M. L. Escudero

Corrosion behaviour of AZ31 magnesium alloy with different grain sizes in simulated biological fluids

The corrosion behaviour of AZ31 magnesium alloy with different grain sizes immersed in simulated body fluids was compared in chloride solution (8 gl(-1)) and in phosphate-buffer solution (PBS). The influence of immersion time was also analyzed. Electrochemical techniques such as open circuit potential, polarization curves, transient currents and electrochemical impedance spectroscopy, complemented with scanning electron microscopy and energy dispersive spectroscopy, were used. Immediately after the immersion in the corrosive media the corrosion resistance was similar for both grain sizes of the AZ31 alloy and higher in NaCl solutions than in PBS. However, this corrosion behaviour was reversed after longer periods of immersion due to the stabilizing of the corrosion products of MgO by P-containing compounds. These P-compounds contribute to a higher level of protection by hindering the aggressive action of chloride ions. The best corrosion behaviour of the AZ31 alloy was obtained for the finest grain alloy associated with the highest transfer resistance value, after long periods of immersion in PBS.

Influence of the microstructure and topography on the barrier properties of oxide scales generated on blasted Ti6Al4V surfaces.

The long-term interfacial bond between an implant and bone may be improved by creating a rough surface on the implant in order to increase the surface area available for bone/implant apposition. A natural consequence of surface roughening is an increase in metal ion release, which is itself a surface dominated process. Based on this fact, the aim of this work is to study the influence of the microstructure and topography on the barrier properties of oxide scales thermally generated at 700 °C for 1h on Ti6Al4V surfaces after blasting with Al(2)O(3) particles (coarse) or SiO(2) and ZrO(2) particles (fine). The microstructural and topographical characterization of the thermally treated blasted surfaces has been studied by means of scanning electron microscopy coupled with energy dispersive X-ray analysis, contact profilometry and X-ray diffraction. The barrier properties and corrosion behaviour of the oxide layers have been studied by means of electrochemical impedance spectroscopy (EIS) in Hanks solution. Thermal treatment at 700 °C for 1h promotes the formation of oxide scales with different morphologies and crystalline structures depending on the degree of deformation of the blasted surface. The oxide scale grown on the finely blasted sample has a pine needle-like morphology which is mainly formed of anatase TiO(2). In contrast, the oxide scale grown on the coarsely blasted sample has a globular morphology formed mainly of rutile TiO(2). The differences in morphology, i.e. fine or coarse, of the oxide scales influence the corrosion response of the blasted thermally treated samples in Hanks solution. The EIS results permit evaluation of the different oxide scales from the capacitance and resistance values obtained in the high-frequency region and show a good correlation between the morphology and barrier properties. Oxidation treatment at 700 °C for 1h of Ti6Al4V samples coarsely blasted with Al(2)O(3) improves the corrosion behaviour due to an increase in the thickness of a compact, ordered and more structurally stable oxide scale. This is due to the globular morphology of the rutile (TiO(2)) structure maintaining an average surface roughness suitable for optimal osseo-integration with long-term interfacial bonding between the implant and bone.

Comparative study of the corrosion behavior of MA‐956 and conventional metallic biomaterials

In this work the corrosion behavior of a new biomaterial, the MA-956 superalloy, immersed in Hanks solution is evaluated. A comparison with conventional metallic alloys used as articular implants is established. To determine the corrosion behavior we employed electrochemical methods: evaluation of corrosion potential Ecorr, electrochemical impedance spectroscopy (EIS), and anodic polarization curves. The corrosion resistance of the MA-956 superalloy preoxidized at 1100 degrees C during 100 h is at least two orders of magnitude higher than for the other alloys. This satisfactory behavior is stationary with time. Also the probability of the appearance of the pitting corrosion process is very low. When cracking is generated in the alpha-alumina layer the repassivation process is assured because of the high Cr content in the superalloy. This study is the first step in proposing this new alloy as a biomaterial. The low toxicity of these metallic alloys in the physiological environment suggests that in vivo their biocompatibility could be satisfactory.

Corrosion behaviour of an Fe3Al-type intermetallic in a chloride containing solution

Abstract The corrosion behaviour of an Fe 3 Al-base intermetallic compound with different crystal structures in a chloride containing solution has been investigated. The corrosion current densities of this intermetallic were independent of the material crystal structure showing a passive state stable with time. These corrosion rates were of the same order of magnitude as for 316L stainless steel. The pitting corrosion resistance evaluated by means of cyclic anodic polarization curves was high for all different states. Amongst the different crystal structures of this intermetallic alloy, the two ordered states present the lowest pitting probability. This Fe 3 Al intermetallic shows higher pitting corrosion resistance than the 316L stainless steel but its capacity for repassivation is lower. A damaging factor of influence on the pitting corrosion behaviour is the presence of non-metallic inclusions on the surface which reduce the pitting corrosion resistance by almost a half.

