Doina-Margareta Gordin

Comparative corrosion study of Ti-Ta alloys for Dental applications

Besides other important material features, the corrosion parameters and corrosion products are responsible for limiting the biocompatibility of metallic materials, and can produce undesirable reactions in implant-adjacent and/or more distant tissues. Titanium and some of its alloys are known as being the most biocompatible metallic materials due to their high strength, low modulus, high corrosion resistance in biological media, etc. More recently, Ti-Ta alloys have been developed, and these are expected to become more promising candidates for biomedical and dental applications than commercially pure Ti, Ti-6Al-4V or Ti-6Al-7Nb alloy. The corrosion behavior of the studied Ti-Ta alloys with Ta contents of 30, 40, 50 and 60 wt.% together with the currently used Ti-6Al-7Nb alloy were investigated for dental applications. All alloys were tested by open-circuit potential measurement, linear polarization, potentiodynamic polarization, coulometric zone analysis and electrochemical impedance spectroscopy performed in artificial saliva with different pH, acid lactic and fluoride contents. The passive behavior for all the titanium alloys is observed for artificial saliva, acidified saliva (9.8 gl(-1) lactic acid, pH 2.5) and for fluoridated saliva (1.0 gl(-1) F(-), pH 8). A decrease in corrosion resistance and less protective passive oxide films are observed for all titanium alloys in fluoridated acidified saliva (9.8 gl(-1) lactic acid, 1.0 gl(-1) F(-), pH 2.5) in regard to other electrochemical media used within this work. It is worthy of note that the most important decrease was found for Ti-6Al-7Nb alloy. These conclusions are confirmed by all the electrochemical tests undertaken. However, the results confirm that the corrosion resistance of the studied Ti-Ta alloys in all saliva is better or similar to that of Ti-6Al-7Nb alloy, suggesting that the Ti-Ta alloys have potential for dental applications.

Synthesis and characterisation of a new superelastic Ti–25Ta–25Nb biomedical alloy

In this study, a new Ti-25Ta-25Nb (mass%) beta alloy was synthesised by cold crucible semi-levitation melting. This technique made it possible to obtain homogeneous ingots although the elements used have very different melting points. After melting, a thermo-mechanical treatment was applied in order to obtain a perfectly recrystallised beta microstructure. For this alloy composition, the tensile tests showed a very low Youngs modulus associated with an important super-elastic behaviour, which contributes to decrease the elastic modulus under stress and to increase the recoverable strain. On the other hand, the corrosion tests, which were carried out in a neutral Ringer solution, indicated a corrosion resistance higher than that of the commercially pure CP Ti alloy. These results show that this new alloy possesses all the characteristics necessary for its long-term use in medical implants.

Microstructure, mechanical properties and cytocompatibility of stable beta Ti-Mo-Ta sintered alloys.

We have synthesized titanium-based alloys containing molybdenum and tantalum elements by powder metallurgy. The microstructure, the residual porosity and the mechanical properties of the sintered Ti-Mo and Ti-Ta-Mo alloys were investigated by using optical and electronic microscopy, X-ray diffraction, microhardness and compression tests. The cytocompatibility of the different alloys was evaluated by the assessment of bone cell density, migration and adhesion after 14 days incubation. All the alloys present a high ductility and an excellent cytocompatibility, which make these materials useful for medical implants.

In vitro bio-functional performances of the novel superelastic beta-type Ti–23Nb–0.7Ta–2Zr–0.5N alloy

