Microstructure and in vitro degradation performance of Mg-Zn-Mn alloys for biomedical application.

Manganese and zinc were selected as alloying elements to develop a Mg-based ternary alloy for biomedical applications, taking into account the good biocompatibility of these metals. The microstructures of Mg-Zn-Mn alloys containing 0.5 or 1.0 mass% of manganese and 1.0 or 1.5 mass% of zinc were investigated by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. Their corrosion properties were assessed by means of potentiodynamic polarization and electrochemical impedance spectroscopy measurements performed in Ringer's physiological solution that simulates bodily fluids. All tested samples are two-phase alloys formed by a Mg-based matrix, consisting of a Mg-Zn-Mn solid solution, and a Mg-Zn binary phase. The electrochemical results show an improvement of the corrosion behavior of the investigated alloys with increasing Zn and Mn content. This is attributed to the formation of a partially protective Mg(OH)(2) surface film whose protective capabilities are increased by the alloying elements. The reduced influence of the Mg-Zn intermetallic compound on the corrosion rate of Mg-Zn-Mn alloys in the presence of a partially protective surface layer can be ascribed to an increasing resistance between the Mg-Zn-Mn solid solution and the second phase, thereby decreasing the effective driving force for microgalvanic corrosion. Owing to its highest corrosion protective ability, the Mg-1.5Zn-1Mn alloy is a promising candidate for the development of degradable implants, such as screws, plates, and rods.

Influence of noble metals alloying additions on the corrosion behaviour of titanium in a fluoride-containing environment.

Titanium alloys exhibit excellent corrosion resistance in most aqueous media due to the formation of a stable oxide film, and some of these alloys (particularly Ti-6Al-7Nb) have been chosen for surgical and odontological implants for their resistance and biocompatibility. Treatment with fluorides (F(-)) is known to be the main method for preventing plaque formation and dental caries. Toothpastes, mouthwashes, and prophylactic gels can contain from 200 to 20,000 ppm F(-) and can affect the corrosion behaviour of titanium alloy devices present in the oral cavity. In this work, the electrochemical corrosion behaviour of Ti-1M alloys (M = Ag, Au, Pd, Pt) was assessed in artificial saliva of pH = 3.0 containing 910 ppm F(-) (0.05 M NaF) through open circuit potential, E(OC), and electrochemical impedance spectroscopy (EIS) measurements. The corrosion behaviour of the Ti-6Al-7Nb commercial alloy was also evaluated for comparison. E (OC) measurements show an active behaviour for all the titanium alloys in fluoridated acidified saliva due to the presence of significant concentrations of HF and HF(2) (-) species that dissolve the spontaneous air-formed oxide film giving rise to surface activation. However, an increase in stability of the passive oxide layer and consequently a decrease in surface activation is observed for the Ti-1M alloys. This behaviour is confirmed by EIS measurements. In fact, the Ti-6Al-7Nb alloy exhibits lower impedance values as compared with Ti-1M alloys, the highest values being measured for the Ti-1Au alloy. The experimental results show that the corrosion resistance of the studied Ti-1M alloys is similar to or better than that of Ti-6Al-7Nb alloy currently used as biomaterial, suggesting their potential for dental applications.

In vitro corrosion behaviour of Ti-Nb-Sn shape memory alloys in Ringer's physiological solution.

The nearly equiatomic Ni-Ti alloy (Nitinol) has been widely employed in the medical and dental fields owing to its shape memory or superelastic properties. The main concern about the use of this alloy derives form the fact that it contains a large amount of nickel (55% by mass), which is suspected responsible for allergic, toxic and carcinogenic reactions. In this work, the in vitro corrosion behavior of two Ti-Nb-Sn shape memory alloys, Ti-16Nb-5Sn and Ti-18Nb-4Sn (mass%) has been investigated and compared with that of Nitinol. The in vitro corrosion resistance was assessed in naturally aerated Ringer's physiological solution at 37°C by corrosion potential and electrochemical impedance spectroscopy (EIS) measurements as a function of exposure time, and potentiodynamic polarization curves. Corrosion potential values indicated that both Ni-Ti and Ti-Nb-Sn alloys undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Ti-18Nb-5Sn alloy. Significantly low anodic current density values were obtained from the polarization curves, indicating a typical passive behaviour for all investigated alloys, but Nitinol exhibited breakdown of passivity at potentials above approximately 450 mV(SCE), suggesting lower corrosion protection characteristics of its oxide film compared to the Ti-Nb-Sn alloys. EIS studies showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The obtained EIS spectra were analyzed using an equivalent electrical circuit representing a duplex structure oxide film, composed by an outer and porous layer (low resistance), and an inner barrier layer (high resistance) mainly responsible for the alloys corrosion resistance. The resistance of passive film present on the metals' surface increases with exposure time displaying the highest values to Ti-18Nb-4Sn alloy. All these electrochemical results suggest that Ti-Nb-Sn alloys are promising materials for biomedical applications.

