Cláudia E. B. Marino

The Electrochemical Behavior of the NiTi Alloy; in Different Simulated Body Fluids

In order to improve the NiTi alloy biocompatibility, surface treatments become very important. Nevertheless, researchers use different solutions to simulate the body fluids in electrochemical assays, and the correlation between the obtained results is difficult and might not even be possible. The present paper evaluated the electrochemical behavior of polished NiTi surfaces exposed to different simulated body fluid solutions: Hanks solution, Hanks’ balanced salt (HBSS) solution, saline body fluid (SBF) solution, and Ringer solution. The electrochemical behavior of NiTi was evaluated by open circuit potential (OCP) and cyclic voltammetry tests. The surfaces of the samples were also characterized by scanning electron microscopy, which was performed after the electrochemical tests. The results demonstrated that the NiTi alloy shows the same corrosion mechanism (pitting) in all simulated body fluids that were studied. However, the corrosion potential changes for each electrolyte, being HBSS, SBF and Ringer the most corrosive solutions. Furthermore, the Hanks and HBSS solutions demonstrated good reproducibility of the electochemical results. Considering that the HBSS represents an extreme environment, this solution seems to be the most indicated to study the corrosion behavior of NiTi treated surfaces.

Bioactivity of self-organized TiO2 nanotubes used as surface treatment on Ti biomaterials

Titanium and its alloys are widely used as implants due to their excellent mechanical properties, corrosion resistance and biocompatibility. TiO2 nanotubes have been studied as surface treatment to increase the specific area and to improve osseointegration. However, the thermodynamic stability and bioactivity of these nanostructures must be evaluated. The objective of this research was to obtain nanotubes oxides on Ti6Al4V alloy and to analyze the electrochemical stability in physiological solution at 37 °C and the bioactive response of the biomaterial. The nanotubes were obtained by potentiostatic anodization. The morphology of the oxides was evaluated by scanning electron microscopy. The chemical characterization was analyzed by energy dispersive spectroscopy and x-ray photoelectron spectroscopy techniques. The electrochemical stability was analyzed by open circuit potential (OCP) and the bioactivity by biomimetic test in a simulated body fluid (SBF) solution. The OCP of the nanotubes oxides was shown to be more noble and stable than the compacted oxides. The biomaterial covered with theses oxides showed sealing by Ca and P after 30 d immersion in artificial blood. And after 15 d of immersion in SBF, the hydroxyapatite could be seen on the non-sealed nanotubes. TiO2 nanotube layers could improve the superficial chemical stability and also the osseointegration process.

Elastic modulus evaluation of Titania nanotubes obtained by anodic oxidation

The use of titania (TiO2) nanotubes is becoming one of the most attractive techniques as surface treatment for implants due its combination of morphology (that accelerates osteoblast adhesion and proliferation), bioactivity and possibility of being use as a drug vehicle. Anodic oxidation is one of the cheapest and simplest approaches to obtain highly ordered nanotubes. Parameters such as applied potential, reaction time and fluoride containing in the electrolyte define the nanotubes morphology. However, the mechanical properties of the nanotubes layer do not have been completely elucidated and they play a crucial role in the implant long term stability. The objective of this research was to obtain TiO2nanotubes using anodic oxidation and to determine their elastic modulus and hardness. The TiO2nanotubes layer was obtained in a fluoride containing electrolyte for 1 hour, one group at 15 V and another one at 25 V. The TiO2nanotubes morphology was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The elastic modulus and hardness were evaluated by nanoindentation experiments using a spherical tip. SEM images showed highly ordered nanotubes on all titanium surfaces and it was observed that the nanotubes diameters are directly related with the applied potential. Nanotubes diameters are 66 ± 9 nm and 131 ± 22 nm for nanotubes obtained at 15 V and 25 V, respectively. Nanoindentation test results showed a decrease in the elastic modulus comparing with titanium reference and these values approach to cortical bone elastic modulus. These results demonstrate that it was possible to obtain a homogeneous TiO2nanotubes layer that has mechanical properties adequate to improve implant long-term stability.

