Zn and Ag Co-doped Anti-microbial TiO2 Coatings on Ti by Micro-arc Oxidation

doi:10.1016/j.jmst.2016.01.008

材料科学与技术 ›› 2016, Vol. 32 ›› Issue (9): 919-924.DOI: 10.1016/j.jmst.2016.01.008

收稿日期:2015-06-15 接受日期:2015-10-21 出版日期:2016-09-20 发布日期:2016-11-02

Zn and Ag Co-doped Anti-microbial TiO₂ Coatings on Ti by Micro-arc Oxidation

Zhang Lan,Gao Qin,Han Yong()

State-key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an 710049, China

Received:2015-06-15 Accepted:2015-10-21 Online:2016-09-20 Published:2016-11-02
Contact: Han Yong

摘要/Abstract

Abstract:

Micro-porous TiO₂ coatings co-doped with Zn²⁺ and Ag nanoparticles were fabricated on Ti by micro-arc oxidation (MAO) for 0.5, 1.5, 2 and 4?min, respectively. The evolutions of morphology and phase component of the coating as a function of processing time were investigated. The microstructure of the 2?min treated coating was further observed by transmission electron microscopy to explore the coating formation mechanism. The amounts of Ag and Zn released from the 2?min treated coating were measured and the antibacterial properties of the coatings against Staphylococcus aureus (S.?aureus) were also investigated. The obtained results showed that with prolonged MAO time, the contents of Ag and Zn on the coating surfaces increased. All the coatings were micro-porous with pore diameters of 1-4?μm; however, some pores were blocked by deposits on the 4?min treated coating. The 2?min treated coating was composed of amorphous TiO₂, anatase, rutile, ZnO, Zn₂TiO₄ and homogenously distributed Ag nanoparticles. After immersion, Zn²⁺, Ag⁺, Ti²⁺ and Ca²⁺ were released from the coating and with the immersion time prolonged, the accumulated concentrations of these ions increased. After immersion for 36 weeks, the accumulated Zn²⁺ and Ag⁺ concentrations were 6.88 and 0.684?ppm, respectively, which are higher than the minimal inhibitory concentration but much lower than the cytotoxic concentration. Compared with polished Ti control, the coatings co-doped with Zn²⁺ and Ag nanoparticles significantly inhibited the adhesions of S.?aureus and reduced the amounts of planktonic bacteria in culture medium, indicating that the Zn and Ag co-doped TiO₂ could be a bio-adaptable coating for long-lasting anti-microbial performance.

Key words: Zn, Ag nanoparticle, Co-doped TiO2, Micro-arc oxidation, Bio-adaptable

. [J]. 材料科学与技术, 2016, 32(9): 919-924.

Zhang Lan,Gao Qin,Han Yong. Zn and Ag Co-doped Anti-microbial TiO₂ Coatings on Ti by Micro-arc Oxidation[J]. J. Mater. Sci. Technol., 2016, 32(9): 919-924.

图/表 6

Fig. 1. Surface morphologies and the corresponding EDX results of the MAO treated coatings for 0.5 (a), 1.5 (b), 2 (c) and 4?min (d).

Fig. 2. XRD patterns of the coatings prepared for different time.

Fig. 3. (a) Cross-sectional morphology of the 2?min coating; (b) Ag 3d and (c) Zn 2p XPS high-resolution spectra of the 2?min coating.

Fig. 4. TEM images of the 2?min coating surface: (a) bright-field image; (b) a magnified bright-field image of the ring marked in (a); (c) the corresponding SAED pattern of (b); (d) and (e) dark-field images corresponding to rings labeled 1, 2 and 3 in (c), respectively; (f) HRTEM image of the Ag nanoparticle marked with an arrow in (e).

Fig. 5. (a) Ca, Zn, Ag and Ti concentrations of the 2?min coating after immersion for different times; (b) surface morphology of the 2?min coating after immersion for 36 weeks.

Fig. 6. (a) Numbers of adherent S.?aureus on the polished Ti, 0.5, 1.5 and 2?min coating after being cultured for 24?h; (b) numbers of planktonic S.?aureus in the culture medium after being cultured for 24?h; (c) SEM morphologies of the S.?aureus species seeded on the polished Ti, 0.5, 1.5 and 2?min coating surfaces.

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Zn and Ag Co-doped Anti-microbial TiO₂ Coatings on Ti by Micro-arc Oxidation

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