Gregory Davdian

This paper presents the results of a study on two titanium-based alloys — Ti–10wt.%Mo and Ti–15wt.%Mo — aimed at assessing their potential for use as base materials in implantable medical devices for osteosynthesis. The alloy samples were examined in three conditions: as-fabricated, after annealing at 1000 °C, and after high-pressure torsion. The microstructure of the alloys was analyzed using scanning electron microscopy and X-ray diffraction. The Young’s modulus, microhardness, and nanohardness values were measured, and the effect of the alloys on the viability and surface adhesion of human multipotent mesenchymal stromal cells during in vitro incubation was investigated. Comparative analysis of the obtained results revealed that the annealed Ti–15wt.%Mo alloy sample is the most promising candidate for orthopedic applications, as it exhibits an optimal combination of good biocompatibility, enhanced stimulation of cell adhesion, and relatively low microhardness (283 HV) and Young’s modulus (106 GPa).

The effect of preliminary annealing at 1000°C and subsequent high-pressure torsion (HPT) on the phase composition and mechanical properties of titanium alloys with 2, 4, 6, and 8 wt % V is studied. The increase in the V concentration in the initial alloy leads to an increase in the volume fraction of the β-Ti phase and a decrease in the volume fraction of the ω-Ti phase after HPT. The nanohardness Н and Young’s modulus Е were measured by nanoindentation. After HPT, the values of Н and Е are higher than those observed after preliminary annealing by 44 and 20%, respectively. The nanohardness and Young’s modulus of the studied alloy subjected to HPT are independent on the fraction of second constituent and are Н = 6.2 ± 0.2 GPa and Е = 138 ± 3 GPa, respectively. However, the hardness of the alloys subjected to HPT, which was measured by microindentation, also is independent of the fraction of the second constituent. At the same time, the ultimate strength and Young’s modulus measured by three-point bending technique have significant differences and, as the V concentration increases, decrease from 3.1 to 2.4 GPa and from 204 to 165 GPa, respectively. The decrease correlates with changing the volume fractions of the ω-Ti and β-Ti phases. The correlation between the vanadium content, phase composition, and ultimate strength of alloys subjected to HPT is found experimentally.

Three titanium alloys with 0.5, 6, and 9 wt.% iron were investigated, and the samples were pre-annealed in three different regions of the Ti–Fe phase diagram, namely β, α+β, and α+FeTi. After annealing, five samples of different phases and structural compositions were studied. They were then subjected to the high-pressure torsion (HPT). The microstructure of the samples before and after HPT treatment was studied using transmission and scanning electron microscopy. The microstructure of the samples obtained during heat treatment before HPT treatment had a fundamental effect on the microstructure after HPT. Grain boundary layers and chains of particles formed during the annealing process made it difficult to mix the material during HPT, which led to the formation of areas with non-uniform mixing of components. Thus, the grain boundary layers of the α-phase formed in the Ti–6wt % Fe alloy after annealing at 670 °C significantly decreased the mixing of the components during HPT. Despite the fact that the microstructure and phase composition of Ti–6wt % Fe alloys pre-annealed in three different regions of the Ti–Fe phase diagram had significant differences, after HPT treatment, the phase compositions of the studied samples were quite similar. Moreover, the measured micro- and nanohardness as well as the Young’s modulus of Ti–6wt % Fe alloy had similar values. It was shown that the microhardness of the studied samples increased with the iron content. The values of nanohardness and Young’s modulus correlated well with the fractions of β- and ω-phases in the studied alloys.

This investigation delved into the alterations in the mechanical properties of a TiZrHfMoCrCo high-entropy alloy due to phase transformations induced by high-pressure torsion (HPT). The alloy’s genesis involved levitation melting within an argon atmosphere, presenting two distinct states for analysis: the initial, post-manufacturing state and the state subsequent to HPT treatment. The original alloy featured a composition comprising a singular A2 phase with a bcc lattice and two Laves phases, C15 and C14. The HPT process triggered significant phase modifications: a retention of one C15 Laves phase and decomposition of the bcc phase into two distinct phases exhibiting different bcc lattice parameters. The HPT-induced effect prominently manifests as strong grain refinement. However, scanning electron microscopy (SEM) observations unveiled persistent inhomogeneities at a micron scale both before and after HPT treatment. Thus, grain refinement occurs separately within each of the bcc and Laves phases, visible in the light, dark, and gray areas in SEM images, while mixing does not occur on the scale of several microns. The examination of Ti, Cr, Co, Zr, Mo, and Hf via X-ray absorption spectroscopy (EXAFS) at specific K-edges and L3-edge revealed that the HPT treatment conserves the local atomic environment of metal atoms, albeit with a slight elevation in static disorder. Assessments through microhardness and three-point bending tests demonstrated the material’s inherent hardness and brittleness. The microhardness, standing at a substantial value of 600 HV, displayed negligible augmentation post-HPT. However, the microhardness of individual phases exhibited a notable alteration, nearly doubling in magnitude.