Growth and Electrochemical Stability of Compact Tantalum Oxides Obtained in Different Electrolytes for Biomedical Applications

Tantalum has been cited to have many biomaterial applications, exhibiting biocompatibility and outstanding corrosion resistance. Tantalum may be covered with tantalum oxide using the electrochemical process of anodic oxidation. The oxide surface is known to be bioactive and more corrosion resistant. In this research, compact tantalum oxide films were obtained by potentiostatic and potentiodynamic methods in H2SO4 and H3PO4 (1 mol.L-1) electrolytes. By XPS analysis the stoichiometry Ta2O5 was detected. The thermodynamic stability of those oxides was compared and the results indicated that Ta2O5 obtained in H2SO4 has higher thermodynamic stability than Ta2O5 obtained in H3PO4. The incorporation of (PO4)3- ions and the formation of a bilayer oxide are responsible for the reduced stability. Also, the better control of chemical kinetic of oxide formation allows potentiodynamic oxides to be more stable. Ta2O5 shows spontaneous dissolution in artificial blood, nevertheless, it remains stable even after 60 days of immersion. By scratching tests was possible to notice that Ta2O5 is highly adherent to the tantalum metallic substrate and by mechanical indentation was possible to measure a lower elastic modulus for the Ta2O5 than the metallic substrate, what can be considered as distinguished properties for biomedical applications.

Oxide Formation on NiTi Surface: Influence of the Heat Treatment Time to Achieve the Shape Memory

Several studies regarding superficial treatments of Nitinol (NiTi) shape-memory have been developed aiming to the improve corrosion resistance and to block the Ni release to adjacent tissues. The necessary heat treatment to achieve the shape memory effect normally occurs at temperatures between 500 and 600 °C. However, titanium oxide (TiO2) is formed on the NiTi surface during the shape memory process heat treatment. In this work the effects of the heat treatment time on the surface characteristics of the formed NiTi oxide, at temperatures that promote the shape-memory (530 and 570 °C), were evaluated. The TiO2 layers which were obtained were evaluated by X-ray diffraction (XRD), energy dispersive X-ray (EDX), scanning electron microscope (SEM), thermogravimetric analysis (TGA), wettability and roughness. The results show that by increasing the exposure time at the temperature of 570 °C the formation of a thicker oxide is promoted, with less superficial roughness and of a hydrophobic nature. According to the literature, these characteristics indicate that the obtained oxide layer has properties that accelerat the osseointegration process.

Growth and electrochemical stability of self-organized TiO2nanotubes on Ti-2 grade and orthopedic Ti6Al4V alloy for biomedical application

Titanium and its alloys are biomaterials used in endosseous implants, due to desirable mechanical properties, high corrosion resistance and biocompatibility. Using electrochemical anodization technique these materials can be recovered with self-organized TiO2 nanotubes layer resulting in increased specific surface area and probable bioactivity improvement. This research aimed determine potentiostatic anodization parameters to obtain self-organized TiO2nanotubes layer with reproducibility and ideal diameters for probable bioactive response on Ti - 2 grade (ASTM F67) and Ti6Al4V (ASTM F136) orthopedic alloy and evaluation the electrochemical stability behavior in simulated body fluid media. The self-organized nanotubes layer were obtained by potentiostatic electrochemical method in electrolyte containing fluoride ions, H3PO4/HF for Ti 2 grade and H3PO4/NH4F for Ti6Al4V alloy, the applied potentials were 15 V, 20 V and 25 V for 30, 60 and 90 minutes, for both materials. For morphologic characterization were employed scanning electron microscopy SEM and the Image J software for nanodiameter measurements. The nanoestructure electrochemical stability was evaluated by open circuit potential after immersion for 15, 30 and 60 days in artificial blood plasma, into an electrochemical cell, using SCE (saturated calomel electrode) as reference electrode, in PBS ((phosphate buffered saline) solution electrolyte for 90 minutes. The ideal anodization parameters were 15 V and 20 V for 1 hour and a reproducible, uniform and homogeneous self-organized nanotubes layer were obtained with ideal diameters that probably improve the implant superficial bioactivity with 80 and 120 nm respectively, according to the literature. Open-circuit potentials from metal/oxide system obtained on both materials are stable with potentials in range of -0.031 V to -0,183 V indicating good stability of nanoestructures in simulated body fluid. Nanotubes layer as a superficial treatment is viable with high reproducibility, low cost and electrochemical stability in simulated body fluid media.