The materials used for internal fracture fixations and joint replacements are mainly made of metals which still face problems ranging from higher rigidity than that of natural bone to leaching cytotoxic metallic ions. Beta (β)-type titanium alloys with low elastic modulus made from non-toxic and non-allergenic elements are desirable to reduce stress shielding effect and enhance bone remodeling. In this work, a new β-type Ti-23Nb-0.7Ta-2Zr-0.5N alloy with a Youngs modulus of approximately 50 GPa was designed and characterized. The behavior of MC3T3-E1 pre-osteoblasts on the new alloy, including adhesion, proliferation and differentiation, was evaluated by examining the cytoskeleton, focal adhesion formation, metabolic activity and extracellular matrix mineralization. Results indicated that the pre-osteoblast cells exhibited a similar degree of attachment and growth on Ti-23Nb-0.7Ta-2Zr-0.5N and Ti-6Al-4V. However, the novel alloy proved to be significantly more efficient in sustaining mineralized matrix deposition upon osteogenic induction of the cells than Ti-6Al-4V control. Further, the analysis of RAW 264.7 macrophages cytokine gene and protein expression indicated no significant inflammatory response. Collectively, these findings suggest that the Ti-23Nb-0.7Ta-2Zr-0.5N alloy, which has an increased mechanical biocompatibility with bone, allows a better osteogenic differentiation of osteoblast precursor cells than Ti-6Al-4V and holds great potential for future clinical prosthetic applications.

Design of a nitrogen-implanted titanium-based superelastic alloy with optimized properties for biomedical applications.

In this study, a superelastic Ni-free Ti-based biomedical alloy was treated in surface by the implantation of nitrogen ions for the first time. The N-implanted surface was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and secondary ion mass spectroscopy, and the superficial mechanical properties were evaluated by nano-indentation and by ball-on-disk tribological tests. To investigate the biocompatibility, the corrosion resistance of the N-implanted Ti alloy was evaluated in simulated body fluids (SBF) complemented by in-vitro cytocompatibility tests on human fetal osteoblasts. After implantation, surface analysis methods revealed the formation of a titanium-based nitride on the substrate surface. Consequently, an increase in superficial hardness and a significant reduction of friction coefficient were observed compared to the non-implanted sample. Also, a better corrosion resistance and a significant decrease in ion release rates have been obtained. Cell culture experiments indicated that the cytocompatibility of the N-implanted Ti alloy was superior to that of the corresponding non-treated sample. Thus, this new functional N-implanted titanium-based superelastic alloy presents the optimized properties that are required for various medical devices: superelasticity, high superficial mechanical properties, high corrosion resistance and excellent cytocompatibility.

Osteoblast cell behavior on the new beta-type Ti-25Ta-25Nb alloy.

Among metallic materials used as bone substitutes, β titanium alloys gain an increasing importance because of their low modulus, high corrosion resistance and good biocompatibility. In this work, an investigation of the in vitro cytocompatibility of a recently new developed β-type Ti-25Ta-25Nb alloy was carried out by evaluating the behavior of human osteoblasts. The metallic Ti-6Al-4V biomaterial, which is one of representative α+β type titanium alloys for biomedical applications, and Tissue Culture Polystyrene (TCPS), were also investigated as reference Ti-based material and control substrate, respectively. Both metallic surfaces were analyzed by X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy. The cellular response was quantified by assessments of viability, cell attachment and spreading, cell morphology, production and extracellular organization of fibronectin and cell proliferation. Polished surfaces from both materials having an equiaxed grain microstructure and nanometre scale surface roughness elicited an essentially identical osteoblast response in terms of all analyzed cellular parameters. Thus, on both surfaces the cells displayed high survival rates, good cell adhesion and spreading, a dense and randomly dispersed fibronectin matrix and increasing cell proliferation rates over the incubation time. Furhermore, the enhanced biological performance of Ti-25Ta-25Nb was highly supported by the results obtained in comparison with TCPS. These findings, together with previously shown superelastic behavior, low Youngs modulus and high corrosion resistance, recommend Ti-25Ta-25Nb as good candidate for applications in bone implantology.

