Titania-based films on selective laser melted Ti13Zr13Nb have been formed by micro-arc oxidation (MAO) at different process parameters (voltage, current, processing time) in order to evaluate the impact of MAO process parameters in calcium and phosphate (Ca + P) containing electrolyte on surface characteristic, early-stage bioactivity, nanomechanical properties, and adhesion between the oxide coatings and substrate. The surface topography, surface roughness, pore diameter, elemental composition, crystal structure, surface wettability, and the early stage-bioactivity in Hank’s solution were evaluated for all coatings. Hardness, maximum indent depth, Young’s modulus, and Ecoating/Esubstrate, H/E, H3/E2 ratios were determined in the case of nanomechanical evaluation while the MAO coating adhesion properties were estimated by the scratch test. The study indicated that the most important parameter of MAO process influencing the coating characteristic is voltage. Due to the good ratio of structural and nanomechanical properties of the coatings, the optimal conditions of MAO process were found at 300 V during 15 min, at 32 mA or 50 mA of current, which resulted in the predictable structure, high Ca/P ratio, high hydrophilicity, the highest demonstrated early-stage bioactivity, better nanomechanical properties, the elastic modulus and hardness well close to the values characteristic for bones, as compared to specimens treated at a lower voltage (200 V) and uncoated substrate, as well as a higher critical load of adhesion and total delamination.
Spacers, in terms of instruments used in revision surgery for the local treatment of postoperative infection, are usually made of metal rod covered by antibiotic-loaded bone cement. One of the main limitations of this temporary implant is the debonding effect of metal–bone cement interface, leading to aseptic loosening. Material selection, as well as surface treatment, should be evaluated in order to minimize the risk of fraction and improve the implant-cement fixation the appropriate manufacturing. In this study, Ti13Zr13Nb alloys that were prepared by Selective Laser Melting and surface treated were coated with bone cement loaded with either gentamicin or nanosilver, and the effects of such alloy modifications were investigated. The SLM-made specimens of Ti13Zr13Nb were surface treated by sandblasting, etching, or grounding. For each treatment, Scanning Electron Microscope (SEM), contact profilometer, optical tensiometer, and nano-test technique carried out microstructure characterization and surface analysis. The three types of bone cement i.e., pure, containing gentamicin and doped with nanosilver were applied to alloy surfaces and assessed for cement cohesion and its adhesion to the surface by nanoscratch test and pull-off. Next, the inhibition of bacterial growth and cytocompatibility of specimens were investigated by the Bauer-Kirby test and MTS assay respectively. The results of each test were compared to the two control groups, consisting of commercially available Ti13Zr13Nb and untreated SLM-made specimens. The highest adhesion bone cement to the titanium alloy was obtained for specimens with high nanohardness and roughness. However, no explicit relation of adhesion strength with wettability and surface energy of alloy was observed. Sandblasting or etching were the best alloys treatments in terms of the adhesion of either pure or modified bone cements. Antibacterial additives for bone cement affected its properties. Gentamicin and nanosilver allowed for adequate anti-bacterial protection while maintaining the overall biocompatibility of obtained spacers. However, they had different effects on the cement’s adhesive capacity or its own cohesion. Furthermore, the addition of silver nanoparticles improved the nanomechanical properties of bone cements. Surface treatment and method of fabrication of titanium affected surface parameters that had a significant impact on cement-titanium fixation.
Porous structures made of metal or biopolymers with a structure similar in shape and mechanical properties to human bone can easily be produced by stereolithographic techniques, e.g. selective laser melting (SLM). Numerical methods, like Finite Element Method (FEM) have great potential in testing new scaffold designs, according to their mechanical properties before manufacturing, i.e. strength or stiffness. An example of such designs are scaffolds used in biomedical applications, like in orthopedics' and mechanical properties of these structures should meet specific requirements. This paper shows how mechanical properties of proposed scaffolds can be estimated with regard to total porosity and pore shape.
The main objective of here presented research is to develop the titanium (Ti) alloy base composite materials possessing better biocompatibility, longer lifetime and bioactivity behaviour for load-bearing implants, e.g. hip joint and knee joint endoprosthesis. The development of such materials is performed through: modeling the material behaviour in biological environment in long time and developing of new procedures for such evaluation; obtaining of a Ti alloy with designed porosity; developing of an oxidation technology resulting in high corrosion resistance and bioactivity; developing of technologies for hydroxyapatite (HA) deposition aimed at composite bioactive coatings; developing of technologies of precipitation of the biodegradable core material placed within the pores. The examinations of degradation of Ti implants are carried out in order to recognize the sources of both early allergies and inflammation, and of long term degradation. The theoretical assessment of corrosion is made assuming three processes: electrochemical dissolution through imperfections of the anodic oxide layer, diffusion of metallic ions through the oxide layer, and dissolution of oxides themselves. In order to increase the biocompatibility, the toxic elements, aluminium (Al) and vanadium (V) are eliminated. The experiments have shown that titanium -zirconium -niobium (Ti-Zr-Nb) alloy may be a such a material which can also be prepared by both powder metallurgy (P/M) technique and selective laser melting. The porous (scaffold) Ti-Zr-Nb alloy is now obtained by powder metallurgy, classical and with space holders used before melting and decomposed, or remained during melting and removed by subsequent water dissolution. The oxidation of porous materials is performed either by electrochemical technique in special electrolytes or by chemical and/or hydrothermal method in order to obtain the optimal oxide layer well adjacent to an interface, preventing the base metal against corrosion and bioactive because of its nanotubular structure, permitting injection of some species into the pores. The Ca, O and N ion implantation or deposition of zirconia sublayers may be used to increase the biocompatibility, bioactivity and corrosion resistance. The HA coating obtained by either electrophoretic, biomimetic or by sol-gel deposition should result in gradient structure similar to bone structure, possessing high adhesion strength. The core material of the porous material should result in a biodegradable material, allowing slower dissolution followed by stepwise growth of bone tissue and angiogenesis, preventing local inflammation processes, sustaining the mechanical strength close to that of non-porous material.
The main objective of here presented research is a design the scaffold/porous titanium (Ti) alloy based composite material demonstrating better biocompatibility, longer lifetime and bioactivity behaviour for load-bearing implants. The development of such material is proposed by making a number of consecutive tasks. Modelling the mechanical, biomechanical and biological behavior of porous titanium structure and an elaboration of results is performed by mathematical methods, including FEM and fuzzy logic. The development of selected Ti-13Zr-Nb alloy with designed porosity and no harmful effects is made by powder metallurgy (PM) with and without space holders, and by rapid prototyping with an use of selective laser melting (SLM). The development of an oxidation technology resulting in high corrosion resistance and bioactivity is carried out by electrochemical oxidation, gaseous oxidation and chemical oxidation, and their combination. The HA depositon is made by electrochemical and chemical (alternate immersion) methods. The core material is designed as a combination of natural polymer and bioceramics in order to allow slow dissolution followed by stepwise growth of bone tissue and angiogenesis, preventing local inflammation processes, and sustaining the mechanical strength close to that of non-porous material.
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