science and Engineering: C, 49 pp. 364- 372, 2015. DOI: 10.1016/j.msec.2015.01.046.

Yu, H., Dong, Q., Dou, J., Pan, Y. and Chen, C., Structure and in vitro bioactivity of ceramic coatings on magnesium alloys by microarc oxidation. Applied Surface Science, 388(Part A), pp. 114-119, 2016. DOI: 10.1016/j.apsusc.2016.03.028

Bakhsheshi-Rad, H., Hamzah, E., Ismail, A., Kasiri-Asgarani, M., Daroonparvar, M., Parham, S., Iqbal, N. and Medraj, M., Novel bilayered nanostructured SiO2/Ag-FHAp coating on biodegradable magnesium alloy for biomedical applications. Ceramics International, 42(10), pp. 11941-11950, 2016. DOI: 10.1016/j.ceramint.2016.04.119

Velasco-Peña, M. y Garzón-Alvarado, D., Implantes Scaffolds para regeneración ósea: Materiales, técnicas y modelado mediante sistemas de reacción-difusión. Revista Cubana de Investigaciones Biomédicas, [en línea]. 29(1), 2010. Available at: http://scielo.sld.cu/scielo.php?script=sci_arttext&pid=S0864- 03002010000100008&lng=es&nrm=iso&tlng=es>

Zhang, H., Han, J., Sun, Y., Huang, Y. and Zhou, M., MC3T3-E1 Cell response to stainless steel 316L with different surface treatments. Materials Science & Engineering. C, Materials for Biological Applications, 56, pp. 22-29, 2015. DOI: 10.1016/j.msec.2015.06.017

Diebold, U., The surface science of titanium dioxide. Surface Science Reports, 48(5–8), pp. 53-229, 2003. DOI: 10.1016/S0167- 5729(02)00100-0

Singh, S., Mahalingam, H. and Singh, P., Polymer-supported titanium dioxide photocatalysts for environmental remediation: A review. Applied Catalysis A: General, 462-463, pp. 178-195, 2013. DOI: 10.1016/j.apcata.2013.04.039

Sakaguchi, A., Nakano, M., Hieda, J., Ohtake, N. and Akasaka, H., Dependence of ion concentration in simulated body fluid on apatite precipitation on titania surface. Applied Surface Science, 347, pp. 610-618, 2015. DOI: 10.1016/j.apsusc.2015.04.107

Kokubo, T., Kim, H., Kawashita, M. and Nakamura, T., Bioactive metals: Preparation and properties. Journal of Materials Science. Materials in Medicine, 15(2), pp. 99-107, 2004. DOI: 10.1023/B:JMSM.0000011809.36275.0c

Kim, H., Miyaji, F., Kokubo, T. and Nakamura, T., Bonding strength of bonelike apatite layer to Ti metal substrate. Journal of Biomedical Materials Research, 38(2), pp. 121-127, 1997. DOI: 10.1002/(SICI)1097-4636(199722)38:2<121::AID-JBM6>3.0.CO;2- S

Guo, L., Feng, W., Liu, X., Lin, C., Li, B. and Qiang Y., Sol-Gel synthesis of antibacterial hybrid coatings on titanium. Materials Letters, 2015. DOI: 10.1016/j.matlet.2015.08.027

Fu, G., Vary, P. and Lin, C., Anatase TiO2 nanocomposites for antimicrobial coatings. The Journal of Physical Chemistry. B, 109(18), pp. 8889-8898, 2005. DOI: 10.1021/jp0502196

Kubacka, A., Diez, M., Rojo, D., Bargiela, R., Ciordia, S., Zapico, I., Albar, J. et al., Understanding the antimicrobial mechanism of TiO₂- based nanocomposite films in a pathogenic bacterium. Scientific Reports, 4, pp. 4134, 2014. DOI: 10.1038/srep04134

Wang, T., Jiang, H., Wan, L., Zhao, Q., Jiang, T., Wang, B. and Wang, S., Potential application of functional porous TiO2 nanoparticles in light-controlled drug release and targeted drug delivery. Acta Biomaterialia, 13, pp. 354-363, 2015. DOI: 10.1016/j.actbio.2014.11.010

Faria, H. and De Queiroz, A., A novel drug delivery of 5-fluorouracil device based on TiO2/ZnS nanotubes. Materials Science and Engineering: C, 56, pp. 260-268, 2015. DOI: 10.1016/j.msec.2015.06.008

Xie, C., Li, P., Liu, Y., Luo, F. and Xiao, X., Preparation of TiO2 nanotubes/mesoporous calcium silicate composites with controllable drug release. Materials Science and Engineering: C, 67, pp. 433-439, 2016. DOI: 10.1016/j.msec.2016.05.041

Frandsen,C., Noh, K., Brammer, K., Johnston, G. and Jin, S., Hybrid micro/nano-topography of a TiO2 nanotube-coated commercial zirconia femoral knee implant promotes bone cell adhesion in vitro. Materials Science and Engineering: C, 33(5), pp. 2752-2756, 2013. DOI: 10.1016/j.msec.2013.02.045