Study of the in vitro corrosion behavior and biocompatibility of Zr-2.5Nb and Zr-1.5Nb-1Ta (at%) crystalline alloys.

The in vitro corrosion behavior and biocompatibility of two Zr alloys, Zr-2.5Nb, employed for the manufacture of CANDU reactor pressure tubes, and Zr-1.5Nb-1Ta (at%), for use as implant materials have been assessed and compared with those of Grade 2 Ti, which is known to be a highly compatible metallic biomaterial. The in vitro corrosion resistance was investigated by open circuit potential and electrochemical impedance spectroscopy (EIS) measurements, as a function of exposure time to an artificial physiological environment (Ringer's solution). Open circuit potential values indicated that both the Zr alloys and Grade 2 Ti undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Zr-1.5Nb-1Ta alloy and that this oxide has better corrosion protection characteristics than the ones formed on Grade 2 Ti or on the Zr-2.5Nb alloy. EIS study showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The fit obtained suggests a single passive film presents on the metals surface, improving their resistance with exposure time, presenting the highest values to the Zr-1.5Nb-1Ta alloy. For the biocompatibility analysis human osteosarcoma cell line (Saos-2) and human primary bone marrow stromal cells (BMSC) were used. Biocompatibility tests showed that Saos-2 cells grow rapidly, independently of the surface, due to reduced dependency from matrix deposition and microenvironment recognition. BMSC instead display a reduced proliferation, possibly caused by a reduced crosstalk with the metal surface microenvironment. However, once the substrate has been colonized, BMSC seem to respond properly to osteoinduction stimuli, thus supporting a substantial equivalence in the biocompatibility among the Zr alloys and Grade 2 titanium. In summary, high in vitro corrosion resistance together with satisfactory biocompatibility make the Zr-2.5Nb and Zr-1.5Nb-1Ta crystalline alloys promising biomaterials for surgical implants.

Bio-corrosion characterization of Mg-Zn-X (X = Ca, Mn, Si) alloys for biomedical applications.

The successful applications of magnesium-based alloys as biodegradable orthopedic implants are mainly inhibited due to their high degradation rates in physiological environment. This study examines the bio-corrosion behaviour of Mg-2Zn-0.2X (X = Ca, Mn, Si) alloys in Ringer's physiological solution that simulates bodily fluids, and compares it with that of AZ91 magnesium alloy. Potentiodynamic polarization and electrochemical impedance spectroscopy results showed a better corrosion behaviour of AZ91 alloy with respect to Mg-2Zn-0.2Ca and Mg-2Zn-0.2Si alloys. On the contrary, enhanced corrosion resistance was observed for Mg-2Zn-0.2Mn alloy compared to the AZ91 one: Mg-2Zn-0.2Mn alloy exhibited a four-fold increase in the polarization resistance than AZ91 alloy after 168 h exposure to the Ringer's physiological solution. The improved corrosion behaviour of the Mg-2Zn-0.2Mn alloy with respect to the AZ91 one can be ascribed to enhanced protective properties of the Mg(OH)(2) surface layer. The present study suggests the Mg-2Zn-0.2Mn alloy as a promising candidate for its applications in degradable orthopedic implants, and is worthwhile to further investigate the in vivo corrosion behaviour as well as assessed the mechanical properties of this alloy.

New chemical treatment for bioactive titanium alloy with high corrosion resistance.

