Effects of Micro-Arc Oxidation Process Parameters on Characteristics of Calcium-Phosphate Containing Oxide Layers on the Selective Laser Melted Ti13Zr13Nb Alloy

M. Dziaduszewska , A. Zieliński , T. Seramak , M. Shimabukuro, T. Hanawa – Coatings – 2020
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 stagebioactivity 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.

Powder metallurgy of the porous Ti-13Nb-13Zr alloy of different powder grain size

The objective of the present project was to determine the effects of powder granulation (fraction of grain size) for the Ti-13Nb-13Zr alloy, produced by powder metallurgy, on its porosity, grain cohesion, compressive strength, and Young`s modulus. Two powder fractions, 45–105 µm, and 106–250 µm were applied. The 50 mass pct of NH4HCO3 was added as a space holder. The specimens were in compaction stage uniaxially pressed at pressure 625 MPa for 120 s. The brown bodies were sintered at a temperature 1150°C for 3.5 h. The well-joined grains were observed for both powder granulations. The increase in powder granulation resulted in an increase of porosity from 51% to 59%, and it was only 30% with no space holder used. The compressive strength increased with decreased porosity from 57 to 236 MPa. Young`s modulus was measured as 4.8 GPa for finer powder and 0.9 GPa for coarser powder. It is evident from the results obtained that the applied process parameters, the space holder and its fraction, and the use powder granulation between 45 and 105 µm bring out the porous material fulfilling mechanical and biological requirements specific of load-bearing titanium implants.

The Effect of Surface Modification of Ti13Zr13Nb Alloy on Adhesion of Antibiotic and Nanosilver-Loaded Bone Cement Coatings Dedicated for Application as Spacers

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.

Determinants of the surface quality, density and dimensional correctness in selective laser melting of the Ti-13Zr-13Nb alloy

Selective laser melting is widely used for custom-designed elements. Successful manufacturing depends on laser treatment parameters and material features. This research aimed to determine the effects of laser power, scan time and hatch distance on surface quality, relative density and dimensional precision for cuboids made of the Ti-13Zr-13Nb alloy. The influence of energy density, energy flux and pre-heating was seen to be decisive to different degrees for the quality of the final specimen. The results obtained were used to produce prosthetic crowns and bridges. The thermal stresses that appeared resulted in a deflection of the bridges and consequently in a change in design approach.

3D Printing of Metallic Implants

The fabrication of various elements, solid and open porous structures of stainless steel and Ti alloy is described. The process was started with the design of 3D models in CAD/CAM system. The 3D models were transformed into *.stl files and then the manufacturing process of the real structures by means of the selective laser melting with the SLM Realizer 100 3D printer was made. The paper shows the porous specimens made for possible application in medicine and the prosthetic bridges. The appropriate mechanical strength is the important property of porous structures for medical application and for curved prosthetic bridges it is necessary to take into account the thermal stresses, which appear during their SLM/DMLS manufacturing process.

Deposition of phosphate coatings on titanium within scaffold structure

Purpose: Existing knowledge about the appearance, thickness, and chemical composition of phosphate coatings on titanium inside porous structures is insufficient. Such knowledge is important for the design and fabrication of porous implants. Methods: Metallic scaffolds were fabricated by selective laser melting of 316L stainless steel powder. Phosphate coatings were deposited on Ti sensors placed either outside the scaffolds or in the holes in the scaffolds. The electrochemically-assisted cathodic deposition of phosphate coatings was performed under galvanostatic conditions in an electrolyte containing the calcium and phosphate ions. The phosphate deposits were microscopically investigated; this included the performance of mass weight measurements and chemical analyses of the content of Ca2+ and 2 PO4 ions after the dissolution of deposits. Results: The thicknesses of the calcium phosphate coatings were about 140 and 200 nm for isolated titanium sensors and 170 and 300 nm for titanium sensors placed inside pores. Deposition of calcium phosphate occurred inside the pores up to 150 mm below the scaffold surface. The deposits were rich in Ca, with a Ca/P ratio ranging from 2 to 2.5. Conclusions: Calcium phosphate coatings can be successfully deposited on a Ti surface inside a model scaffold. An increase in cathodic current results in an increase in coating thickness. Any decrease in the cathodic current inside the porous structure is slight. The calcium phosphate inside the pores has a much higher Ca/P ratio than that of stoichiometric HAp, likely due to a gradual increase in Ca fraction with distance from the surface.

Prosthetic Elements Made of the Ti-13Zr-13Nb Alloy by Selective Laser Melting

T. Seramak , K. Zasińska , A. Zieliński , J. Andryskowski, A. Andryskowska-Ignaczak, M. Motyl Advances in Materials Science – 2017
The fabrication of the prosthetic foundations and bridges from the Ti-13Zr-13Nb alloy is described. The process was started from CAD/CAM design of 3D models of the foundations based on scanning of patient`s mouth. Next, 3D models were transformed into *.stl files for the manufacturing stage and then the manufacturing process by means of the selective laser melting with the SLM Realizer 100 equipment was made. The intrinsic structure of the obtained parts was investigated with X-ray microtomography. The observed imperfections in the foundation's internal structure can be eliminated by a proper setting of the laser melting process. The thermal stresses, which resulted of the temperature change during melting and caused the bending of titanium made bridges, were eliminated at a design stage.

Selective Laser Melting of Ti Alloy for Manufacturing The Prosthetic Elements

The selective laser melting (SLM) is the additive manufacturing method of custom-designed parts. The used materials and the applications are various, including medicine. The titanium and its alloys are materials for which the dimensional quality, surface smoothness and no or extremely low porosity are difficult to reach. In this paper, the successful attempt to obtain by SLM the individually designed prosthetic bridges is described. The desired elements were obtained by the proper design, the adjustment of laser equipment parameters and necessary surface post-treatment.


Metal – polymer sliding contacts are a typical combination in industry and medicine. For decades such a set of materials has been the primary choice in human joints endoprosthetic technology. In this paper tribological issues of are presented from a research on the potential for practical use of Ti-13Nb-13Zr/UHMW-PE couple for orthopedic endoprosthesis. In tests on simplified models it is critically important to carefully select geometry of contact, load and velocity magnitudes and profiles to the later interpretation of results. In case of organic polymers interacting with metallic components the problem is even more prominent, than in the case of all metal systems because of great differences in the modulus of elasticity between the specimens in contact. High local loading can cause excessive heat generation and accelerated loss in polymer’s strength induced by thermal plastification. The process may not be manifested in the course of the experiment in any way detectable and might compromise the accuracy of wear measurement. In the case of the presented research an analysis has been performed to evaluate the observed wear profile of UHMW-PE with respect to non-uniform distribution of contact stress. A simulation was run with the use of FEM to evaluate the contact conditions between the titanium alloy and UHMW-PE specimens and the results were confronted with the wear profiles. Interesting similarities were discovered yielding useful information on the fundamentals of the wear in and for future research on similar systems.