Bao, L., Liu, J., Shi, F., Jiang, Y. and Liu, G., Preparation and characterization of TiO2 and Si-doped octacalcium phosphate composite coatings on zirconia ceramics (Y-TZP) for dental implant applications. Applied Surface Science, 290, pp. 48-52, 2014. DOI: 10.1016/j.apsusc.2013.10.185

Mirak, M., Alizadeh, M., Ghaffari, M. and Ashtiani, M., Characterization, mechanical properties and corrosion resistance of biocompatible Zn-HA/TiO2 nanocomposite coatings. Journal of the Mechanical Behavior of Biomedical Materials, 62, pp. 282-290, 2016. DOI: 10.1016/j.jmbbm.2016.05.016

Pradhan, D., Wren, A., Misture, S. and Mellott. N., Investigating the structure and biocompatibility of niobium and titanium oxides as coatings for orthopedic metallic implants. Materials Science and Engineering: C, 58, pp. 918-926, 2016. DOI: 10.1016/j.msec.2015.09.059

Fukuda, H. and Matsumoto, Y., Formation of Ti–Si composite oxide films on Mg–Al–Zn alloy by electrophoretic deposition and anodization. Electrochimica Acta, 50(27), pp. 5329-5333, 2005. DOI: 10.1016/j.electacta.2005.03.010

Ohko, Y., Saitoh, S., Tatsuma, T and Fujishima, A., Photoelectrochemical anticorrosion and self-cleaning effects of a TiO2 coating for type 304 stainless steel. Journal of the Electrochemical Society, 148(1), pp. B24, 2001. DOI: 10.1149/1.1339030

Hu, J., Shaokang, G., Zhang, C., Ren, C., Wen, C., Zeng, Z. and Peng, L., Corrosion protection of AZ31 magnesium alloy by a TiO2 coating prepared by LPD method. Surface and Coatings Technology. 203(14), pp. 2017-2020, 2009. DOI: 10.1016/j.surfcoat.2009.01.036

Marin, E., Lanzutti, A., Guzman, L. and Fedrizzi, L., Chemical and electrochemical characterization of TiO2/Al2O3 atomic layer depositions on AZ-31 magnesium alloy. Journal of Coatings Technology and Research, 9(3), pp. 347-355, 2012. DOI: 10.1007/s11998-011-9372-8

Cordero-Arias, L., Boccaccini, A. and Virtanen, S., Electrochemical behavior of nanostructured TiO2/alginate composite coating on magnesium alloy AZ91D via electrophoretic deposition. Surface and Coatings Technology, 265, pp. 212-217, 2015. DOI: 10.1016/j.surfcoat.2015.01.007

Fujita, R., Sakairi, M., Kikuchi, T. and Nagata, S., Corrosion resistant TiO2 film formed on magnesium by liquid phase deposition treatment. Electrochimica Acta, 56(20), pp. 7180-7188, 2011. DOI: 10.1016/j.electacta.2011.03.146

Li, Q., Jiang, G., Wang, C., Dong, J. and He, G., Mechanical degradation of porous titanium with entangled structure filled with biodegradable magnesium in Hanks’ solution. Materials Science and Engineering: C, 57, pp. 349-354, 2015. DOI: 10.1016/j.msec.2015.08.008

Bakhsheshi-Rad, H., Hamzah, E., Kasiri-Asgarani, M., Jabbarzare, S., Daroonparvar, M. and Najafinezhad, A., Fabrication, degradation behavior and cytotoxicity of nanostructured hardystonite and titania/hardystonite coatings on Mg alloys. Vacuum. 2016. DOI: 10.1016/j.vacuum.2016.03.021

Abdal-hay, A., Dewidar, M., Lim, J. and Lim, J., Enhanced biocorrosion resistance of surface modified magnesium alloys using inorganic/organic composite layer for biomedical applications. Ceramics International, 40(1), pp. 2237-2247, 2014. DOI: 10.1016/j.ceramint.2013.07.142

Shi, P., Ng, W., Wong, M. and Cheng, F., Improvement of corrosion resistance of pure magnesium in Hanks’ solution by microarc oxidation with sol–gel TiO2 sealing. Journal of Alloys and Compounds, 469(1), pp. 286-292, 2009. DOI: 10.1016/j.jallcom.2008.01.102

Bakhsheshi-Rad, H., Hamzah, E., Daroonparvar, M., Kasiri- Asgarani, M. and Medraj, M., Synthesis and biodegradation evaluation of Nano-Si and Nano-Si/TiO2 coatings on biodegradable Mg–Ca alloy in simulated body fluid. Ceramics International, 40(9), pp. 14009-14018, 2014. DOI: 10.1016/j.ceramint.2014.05.126

