A detailed mechanism of degradation behaviour of biodegradable as-ECAPed Zn-0.8Mg-0.2Sr with emphasis on localized corrosion attack.

In this study, advanced techniques such as atom probe tomography, atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy were used to determine the corrosion mechanism of the as-ECAPed Zn-0.8Mg-0.2Sr alloy. The influence of microstructural and surface features on the corrosion mechanism was investigated. Despite its significance, the surface composition before exposure is often neglected by the scientific community. The analyses revealed the formation of thin ZnO, MgO, and MgCO3 layers on the surface of the material before exposure. These layers participated in the formation of corrosion products, leading to the predominant occurrence of hydrozincite. In addition, the layers possessed different resistance to the environment, resulting in localized corrosion attacks. The segregation of Mg on the Zn grain boundaries with lower potential compared with the Zn-matrix was revealed by atom probe tomography and atomic force microscopy. The degradation process was initiated by the activity of micro-galvanic cells, specifically Zn - Mg2Zn11/SrZn13. This process led to the activity of the crevice corrosion mechanism and subsequent attack to a depth of 250 µm. The corrosion rate of the alloy determined by the weight loss method was 0.36 mm·a-1. Based on this detailed study, the degradation mechanism of the Zn-0.8Mg-0.2Sr alloy is proposed.

The Use of Electrochemical Methods to Determine the Effect of Nitrides of Alloying Elements on the Electrochemical Properties of Titanium ß-Alloys.

Titanium beta alloys represent the new generation of materials for the manufacturing of joint implants. Their Young's modulus is lower and thus closer to the bone tissue compared to commonly used alloys. The surface tribological properties of these materials should be improved by ion implantation. The influence of this surface treatment on corrosion behaviour is unknown. The surface of Ti-36Nb-6Ta, Ti-36Nb-4Zr, and Ti-39Nb titanium ß-alloys was modified using nitrogen ion implantation. X-ray photoelectron spectroscopy was used for surface analysis, which showed the presence of titanium, niobium, and tantalum nitrides in the treated samples and the elimination of less stable oxides. Electrochemical methods, electrochemical impedance spectra, polarisation resistance, and Mott-Schottky plot were measured in a physiological saline solution. The results of the measurements showed that ion implantation does not have a significant negative effect on the corrosion behaviour of the material. The best results of the alloys investigated were achieved by the Ti-36Nb-6Ta alloy. The combination of niobium and tantalum nitrides had a positive effect on the corrosion resistance of this alloy. After surface treatment, the polarization resistance of this alloy increased, 2.3 × 106 Ω·cm2, demonstrating higher corrosion resistance of the alloy. These results were also supported by the results of electrochemical impedance spectroscopy.

A Ru/RuO2-Doped TiO2 Nanotubes as pH Sensors for Biomedical Applications: The Effect of the Amount and Oxidation of Deposited Ru on the Electrochemical Response.

In the field of orthopedic or dental implants, titanium and its alloys are most commonly used because of their excellent mechanical and corrosion properties and good biocompatibility. After implantation into the patient's body, there is a high risk of developing bacterial inflammation, which negatively affects the surrounding tissues and the implant itself. Early detection of inflammation could be done with a pH sensor. In this work, pH-sensitive systems based on TiO2-Ru and TiO2-RuO2 combinations were fabricated and investigated. As a base material, Ti-6Al-4V alloy nanostructured by anodic oxidation was used. Ruthenium was successfully deposited on nanotubular TiO2 using cyclic polarization, galvanostatic and potentiostatic mode. Potentiostatic mode proved to be the most suitable. The selected samples were oxidized by cyclic polarization to form a TiO2-RuO2 system. The success of the oxidation was confirmed by XPS analysis. The electrochemical response of the systems to pH change was measured in saline solution using different techniques. The measurement of open circuit potential showed that unoxidized samples (TiO2-Ru) exhibited sub-Nernstian behavior (39.2 and 35.8 mV/pH). The oxidized sample (TiO2-RuO2) containing the highest amount of Ru exhibited super-Nernstian behavior (67.3 mV/pH). The Mott-Schottky analysis proved to be the best method. The use of the electrochemical impedance method can also be considered, provided that greater stability of the samples is achieved.

