The corrosion resistance of nanostructured nitinol (NiTi) was investigated using long-term tests in solutions simulating physiological fluids at static conditions, reflecting the material structure and metal concentration in the solutions. Mechanical polishing reduced the ion release by a factor of two to three, whereas annealing deteriorated the corrosion resistance. The depassivation and repassivation of nitinol surfaces were considered. We found that nanostructured nitinol might increase the corrosion leaching of titanium into solutions, although the nickel release decreased. Metal dissolution did not occur in the alkaline environment or artificial plasma. A Ni-free surface with a protective 25 nm-thick titanium oxide film resulted from soaking mechanically treated samples of the NiTi wire in a saline solution for two years under static conditions. Hence, the medical application of nanostructured NiTi, such as for the production of medical devices and implants such as stents, shows potential compared with microstructured NiTi.
A technology for obtaining materials from nanostructured nitinol with titanium- or tantalum-enriched surface layers was developed. Surface layers enriched with titanium or tantalum were shown to provide a decrease in the formation of reactive oxygen species and long-lived protein radicals in comparison to untreated nitinol. It was determined that human peripheral vessel myofibroblasts and human bone marrow mesenchymal stromal cells grown on nitinol bases coated with titanium or tantalum-enriched surface layers exhibit a nearly two times higher mitotic index. Response to implantation of pure nitinol, as well as nano-structure nitinol with titanium or tantalum-enriched surface layers, was expressed though formation of a mature uniform fibrous capsule peripherally to the fragment. The thickness of this capsule in the group of animals subjected to implantation of pure nitinol was 1.5 and 3.0-fold greater than that of the capsule in the groups implanted with nitinol fragments with titanium- or tantalum-enriched layers. No signs of calcinosis in the tissues surrounding implants with coatings were observed. The nature and structure of the formed capsules testify bioinertia of the implanted samples. It was shown that the morphology and composition of the surface of metal samples does not alter following biological tests. The obtained results indicate that nano-structure nitinol with titanium or tantalum enriched surface layers is a biocompatible material potentially suitable for medical applications.
A Ti–25Nb–13Ta–5Zr alloy was produced and studied in this work, and plates and wires were made from this alloy. It is shown that the Ti–25Nb–13Ta–5Zr alloy has the required mechanical properties and a β-crystal phase. Microstructures were present on the surface of the alloy with a height of several hundred nm, located at a distance of 1.5–2 μm from each other. Ti–25Nb–13Ta–5Zr was superior to nitinol in terms of the formation of long-living reactive protein species and the generation of reactive oxygen species. Cell cultivation on Ti–25Nb–13Ta–5Zr alloy surfaces revealed a significant mitotic index (2%) and a small number of nonviable cells (<5%). The cells were actively attached and spread over the alloy. The biocompatibility of Ti–25Nb–13Ta–5Zr was verified by experiments on the implantation of the alloy in the form of plates and coiled wires. The surface morphology of the specimens after biological trials was not significantly altered. The experimental data we obtained suggest that Ti–25Nb–13Ta–5Zr is suitable for potential applications in biology and medicine.
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