Harle, J., Kim, H., Mordan, N., Knowles, J. and Salih, V., Initial responses of human osteoblasts to sol-gel modified titanium with hydroxyapatite and titania composition. Acta Biomaterialia, 5, pp. 547-556, 2006. DOI: 10.1016/j.actbio.2006.05.005

Guglielmi, M., Kickelbick, G. and Martucci, A., Sol-Gel nanocomposites. Springer New York, 2014. DOI: 10.1007/978-1- 4939-1209-4

Wang, X., Shi, F., Gao, X., Fan, C., Huang, W. and Feng, X., A sol– gel dip/spin coating method to prepare titanium oxide films. Thin Solid Films, 548, pp. 34-39, 2013. DOI: 10.1016/j.tsf.2013.08.056

Advincula, M., Fan, X., Lemons, J. and Advincula, R., Surface modification of surface sol-gel derived titanium oxide films by selfassembled monolayers (SAMs) and non-specific protein adsorption studies. Colloids and Surfaces. B, Biointerfaces, 42(1), pp. 29-43, 2005. DOI: 10.1016/j.colsurfb.2004.12.009

Advincula, M., Rahemtulla, F., Advincula, R., Ada, E., Lemons, J. and Bellis, S., Osteoblast adhesion and matrix mineralization on solgel- derived titanium oxide. Biomaterials, 27(10), pp. 2201-2212, 2006. DOI: 10.1016/j.biomaterials.2005.11.014

Paldan, H., Areva, S., Tirri, T., Peltola, T., Lindholm, T., Lassila, LPelliniemi, L., Happonen, R. and Närhi, T., Soft tissue attachment on sol–gel-treated titanium implants in vivo. Journal of Materials Science: Materials in Medicine, 19(3), pp. 1283-1290, 2008. DOI: 10.1007/s10856-007-3234-z

Ochsenbein, A., Chai, F., Winter, S., Traisnel, M., Breme, J. and Hildebrand, H., Osteoblast responses to different oxide coatings produced by the sol-gel process on titanium substrates. Acta Biomaterialia, 4(5), pp. 1506-1517, 2008. DOI: 10.1016/j.actbio.2008.03.012

Areva, S., Paldan, H., Peltola, T., Närhi, T Jokinen, M. and Lindén, M., Use of sol-gel-derived titania coating for direct soft tissue attachment. Journal of Biomedical Materials Research Part A, 70A(2), pp. 169-178, 2004. DOI: 10.1002/jbm.a.20120

Li, B., Zhang, K., Yang, W., Yin, X. and Liu, Y., Enhanced corrosion resistance of HA/CaTiO3/TiO2/PLA coated AZ31 alloy. Journal of the Taiwan Institute of Chemical Engineers, 59, pp. 465-473, 2016. DOI: 10.1016/j.jtice.2015.07.028

Hu, Y., Pan, F., Wang, J. and Peng, J., The anticorrosive properties of sol-gel coating on AZ31 magnesium alloy. Materials Science Forum, 610–613, pp. 899-904, 2009. DOI: 10.4028/www.scientific.net/MSF.610-613.899

Hu, J., Zhang, C., Cui, B., Bai, K., Guan, S., Wang, L. and Zhu. S., In vitro degradation of AZ31 magnesium alloy coated with nano TiO2 film by sol–gel method. Applied Surface Science, 257(21), pp. 8772- 8777, 2011. DOI: 10.1016/j.apsusc.2011.03.148

Li, M., Chen, Q., Zhang, W Hu, W. and Su, Y., Corrosion behavior in SBF for titania coatings on Mg-Ca alloy. Journal of Materials Science, 46(7), pp. 2365-2369, 2011. DOI: 10.1007/s10853-010- 5083-2

Tang, H., Xin, T. and Wang, F., Calcium phosphate / titania sol-gel coatings on AZ31 magnesium alloy for biomedical applications. International Journal of Electrochemical Science, [online]. 8, pp. 8115-8125, 2013. Available at: http://www.electrochemsci.org/papers/vol8/80608115.pdf

Hernández-Barrios, C., Duarte, N., Hernández, L., Peña, D., Coy, A. and Viejo, F., Synthesis of hybrid sol-gel coatings for corrosion protection of we54-Ae magnesium alloy. Journal of Physics: Conference Series, 466(1), 012011, 2013. DOI: 10.1088/1742- 6596/466/1/012011

Amaravathy, P., Rose, C., Sathiyanarayanan, S. and Rajendran, N., Evaluation of in vitro bioactivity and MG63 oesteoblast cell response for TiO2 coated magnesium alloys. Journal of Sol-Gel Science and Technology, 64(3), pp. 694-703, 2012. DOI: 10.1007/s10971-012- 2904-6

Amaravathy, P., Sathyanarayanan, S., Sowndarya, S. and Rajendran, N., Bioactive HA/TiO2 coating on magnesium alloy for biomedical applications. Ceramics International, 40(5) pp. 6617-6630, 2014. DOI: 10.1016/j.ceramint.2013.11.119