In vitro evaluation of a novel nanostructured Ti-36Nb-6Ta alloy for orthopedic applications.

Aim: To evaluate the impact of a nanostructured surface created on ß-titanium alloy, Ti-36Nb-6Ta, on the growth and differentiation of human mesenchymal stem cells. Materials & methods: The nanotubes, with average diameters 18, 36 and 46 nm, were prepared by anodic oxidation. Morphology, hydrophilicity and mechanical properties of the nanotube layers were characterized. The biocompatibility and osteogenic potential of the nanostructured surfaces were established using various in vitro assays, scanning electron microscopy and confocal microscopy. Results: The nanotubes lowered elastic modulus close to that of bone, positively influenced cell adhesion, improved ALP activity, synthesis of type I collagen and osteocalcin expression, but diminished early cell proliferation. Conclusion: Nanostructured Ti-36Nb-6Ta with nanotube diameters 36 nm was the most promising material for bone implantation.

Characterization of Newly Developed Zinc Composite with the Content of 8 wt.% of Hydroxyapatite Particles Processed by Extrusion.

Zinc and its alloys belong to a group of biodegradable materials, which can be potentially used for the preparation of temporary orthopedic implants. The research of biodegradable zinc materials revealed a lot of limitations; however, the new processing approaches of those materials can enhance their properties, which are insufficient for now. In this study, the zinc composite with 8 wt.% of hydroxyapatite (Zn/HA8) prepared for the first time by extrusion process was characterized from the point of view of the structural, mechanical and corrosion properties. The extrusion process led to good integrity of the interfaces between the zinc and hydroxyapatite particles. Mechanical behavior confirmed the role of hydroxyapatite as a defect in the material structure, which led to a decrease of the Zn/HA8 mechanical properties by approximately 30% (compressive yield strength (CYS) = 154 MPa Zn, 113 MPa Zn/HA8). Despite that, the Zn/HA8 composite showed sufficient mechanical properties for cancellous bone replacement and reached the lower limit for cortical bone. Additionally, the presence of hydroxyapatite caused the preferential precipitation of hydroxyapatite (HA) from the solution and can lead to a significant enhancement of the tissue/implant interface interactions.

Mesenchymal stem cell interaction with Ti6Al4V alloy pre-exposed to simulated body fluid.

Titanium and its alloys are widely used for substitution of hard tissues, especially in orthopaedic and dental surgery. Despite the benefit of the use of titanium for such applications, there are still questions which must be sorted out. Surface properties are crucial for cell adhesion, proliferation and differentiation. Mainly, micro/nanostructured surfaces positively influence osteogenic differentiation of human mesenchymal stem cells. Ti6Al4V is a biocompatible α + ß alloy which is widely used in orthopaedics. The aim of this study was to investigate the interaction of the nanostructured and ground Ti6Al4V titanium alloys with simulated body fluid complemented by the defined precipitation of hydroxyapatite-like coating and to study the cytotoxicity and differentiation capacity of cells with such a modified titanium alloy. Nanostructures were fabricated using electrochemical oxidation. Human mesenchymal stem cells (hMSC) were used to evaluate cell adhesion, metabolic activity and proliferation on the specimens. The differentiation potential of the samples was investigated using PCR and specific staining of osteogenic markers collagen type I and osteocalcin. Our results demonstrate that both pure Ti6Al4V, nanostructured samples, and hydroxyapatite-like coating supported hMSC growth and metabolic activity. Nanostructured samples improved collagen type I synthesis after 14 days, while both nanostructured and hydroxyapatite-like coated samples enhanced collagen synthesis on day 21. Osteocalcin synthesis was the most enhanced by hydroxyapatite-like coating on the nanostructured surfaces. Our results indicate that hydroxyapatite-like coating is a useful tool guiding hMSC osteogenic differentiation.

