Titanium dental implants show very good properties, unfortunately there are still issues regarding material wear due to corrosion, implant loosening, as well as biological factors—allergic reactions and inflammation leading to rejection of the implanted material. In order to avoid performing reimplantation operations, changes in the chemical composition and/or modifications of the surface layer of the materials are used. This research is aimed at explaining the possible mechanisms of titanium dissolution and the role of oxide coating, and its damage, in the enhancement of the corrosion process. The studies of new and used implants were made by scanning electron microscopy and computer tomography. The long-term chemical dissolution of rutile was studied in Ringer’s solution and artificial saliva at various pH levels and room temperature. Inductively coupled plasma mass spectrometry (ICP-MS) conjugated plasma ion spectrometry was used to determine the number of dissolved titanium ions in the solutions. The obtained results demonstrated the extremely low dissolution rate of rutile, slightly increasing along with pH. The diffusion calculations showed that the diffusion of titanium through the oxide layer at human body temperature is negligible. The obtained results indicate that the surface damage followed by titanium dissolution is initiated at the defects caused by either the manufacturing process or implantation surgery. At a low thickness of titanium oxide coating, there is a stepwise appearance and development of cracks that forms corrosion tunnels within the oxide coating.
The increasing demand for titanium and its alloys used for implants results in the need for innovative surface treatments that may both increase corrosion resistance and biocompatibility and demonstrate antibacterial protection at no cytotoxicity. The purpose of this research was to characterize the effect of two-stage anodization—performed for 30 min in phosphoric acid—in the presence of hydrofluoric acid in the second stage. Scanning electron microscopy, atomic force microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, glow discharge optical emission spectroscopy, nanoindentation and nano-scratch tests, potentiodynamic corrosion studies, and water contact angle measurements were performed to characterize microstructure, mechanical, chemical and physical properties. The biologic examinations were carried out to determine the cytotoxicity and antibacterial effects of oxide coatings. The research results demonstrate that two-stage oxidation affects several features and, in particular, improves mechanical and chemical behavior. The processes influencing the formation and properties of the oxide coating are discussed.
The growing demand for implants has seen increasing interest in the introduction of new technologies and surface modification methods of metal biomaterials. This research aimed to produce and characterize a porous layer grown on austenitic stainless steel 316L, obtained via the anodization process near the micro-arc oxidation, i.e., low voltage micro-arc oxidation (LVMAO). The discussed layer significantly influences the properties of metallic biomedical materials. The surface topography, layer thickness, surface roughness, pore diameter, elemental composition, crystal structure, and surface wettability were assessed for all anodized layers, together with the resultant corrosion resistance. Attention was paid to the influence of the process parameters that affect the specification of the produced layer. The obtained results showed surface development and different sized pores in the modified layers, as well as an increase in corrosion resistance in the Ringer’s solution.
The surface condition of an implant has a significant impact on response occurring at the implant-biosystem border. The knowledge of physical-chemical and biological processes allows for targeted modification of biomaterials to induce a specified response of a tissue. The present research was aimed at development of technology composing of obtaining the nanotube oxide layers on a porous titanium alloy Ti13Nb13Zr, followed by the deposition of phosphate coating. The porous substrate (porosity about 50%) was prepared by a selective laser melting of the Ti13Nb13Zr powder with the SLM Realizer 100 equipment. The nanotubular oxide layers were fabricated by electrochemical oxidation in H3PO4 + 0.3% HF mixture for 30 min. at a constant voltage of 20V. The calcium phosphate coatings were formed by the electrochemically assisted deposition (ECAD). The presence of nanotubular oxide layers with their internal diameters ranging from 30 to 100 nm was observed by SEM (JEOL JSM-7600F). The nanotubes have dimensions that facilitated the deposition of hydroxyapatite.
The development of composite oxide layers on the Ti13Nb13Zr alloy, their structure and properties, were demonstrated. Two subsequent methods were applied to prepare the composite layers. During the first stage, gas oxidation produced a dense compact oxide layer, and subsequent oxide nanotubes were formed applied an electrochemical oxidation. The scanning electron microscopy, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, and Raman spectroscopy were used to examine the appearance, thickness, chemical and phase composition of the oxide layers. The results obtained revealed that the composite layers composed of two zones. The electrochemical formation of the outer nanotubular oxide zone occurred if the thickness of the first inner oxide zone was small enough because of resistance increasing with the inner zone thickness followed by a decrease in electrochemical reaction rate. The decreasing corrosion resistance of the Ti13Nb13Zr alloy was observed and explained by a model electric circuit.