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It has been shown that the synthesis of TiO 2 nanotubes by anodization provides outstanding properties to Ti surfaces intended for dental and orthopedic implants applications. Beyond the very well-known potential of these surfaces to improve osseointegration and avoid infection, the knowledge on the adhesion and degradation behavior of TiO 2 nanotubes under the simultaneous action of wear and corrosion is still poorly understood and these are issues of tremendous importance. The main aim of this work is to investigate, for the first time, the tribo-electrochemical degradation behavior of Ti surfaces decorated with TiO 2 nanotubes before and after biofunctionalization treatments. Well-aligned TiO 2 nanotubes (NTs) were produced containing elements natively present in bone such as calcium (Ca) and phosphorous (P), in addition of zinc (Zn) as an antimicrobial agent and stimulator of bone formation. The synthesis of Ca/P/Zn-doped nanotubes (NT-Ca/P/Zn) was achieved by reverse polarization and anodization treatments applied to conventional TiO 2 nanotubes grown by two-step anodization. The nanotube surfaces were analyzed by scanning electron microscopy (SEM) while dark-field scanning transmission electron microscopy (STEM-DF) was used to characterize the Ti/TiO 2 nanotubular films interfaces. Tribo-electrochemical tests were conducted under reciprocating sliding conditions in artificial saliva. The open circuit potential (OCP) was monitored before, during and after sliding tests, and the coefficient of friction (COF) values were registered during rubbing action. The wear tracks resulting from sliding tests were characterized by SEM and wear volume measurements were carried out by 2D profilometry. The results show that the tribo-electrochemical behavior of TiO 2 nanotubes was significantly improved after bio-functionalization treatments. The higher electrochemical stability and lower mechanical degradation of these films was correlated with their improved adhesion strength to Ti substrate, which is granted by the nanothick oxide film formed at the interface region, during bio-functionalization processes. A first insight on the degradation mechanisms taking place during tribo-electrochemical action is proposed. The outcomes of this study may contribute in a great extent for the development of new implant surfaces with improved biomechanical stability and thus contribute for the long term success of dental implants.

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Capillarity is pivotal to many important technologies, including capillary self-alignment and self-assembly for heterogeneous microsystem integration and packaging. Lateral capillary forces ensuing from perturbed fluid menisci were the object of substantial theoretical and numerical modeling in recent years. Anyway, those studies were so far unsatisfactorily supported by direct experimental inspections. In this paper we present a comprehensive quasi-static study of lateral capillary forces arising from a constrained cylindrical fluid meniscus subjected to small lateral perturbations. We describe the novel experimental apparatus that we designed to accurately characterize such a fundamental system. We then reproduce our experimental data on lateral meniscus forces and stiffnesses by means of both a finite element and a novel analytical model. The agreement between our measurements and models, while confirming earlier reports, provides a solid foundation for the applications of lateral capillary forces to microsystem assembly. Moreover, our experimental apparatus may enable the exploitation of Gibbs' inequality to measure the advancing contact angles of liquids, and it may be used as a reference testbed for further experimental investigations on constrained fluid menisci.

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Capillarity-driven self-assembly of small chips onto planar target substrates is a promising alternative to robotic pick-and-place assembly. It critically relies on the selective deposition of thin fluid films on patterned binding sites, which is anyway normally non-conformal. We found that the addition of a thin wetting sidewall, surrounding the entire site perimeter, enables the conformal fluid coverage of arbitrarily shaped sites through dip-coating, significantly improves the reproducibility of the coating process and strongly reduces its sensitivity to surface defects. In this paper we support the feasibility and potential of this method by demonstrating the conformal dip-coating of square and triangular sites conditioned with combinations of different hydrophobic and hydrophilic surface chemistries. We present both experimental and simulative evidence of the advantages brought by the introduction of the wetting boundary on film coverage accuracy. Application of our surface preparation method to capillary self-assembly could result in higher precision in die-to-substrate registration and larger freedom in site shape design.