It was recently claimed that titanium metal and its alloys can bond to the living bone, without being coated by apatite (VPS coatings), but by being chemically and heat-treated. The bioactivity of treated titanium is of interest because of the opportunity to obtain orthopaedic or dental implants presenting, at the same time, high toughness, strength and fatigue resistance as well as bone-bonding ability. The bioactive behaviour of the treated implants is due to the presence of a modified surface, which, during soaking in body fluid, promotes the precipitation of apatite. The apatite formed is strongly bonded to the substrate and promotes living bone bonding. In this work were characterised samples of Ti-6Al-7Nb alloy with surfaces presenting a different chemical and mechanical state. The aim of the research was twofold. The first objective was to characterise chemically and heat-treated samples with different surface topography, in order to define the best conditions for osteogenic integration. The second aim was to assess the corrosion behaviour of the bioactive implants, because they expose a microporous and quite thin modified surface layer. No-treated and passivated samples, with a surface state closed to that nowadays used on implants, were used as reference. The surface structure, morphology, electrochemical behaviour and bioactivity of the different samples were assessed by means of XRD, SEM-EDS, anodic polarizations, open circuit measurements and in-vitro tests. Results evidence that it is possible to modify the surface of the Ti-6Al-7Nb alloy in order to obtain the formation of a bioactive layer and that the substrate roughness influences the characteristics of the surface layer formed. It was also evidenced that the as treated surfaces present inadequate corrosion behaviour, so a new two-step chemical treatment has been developed in order to obtain a bioactive material with good corrosion resistance.

Ni-Zr alloys: relationship between surface characteristics and electrocatalytic behavior

A relationship between electrocatalytic activity for the hydrogen evolution reaction and the surface composition of the electrode was established for Ni-Zr crystalline and amorphous alloys by means of secondary ion mass spectrometry (SIMS). Electrocatalytic activity was tested by means of cathodic polarization in 1 M KOH at 25 degrees C and the resulting exchange current density has been taken as a measure of catalytic efficiency. Surface activation treatment involved chemical etching in HF solutions; the consequent morphological and compositional surface changes were studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical behavior of the pure elements (Ni and Zr) was also considered for comparison. All samples submitted to chemical etching in HF solutions showed an increase in electrocatalytic activity, particularly the alloy with the highest Ni content. The beneficial effect of chemical etching is due to dissolution of the zirconium oxide layer and to the formation of nanocrystalline Ni on the surfaces.

Reliability of Pd based dental alloys regarding to corrosion resistance and production processes.

The knowledge of the relationship among chemical composition, microstructure, productive processes, functional properties, quality and price of the final product is an ever greater requirement for the firms producing dental alloys as well as for the dental laboratories making prosthesis. The present study deals with the evaluation of the corrosion resistance of high-Pd and Pd-Ag alloys by quantification of released ions following the recent European regulations suggested. Moreover the reliability of the alloys as far as concern their corrosion resistance was also investigated in relation to the different steps of alloy industrial production and restoration forming processes as well as after homogenization treatments followed by different cooling rate. The very complex microstructure of both alloys was greatly affected by the different casting conditions, deformation rate and thermal treatments used in alloy industrial production and prosthesis manufacturing. However the corrosion resistance of both alloys remained very good in all metallurgical states. The potentiodynamic tests allowed to distinguish among the structural conditions: the homogenization treatments, eliminating segregation inside the different phases, improved further the corrosion resistance of both alloys.

Influence of corrosion on brazed joints' strength.

The influence of corrosion on the bond strength of different brazed joints commonly used in dentistry has been investigated by means of accelerated immersion tests in artificial saliva buffered at pH 2, and in Ringer's solution, both kept at 37 degrees C. Two Co-Cr base metal alloys were brazed with a gold and a non-precious alloy. After 60 days' immersion the tensile strength of the samples brazed with the gold alloy was dramatically reduced because of galvanic corrosion phenomena. The bond strength of the specimens brazed with the non-precious alloy was largely unaffected. Corrosion products rich in nickel were detected. The electrochemical characterization of the base metal alloys and brazing materials was performed by means of polarization curves in the two media investigated. High short circuit currents were only produced with the gold brazing materials.