A two-phase gradual silver release mechanism from a nanostructured TiAlV surface as a possible antibacterial modification in implants.

Titanium biomaterials are widely used in the medical field due to their biocompatibility and excellent corrosion and mechanical resistance. However, these materials have no antibacterial properties. To obtain an antibacterial active surface, a nanostructure of Ti6Al4V alloy was created. This specific nanostructure contained nanotubes and micro-cavities and was used as a substrate for silver anchoring. The electrochemical approach to silver reduction was studied. It is a common approach for silver deposition and in this work, inhomogeneities in the nanostructure were used as a preferential area for silver localisation. The galvanostatic regimen of deposition allowed for a technically quantitative process and the required silver placement. The experimental conditions used enabled testing and silver dissolution rate evaluation within a reasonable time span. Based on the corrosion and analytical results (EDS, XPS and ICP-MS), a two-phase silver release mechanism was confirmed. The openings of the individual nanotubes were filled with silver nanoparticles, whose release was relatively fast. By contrast, the silver anchored inside the cavities allowed the silver to release gradually. Antibacterial efficiency against Staphylococcus aureus and Escherichia coli was successfully demonstrated. Cytotoxicity testing with murine fibroblasts showed cell metabolic activity far above the normative limit of 70%.

Different diameters of titanium dioxide nanotubes modulate Saos-2 osteoblast-like cell adhesion and osteogenic differentiation and nanomechanical properties of the surface.

The formation of nanostructures on titanium implant surfaces is a promising strategy to modulate cell adhesion and differentiation, which are crucial for future application in bone regeneration. The aim of this study was to investigate how the nanotube diameter and/or nanomechanical properties alter human osteoblast like cell (Saos-2) adhesion, growth and osteogenic differentiation in vitro. Nanotubes, with diameters ranging from 24 to 66 nm, were fabricated on a commercially pure titanium (cpTi) surface using anodic oxidation with selected end potentials of 10 V, 15 V and 20 V. The cell response was studied in vitro on untreated and nanostructured samples using a measurement of metabolic activity, cell proliferation, alkaline phosphatase activity and qRT-PCR, which was used for the evaluation of osteogenic marker expression (collagen type I, osteocalcin, RunX2). Early cell adhesion was investigated using SEM and ELISA. Adhesive molecules (vinculin, talin), collagen and osteocalcin were also visualized using confocal microscopy. Moreover, the reduced elastic modulus and indentation hardness of nanotubes were assessed using a TriboIndenter™. Smooth and nanostructured cpTi both supported cell adhesion, proliferation and bone-specific mRNA expression. The nanotubes enhanced collagen type I and osteocalcin synthesis, compared to untreated cpTi, and the highest synthesis was observed on samples modified with 20 V nanotubes. Significant differences were found in the cell adhesion, where the vinculin and talin showed a dot-like distribution. Both the lowest reduced elastic modulus and indentation hardness were assessed from 20 V samples. The nanotubes of mainly 20 V samples showed a high potential for their use in bone implantation.

Corrosion behaviour and cell interaction of Ti-6Al-4V alloy prepared by two techniques of 3D printing.

3D printing seems to be the technology of the future for the preparation of metallic implants. For such applications, corrosion behaviour is pivotal. However, little is published on this topic and with inconsistent results. Therefore, we carried out a complex study in which we compared two techniques of the 3D printing technology - selective laser melting and electron beam melting. The corrosion behaviour was studied in physiological solution by standard electrochemical techniques and susceptibility to localised corrosion was estimated too. All samples showed typical passive behaviour. Localised corrosion was shown to be possible on the original as-printed surfaces. Corrosion experiments were repeated tree times. To reveal possible negative effects of 3D printing on cytocompatibility, direct in vitro tests were performed with U-2 OS cells. The cells showed good viability and proliferation, but their growth was impeded by surface unevenness. Our results suggest that both techniques are suitable for implants production. Statistical evaluation was performed by ANOVA followed by Tukey's test.