Surface characterization and biocompatibility of titanium alloys implanted with nitrogen by Hardion+ technology

In this study, the new Hardion+ micro-implanter technology was used to modify surface properties of biomedical pure titanium (CP-Ti) and Ti–6Al–4V ELI alloy by implantation of nitrogen ions. This process is based on the use of an electron cyclotron resonance ion source to produce a multienergetic ion beam from multicharged ions. After implantation, surface analysis methods revealed the formation of titanium nitride (TiN) on the substrate surfaces. An increase in superficial hardness and a significant reduction of friction coefficient were observed for both materials when compared to non-implanted samples. Better corrosion resistance and a significant decrease in ion release rates were observed for N-implanted biomaterials due to the formation of the protective TiN layer on their surfaces. In vitro tests performed on human fetal osteoblasts indicated that the cytocompatibility of N-implanted CP-Ti and Ti–6Al–4V alloy was enhanced in comparison to that of the corresponding non treated samples. Consequently, Hardion+ implantation technique can provide titanium alloys with better qualities in terms of corrosion resistance, cell proliferation, adhesion and viability.

In vitro performance assessment of new beta Ti-Mo-Nb alloy compositions.

New β-titanium based alloys with low Youngs modulus are currently required for the next generation of metallic implant materials to ensure good mechanical compatibility with bone. Several of these are representatives of the ternary Ti-Mo-Nb system. The aim of this paper is to assess the in vitro biological performance of five new low modulus alloy compositions, namely Ti12Mo, Ti4Mo32Nb, Ti6Mo24Nb, Ti8Mo16Nb and Ti10Mo8Nb. Commercially pure titanium (cpTi) was used as a reference material. Comparative studies of cell activity exhibited by MC3T3-E1 pre-osteoblasts over short- and long-term culture periods demonstrated that these newly-developed metallic substrates exhibited an increased biocompatibility in terms of osteoblast proliferation, collagen production and extracellular matrix mineralization. Furthermore, all analyzed biomaterials elicited an almost identical cell response. Considering that macrophages play a pivotal role in bone remodeling, the behavior of a monocyte-macrophage cell line, RAW 264.7, was also investigated showing a slightly lower inflammatory response to Ti-Mo-Nb biomaterials as compared with cpTi. Thus, the biological performances together with the superior mechanical properties recommend these alloys for bone implant applications.

Nitride coating enhances endothelialization on biomedical NiTi shape memory alloy

Surface nitriding was demonstrated to be an effective process for improving the biocompatibility of implantable devices. In this study, we investigated the benefits of nitriding the NiTi shape memory alloy for vascular stent applications. Results from cell experiments indicated that, compared to untreated NiTi, a superficial gas nitriding treatment enhanced the adhesion of human umbilical vein endothelial cells (HUVECs), cell spreading and proliferation. This investigation provides data to demonstrate the possibility of improving the rate of endothelialization on NiTi by means of nitride coating.

Surface Characterization, Corrosion Resistance and in Vitro Biocompatibility of a New Ti‐Hf‐Mo‐Sn Alloy

A new superelastic Ti-23Hf-3Mo-4Sn biomedical alloy displaying a particularly large recovery strain was synthesized and characterized in this study. Its native passive film is very thick (18 nm) and contains very protective TiO2, Ti2O3, HfO2, MoO2, and SnO2 oxides (XPS analysis). This alloy revealed nobler electrochemical behavior, more favorable values of the corrosion parameters and open circuit potentials in simulated body fluid in comparison with commercially pure titanium (CP-Ti) and Ti-6Al-4V alloy taken as reference biomaterials in this study. This is due to the favorable influence of the alloying elements Hf, Sn, Mo, which enhance the protective properties of the native passive film on alloy surface. Impedance spectra showed a passive film with two layers, an inner, capacitive, barrier, dense layer and an outer, less insulating, porous layer that confer both high corrosion resistance and bioactivity to the alloy. In vitro tests were carried out in order to evaluate the response of Human Umbilical Vein Endothelial Cells (HUVECs) to Ti-23Hf-3Mo-4Sn alloy in terms of cell viability, cell proliferation, phenotypic marker expression and nitric oxide release. The results indicate a similar level of cytocompatibility with HUVEC cells cultured on Ti-23Hf-3Mo-4Sn substrate and those cultured on the conventional CP-Ti and Ti-6Al-4V metallic materials.