Ludek Joska

Corrosion behaviour of titanium after short-term exposure to an acidic environment containing fluoride ions

The negative effect of fluoride ions on titanium has been known in dentistry for a long time. The presented work was aimed at the interaction between titanium and model saliva following a short-term exposure of a specimen to a model medical preparation rich in fluoride ions. The experimental work was carried out using titanium grade 2 in a physiological solution (pH non-adjusted, 5.8, 4.2; 5000xa0ppmxa0F−) and in model saliva. Electrochemical measurement techniques were supplemented with XPS analysis. The presence of fluoride ions resulted in partial degradation of the passive layer even in a slightly acidic environment. The decrease of pH to the value of 4.2 and the presence of 5000xa0ppmxa0F− caused titanium activation followed by a slow repassivation in model saliva. Formation of low soluble compound rich in fluorine explains experimental data. Short medical treatment can result in relatively long period of increased titanium corrosion.

The diameter of nanotubes formed on Ti-6Al-4V alloy controls the adhesion and differentiation of Saos-2 cells.

Ti-6Al-4V-based nanotubes were prepared on a Ti-6Al-4V surface by anodic oxidation on 10 V, 20 V, and 30 V samples. The 10 V, 20 V, and 30 V samples and a control smooth Ti-6Al-4V sample were evaluated in terms of their chemical composition, diameter distribution, and cellular response. The surfaces of the 10 V, 20 V, and 30 V samples consisted of nanotubes of a relatively wide range of diameters that increased with the voltage. Saos-2 cells had a similar initial adhesion on all nanotube samples to the control Ti-6Al-4V sample, but it was lower than on glass. On day 3, the highest concentrations of both vinculin and talin measured by enzyme-linked immunosorbent assay and intensity of immunofluorescence staining were on 30 V nanotubes. On the other hand, the highest concentrations of ALP, type I collagen, and osteopontin were found on 10 V and 20 V samples. The final cellular densities on 10 V, 20 V, and 30 V samples were higher than on glass. Therefore, the controlled anodization of Ti-6Al-4V seems to be a useful tool for preparing nanostructured materials with desirable biological properties.

Cell interaction with modified nanotubes formed on titanium alloy Ti-6Al-4V.

Nanotubes with diameters ranging from 40 to 60nm were prepared by electrochemical oxidation of the Ti-6Al-4V alloy in electrolyte containing ammonium sulphate and ammonium fluoride. The nanotubes were further modified with calcium and phosphate ions or were heat treated. Polished Ti-6Al-4V alloy served as a reference sample. The spreading of human osteoblast-like cells was similar on all nanotube samples but lower than on polished samples. The number of initially adhered cells was higher on non-modified nanotubes, but the final cell number was the highest on Ca-enriched nanotubes and the lowest on heat-treated nanotubes. However, these differences were relatively small and less pronounced than the differences in the concentration of specific molecular markers of cell adhesion and differentiation, estimated by their intensity of immunofluorescence staining. The concentration of vinculin, i.e. a protein of focal adhesion plaques, was the lowest on nanotubes modified with calcium. Collagen I, an early marker of osteogenic cell differentiation, was also the lowest on samples modified with calcium and was highest on polished samples. Alkaline phosphatase, a middle marker of osteogenic differentiation, was observed in lowest concentration on nanotubes modified with phosphorus and the highest on heat-treated samples. Osteocalcin concentrations, a late marker of osteogenic cell differentiation, were similar on all tested samples, although they tended to be the highest on heat-treated samples. Thus, osteogenic differentiation can be modulated by various additional treatments of nanotube coatings on Ti-6Al-4V implants.

Corrosion behavior of Ti–39Nb alloy for dentistry

To increase an orthopedic implants lifetime, researchers are now concerned on the development of new titanium alloys with suitable mechanical properties (low elastic modulus-high fatigue strength), corrosion resistance and good workability. Corrosion resistance of the newly developed titanium alloys should be comparable with that of pure titanium. The effect of medical preparations containing fluoride ions represents a specific problem related to the use of titanium based materials in dentistry. The aim of this study was to determine the corrosion behavior of β titanium alloy Ti-39Nb in physiological saline solution and in physiological solution containing fluoride ions. Corrosion behavior was studied using standard electrochemical techniques and X-ray photoelectron spectroscopy. It was found that corrosion properties of the studied alloy were comparable with the properties of titanium grade 2. The passive layer was based on the oxides of titanium and niobium in several oxidation states. Alloying with niobium, which was the important part of the alloy passive layer, resulted in no significant changes of corrosion behavior. In the presence of fluoride ions, the corrosion resistance was higher than the resistance of titanium.