Corrosion behaviour of amorphous Fe-Cr-Ni-(Si,P) alloys

Abstract The passive layers formed spontaneously via air contact on the surface of amorphous Fe62 Cr10 Ni8 X20 (X = Si,P) alloys were studied by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The results for Fe62 Cr10 Ni8 Si20 showed the formation of a protective film, mainly consisting of oxidized chromium, that greatly enhanced the corrosion resistance of this alloy, whereas in Fe62 Cr10 Ni8 p20 the film was less corrosion resistant. To evaluate the influence of the passive layer composition on the corrosion resistance, standard electrochemical measurements on both alloys in 0.01 M HCl solution were performed. The study reveals that the best corrosion behaviour is given by the Si containing amorphous alloy confirming XPS and AES results.

Electrochemical impedance spectroscopy of preoxidized MA 956 superalloy during in vitro experiments

Preoxidation treatment of MA 956 superalloy at 1100 degrees C produces a fine and tightly adherent alpha-alumina layer at the surface, which provides the alloy with an excellent barrier against a great variety of aggressive environments. In this work the protective capacity of the alumina/alloy system is evaluated in a physiological medium by means of electrochemical impedance spectroscopy. The electrochemical response of the material is modelled by equivalent circuits which provide the most relevant corrosion and protection parameters applicable to MA 956 in both preoxidized and as-received conditions (passivated state). The high protective capacity of preoxidized MA 956 superalloy holds for long-term tests, which indicates that the corrosion phenomena, if any, would be characterized by very slow kinetics. The corrosion resistance of the preoxidized material is at least two orders of magnitude higher than that of the non-treated alloy.

Study of the interaction of inorganic and organic compounds of cell culture medium with a Ti surface.

The interaction between Ti and each component of Dulbeccos modified Eagles medium was studied in depth using different techniques, such as the measurement of the corrosion potential, electrochemical impedance spectroscopy and polarization curves. The characterization of metal surfaces was carried out by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). The adsorption process of each component was studied using the quartz crystal balance (QCM). The QCM and XPS results reveal that the adsorption kinetics for phosphate and calcium ions is slow. However, the bovine serum albumin (BSA) totally covers the Ti surface rapidly. Because the passive film (titanium oxide) has acidic hydroxyl groups, the calcium ions would have a bridging effect on the electrostatic adsorption of phosphate ions as well as that of BSA. The polarization curves reveal that the adsorbed glucose permits the ionic diffusion of the oxygen to the electrode, while the BSA and fetal bovine serum (FBS) adsorbed after 7 days of immersion act as a diffusive barrier. The impedance measurement and data fitting to the electrical equivalent circuit model show that the resistance of the proteins/TiO(2) interface, for Ti immersed in FBS, is higher than those obtained for BSA, due to the proteins present in the solution as well as the fact that the adsorbed proteins on the surface are greater.

In situ cell culture monitoring on a Ti–6Al–4V surface by electrochemical techniques

In this work, the in situ interaction between Ti-6Al-4V alloy and osteoblastic cells has been studied by electrochemical techniques as a function of time. The interaction has been monitored for cell adhesion and growth of human osteoblastic Saos-2 cells on Ti-6Al-4V samples. The study has been carried out by electrochemical techniques, e.g., studying the evolution of corrosion potential with exposure time and by electrochemical impedance spectroscopy. The impedance results have been analyzed by using different equivalent circuit models that simulate the interface state at each testing time. The adhesion of the osteoblastic cells on the Ti-6Al-4V alloy leads to surface areas with different cell coverage rates, thus showing the different responses in the impedance diagrams with time. The effect of the cells on the electrochemical response of Ti-6Al-4V alloy is clearly seen after 4 days of testing, in which two isolated and well-differentiated time constants are clearly observed. One of these is associated with the presence of the cells and the other with a passive film on the Ti-6Al-4V alloy. After 7 days of culture, the system is governed by a resistive component over a wide frequency range which is associated with an increase in the cell coverage rate on the surface due to the extracellular matrix.

Response of MC3T3‐E1 osteoblasts, L929 fibroblasts, and J774 macrophages to fluoride surface‐modified AZ31 magnesium alloy

The present work evaluates the biocompatibility of a fluoride surface-modified AZ31 magnesium alloy (AZ31HF) with different cell lines that coexist in the implant environment to test its potential use as a biodegradable and absorbable biomaterial for bone repair. A clear stimulation of cell proliferation and an enhancement of the mitochondrial respiratory activity were observed when mouse osteoblasts (MC3T3-E1), fibroblasts (L929), and macrophages (J774) cell lines were cultured with the modified alloy. No significant change in apoptosis or viability rates was observed when osteoblasts and fibroblasts cultures were grown in the presence of this alloy. A proteomic analysis of the MC3T3-E1 cell extracts cultured in the presence of AZ31HF showed an overexpression of proteins related with the mineralization process, which is a necessary step for bone repair. An increase in the lactate dehydrogenase activity was observed in the MC3T3-E1 and J774 cell cultures that could be a response of the oxidative stress produced by the presence of the material. This stress could be related to the increase observed in the respiratory mitochondrial activity or respiratory burst measured in theses cultures that indicate damage in the cell membranes and subsequently some cell death. Results reported here, for and against AZ31HF, should be taken into account when considering the potential use of this modified alloy in bone repair applications.

Surface analysis of a heat-treated, Al-containing, iron-based superalloy

This work was supported by the project MAT95-0249-C03-01 of the Spanish Comision Interministerial de Ciencia y Tecnologia (CICYT).