At present, strong requirements in orthopaedics are still to be met, both in bone and joint substitution and in the repair and regeneration of bone defects. In this framework, tremendous advances in the biomaterials field have been made in the last 50 years where materials intended for biomedical purposes have evolved through three different generations, namely first generation (bioinert materials), second generation (bioactive and biodegradable materials) and third generation (materials designed to stimulate specific responses at the molecular level). In this review, the evolution of different metals, ceramics and polymers most commonly used in orthopaedic applications is discussed, as well as the different approaches used to fulfil the challenges faced by this medical field.

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Various oxidation treatments were applied to nearly equiatomic NiTi alloys so as to form a Ni-free protective oxide on the surface. Sample surfaces were analyzed by X-ray Photoelectron Spectroscopy, and NiTi transformation temperatures were determined by differential scanning calorimetry (DSC) before and after the surface treatment. An ion release experiment was carried out up to one month of immersion in SBF for both oxidized and untreated surfaces. The results show that oxidation treatment in a low-oxygen pressure atmosphere leads to a high surface Ti/Ni ratio, a very low Ni surface concentration and a thick oxide layer. This oxidation treatment does not significantly affect the shape memory properties of the alloy. Moreover, the oxide formed significantly decreases Ni release into exterior medium comparing with untreated surfaces. As a consequence, this new oxidation treatment could be of great interest for biomedical applications, as it could minimize sensitization and allergies and improve biocompatibility and corrosion resistance of NiTi shape memory alloys.

Bioactive polymers bearing sulfonate (styrene sodium sulfonate, NaSS) and carboxylate (methylacrylic acid, MA) groups were grafted onto Ti6Al4V alloy surfaces by a two-step procedure. The Ti alloy surfaces were first chemically oxidized in a piranha solution and then directly subjected to radical polymerization at 70°C in absence of oxygen. The grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the Toluidin blue colorimetric method. Toluidin blue results showed 1 to 5 g/cm 2 of polymer was grafted onto the oxidized Ti surfaces. Grafting resulted in a decrease in the XPS Ti and O signals from the underlying Ti substrate and a corresponding increase in the XPS C and S signals from the polymer layer. The ToF-SIMS intensities of the S − and SO − ions correlated linearly with the XPS atomic percent S concentrations and the ToF-SIMS intensity of the TiO 3 H 2 − ion correlated linearly with the XPS atomic percent Ti concentration. Thus, the ToF-SIMS S − , SO − and TiO 3 H 2 − intensities can be used to quantify composition and amount of grafted polymer. ToF-SIMS also detected ions that were more characteristic of the polymer molecular structure (C 6 H 4 SO 3 − and C 8 H 7 SO 3 − from NaSS, C 4 H 5 O 2 − from MA), but the intensity of these peaks depended on the polymer thickness and composition. An in vitro cell culture test was carried out with human osteoblast-like cells to assess the influence of the grafted polymers on cell response. Cell adhesion after 30 min of incubation showed significant differences between the grafted and un-grafted surfaces. The NaSS grafted surfaces showed the highest degree of cell adhesion while the MA-NaSS grafted surfaces showed the lowest degree of cell adhesion. After 4 weeks in vivo in rabbit femoral bones bone was observed to be in direct contact with all implants. The percent of mineralized tissue around the implants was similar for NaSS grafted and non-grafted implants (59 and 57%). The MA-NaSS grafted implant exhibited a lower amount of mineralized tissue (47%). Keywords

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This work studies NiTi orthodontic archwires that have been treated using a new oxidation treatment for obtaining Ni-free surfaces. The titanium oxide on the surface significantly improves corrosion resistance and decreases nickel ion release, while barely affecting transformation temperatures. This oxidation treatment avoids the allergic reactions or toxicity in the surrounding tissues produced by the chemical degradation of the NiTi. In the other hand, the lack of low friction coefficient for the NiTi superelastic archwires makes difficult the optimal use of these materials in Orthodontic applications. In this study, the decrease of this friction coefficient has been achieved by means of oxidation treatment. Transformation temperatures, friction coefficient and ion release have been determined.

This work examines NiTi foams that have been treated using a new oxidation treatment for obtaining Ni-free surfaces that could allow the ingrowth of living tissue, thereby increasing the mechanical anchorage of implants. A significant increase in the real surface area of these materials can decrease corrosion resistance and favour the release of Ni. This chemical degradation can induce allergic reactions or toxicity in the surrounding tissues. This study determines the porosity, surface characteristics, phase transformation, mechanical properties, corrosion behaviour and Ni release into the simulated body fluid medium of foams treated by a new surface oxidation treatment that produces Ni-free surfaces. These foams have pores in an appropriate range of sizes and interconnectivity, and thus their morphology is similar to that of bone. Their mechanical properties are biomechanically compatible with bone. The titanium oxide on the surface significantly improves corrosion resistance and decreases nickel ion release, while barely affecting transformation temperatures.