Corrosion behaviour of TiN and ZrN in the environment containing fluoride ions

Nowadays, a wide range of materials for human implants is used. To reach the required properties of implants, coatings are applied in some cases. This contribution is focused on the corrosion properties of TiN and ZrN layers on cp-titanium (commercially pure titanium) under environment modelling conditions in an oral cavity. Measurements were done in artificial saliva and a physiological solution unbuffered and buffered to a pH value of 4.2 with the addition of fluoride ions up to 4000 ppm. Standard corrosion electrochemical techniques were applied. Both types of layers were stable in both model saliva and physiological solution with non-adjusted pH. The decrease in pH to 4.2 resulted in a minor decrease of corrosion resistance in all cases, but polarization resistance was still in the order of 10(5) Ω cm². An important change in a specimens behaviour was noticed in the presence of fluoride ions. TiN was stable in the highest concentration of fluorides used. The ZrN layers were destabilized in an environment containing a few hundred ppm of fluoride ions. As for TiN, the decisive factor is the influence of porosity; the corrosion resistance of ZrN is limited. From the corrosion point of view, the application of the TiN-based barrier layers in dental implantology is more advisable than the use of ZrN, provided that the application of a barrier is inevitable.

Properties of titanium-alloyed DLC layers for medical applications

DLC-type layers offer a good potential for application in medicine, due to their excellent tribological properties, chemical resistance, and bio-inert character. The presented study has verified the possibility of alloying DLC layers with titanium, with coatings containing three levels of titanium concentration prepared. Titanium was present on the surface mainly in the form of oxides. Its increasing concentration led to increased presence of titanium carbide as well. The behavior of the studied systems was stable during exposure in a physiological saline solution. Electrochemical impedance spectra practically did not change with time. Alloying, however, changed the electrochemical behavior of coated systems in a significant way: from inert surface mediating only exchange reactions of the environment in the case of unalloyed DLC layers to a response corresponding rather to a passive surface in the case of alloyed specimens. The effect of DLC layers alloying with titanium was tested by the interaction with a simulated body fluid, during which precipitation of a compound containing calcium and phosphorus - basic components of the bone apatite - occurred on all doped specimens, in contrast to pure DLC. The results of the specimens surface colonization with cells test proved the positive effect of titanium in the case of specimens with a medium and highest content of this element.

Influence of porosity on corrosion behaviour of Ti-39Nb alloy for dental applications.

Porous materials allow for easier osseointegration of implants and their firmer connection with the bone. The presence of pores in a material may become a source of both mechanical and corrosion problems. The presented study explored a Ti-39Nb alloy with a porosity of 0-33%. Specimens were exposed in the physiological solution of two pH values. In view of this materials possible use in dental applications, the effect of fluoride ions on its corrosion behaviour was studied. The open circuit potential and polarization resistance were measured. Data concerning susceptibility to crevice corrosion were obtained from potentiostatic measurements based on the ASTM F746 standard. In terms of corrosion behaviour, specimens with a lower porosity were not much different from the non-porous material. Porosity produced its effect at the level of 24 and 33%. It is obvious that porosity affects corrosion behaviour of this type of material. This conclusion was confirmed by measurements of susceptibility to crevice corrosion which grew with the specimens increasing porosity. Corrosion resistance of the Ti-39Nb alloy was comparable with that of the compact material, but the presence of pores initiated a local attack of the material.

On the analysis of optical signals from Ti35Nb6Ta and Ti6Al4V surfaces

Chemical components and initial optical responses of Ti35Nb6Ta alloy are reported. Polished titanium and other titanium alloy Ti6Al4V served as reference surfaces. The chemical composition was determined with an X-ray photoelectron spectroscope (XPS) for the surfaces as well as for water, phosphate buffered saline (PBS) and for human plasma fibrinogen (HPF in PBS) exposed surfaces. The reflectance of the surfaces was modeled utilizing Bruggemans model, to evaluate the optical changes that the chemical reaction of each liquid can produce. After the model, a diffractive optical element (DOE) based sensor was used to determine the temporal optical signal from the sample surfaces. The coherent and non-coherent signals gathered with DOE sensor were compared to the reflectance model. Exposing to the liquids showed surface oxidation, which could produce lowered reflectance of the surface. The model and the initial temporal responses showed similarities in non-coherent reflectance.

Corrosion behaviour and cell interaction of Ti-6Al-4V alloy prepared by two techniques of 3D printing

3D printing seems to be the technology of the future for the preparation of metallic implants. For such applications, corrosion behaviour is pivotal. However, little is published on this topic and with inconsistent results. Therefore, we carried out a complex study in which we compared two techniques of the 3D printing technology - selective laser melting and electron beam melting. The corrosion behaviour was studied in physiological solution by standard electrochemical techniques and susceptibility to localised corrosion was estimated too. All samples showed typical passive behaviour. Localised corrosion was shown to be possible on the original as-printed surfaces. Corrosion experiments were repeated tree times. To reveal possible negative effects of 3D printing on cytocompatibility, direct in vitro tests were performed with U-2 OS cells. The cells showed good viability and proliferation, but their growth was impeded by surface unevenness. Our results suggest that both techniques are suitable for implants production. Statistical evaluation was performed by ANOVA followed by Tukeys test.