Titanium bioactivity surfaces obtained by chemical/electrochemical treatments

There are various surface treatments used to modify titanium surfaces to render it bioactive. In this study commercially pure titanium surfaces (cp Ti), grade 2 were modified by acid etching (AE) and anodic oxidation (OA) in order to evaluate the bioactivity in vitro of these surfaces using the simulated body fluid (SBF). The AE was realized using a mixture of acids and AO using 1 mol.L-1 sulfuric acid. The anodic films were obtained under potentiostatic mode, during 60s using as anode a bar of titanium. All the surfaces that means cp Ti, AE and AO were analyzed concerning to morphology, rugosity, structural changes before in vitro bioactivity tests. It was observed by scanning electron microscopy (SEM) that all surfaces presented different morphologies: those with AE showed a surface with peaks and rounded valleys, with Ra = (564±80) nm, the oxidized surfaces with sulfuric acid showed a morphology with small pores uniformly distributed over the surface and Ra = (177±0,02) nm. X-rays diffraction results showed the presence of titanium hydride on the samples with AE and the anatase and rutile phases on the anodic films after heat treatment at 600°C/1h. Bioactivity tests in vitro using SBF at 37°C showed that small aggregates containing Ca and P were observed on surfaces with AE after 30 days soaked in SBF and the surfaces oxidized were fully coated with an apatite layer, identified by SEM.

Electrochemical Stability and Bioactivity Evaluation of Ti6Al4V Surface Coated with Thin Oxide by EIS for Biomedical Applications

To improve the implants biocompatibility many surface modifications were proposed. Investigations about the surface modification on Ti alloys by anodic oxidation are reported. This research presents a study on the stability of thin titanium dioxide grown by potentiodynamic method on Ti6Al4V surfaces up to 5.0 V. Its bioactive surface in phosphate buffer solution (PBS) and the oxide stability after immersion in artificial blood media were measured by Electrochemical Impedance Spectroscopy (EIS). Hydroxyapatite (HAP) presence was evaluated using simulated body fluid (SBF) with different immersion times. The oxides and HAP presence were analyzed by Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The oxide stability was confirmed with low dissolution rates where the Rp was around 106Ω.cm2. The results showed the TiO2 was compact and thin oxide that could prevent the severe corrosion processes and improve in few days the physical-chemical interaction of the Ti alloys with bone in physiological media.

Optical (DRUV-VIS) and magnetic (EPR) behavior of synthetic melanins

The properties of melanins prepared from L-dopa oxidation by both chemical and electrochemical methods are reported, searching for a material with more intense optical absorption in the visible region. The characterization of the samples have been done by cyclic voltammetry (CV), cronoamperometry (CA), Fourier transformed infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR) and diffuse reflectance ultraviolet-visible spectroscopy (DRUV-VIS) techniques. The electrochemical method enhanced the organic free radical (spin) concentration and the absorption intensity in the visible region of the spectrum. The DRUV-VIS technique along with mathematical tools, such as the Kubelka-Munk remission function, were good options for the characterization of the final products.

Elastic Modulus and Hardness of Bioactive Ti Obtained by Anodic Oxidation Using Ca/P-Based Solutions

Anodic oxidation is a promising technique to become titanium surfaces bioactive, by simultaneously changing the surface morphology, structure and chemical properties. Calcium and phosphorus based electrolytes were used to produce anodic films on c.p. Ti with two different current densities, 150 mA/cm2 and 300 mA/cm2. Morphology and structure were examined by SEM, EDS and XRD, and elastic modulus and hardness of the surfaces by instrumented indentation. Besides rutile and anatase TiO2 phases, hydroxyapatite was also identified on the films, as well as the segregation of very soft Ca and P-rich zones. Low values for the elastic modulus and hardness values close to the Ti corroborate to the applicability of Ca and P based TiO2 anodic films in biomedical titanium implants.