The pivotal role of metal implants within the host’s body following reconstructive surgery hinges primarily on the initial phase of the process: the adhesion of host cells to the implant’s surface and the subsequent colonization by these cells. Notably, titanium alloys represent a significant class of materials used for crafting metal implants. This study, however, marks the first investigation into how the phase composition of titanium alloys, encompassing the volume fractions of the α, β, and ω phases, influences cell adhesion to the implant’s surface. Moreover, the research delves into the examination of induced hemolysis and cytotoxicity. To manipulate the phase composition of titanium alloys, various parameters were altered, including the chemical composition of titanium alloys with iron and niobium, annealing temperature, and high-pressure torsion parameters. By systematically adjusting these experimental parameters, we were able to discern the distinct impact of phase composition. As a result, the study unveiled that the colonization of the surfaces of the examined Ti–Nb and Ti–Fe alloys by human multipotent mesenchymal stromal cells exhibits an upward trend with the increasing proportion of the ω phase, concurrently accompanied by a decrease in the α and β phases. These findings signify a new avenue for advancing Ti-based alloys for both permanent implants and temporary fixtures, capitalizing on the ability to regulate the volume fractions of the α, β, and ω phases. Furthermore, the promising characteristics of the ω phase suggest the potential emergence of a third generation of biocompatible Ti alloys, the ω-based materials, following the first-generation α-Ti alloys and second-generation β alloys.

Modern magnesium-based alloys are broadly used in various industries as well as for biodegradable medical implants due to their exceptional combination of light weight, strength, and plasticity. The studied ZEK100 alloy had a nominal composition of 1 wt.% zinc, 0.1 wt.% zirconium, and 0.1 wt.% rare earth metals (REMs) such as Y, Ce, Nd, and La, with the remainder being Mg. It has been observed that between the solidus (T_s = 529.5 ± 0.5 °C) and liquidus temperature (T_l = 645 ± 5 °C), the Mg/Mg grain boundaries can contain either the droplets of a melt (incomplete or partial wetting) or the continuous liquid layers separating the abutting Mg grains (complete wetting). With the temperature increasing from T_s to T_l, the transformation proceeds from incomplete to complete grain boundary wetting. Below 565 °C, all grain boundaries are partially wetted by the melt. Above 565 °C, the completely wetted Mg/Mg grain boundaries appear. Their portion grows quickly with an increasing temperature until reaching 100% at 622 °C. Above 622 °C, all the solid Mg grains are completely surrounded by the melt. After rapid solidification, the REM-rich melt forms brittle intermetallic compounds. The compression strength as well as the compression yield strength parameter σ₀₂ strongly depend on the morphology of the grain boundary layers. If the hard and brittle intermetallic phase has the shape of separated particles (partial wetting), the overall compression strength is about 341 MPa and σ₀₂ = 101 MPa. If the polycrystal contains the continous intergarnular layers of the brittle intermetallic phase (complete wetting), the overall compression strength drops to 247 Mpa and σ₀₂ to 40 Mpa. We for the first time observed, therefore, that the grain boundary wetting phenomena can strongly influence the mechanical properties of a polycrystal. Therefore, grain boundary wetting can be used for tailoring the behavior of materials.

Magnesium-based alloys are highly sought after in the industry due to their lightweight and reliable strength. However, the hexagonal crystal structure of magnesium results in the mechanical properties’ anisotropy. This anisotropy is effectively addressed by alloying magnesium with elements like zirconium, zinc, and rare earth metals (REM). The addition of these elements promotes rapid seed formation, yielding small grains with a uniform orientation distribution, thereby reducing anisotropy. Despite these benefits, the formation of intermetallic phases (IP) containing Zn, Zr, and REM within the microstructure can be a concern. Some of these IP phases can be exceedingly hard and brittle, thus weakening the material by providing easy pathways for crack propagation along grain boundaries (GBs). This issue becomes particularly significant if intermetallic phases form continuous layers along the entire GB between two neighboring GB triple junctions, a phenomenon known as complete GB wetting. To mitigate the risks associated with complete GB wetting and prevent the weakening of the alloy’s structure, understanding the potential occurrence of a GB wetting phase transition and how to control continuous GB layers of IP phases becomes crucial. In the investigation of a commercial magnesium alloy, ZEK100, the GB wetting phase transition (i.e., between complete and partial GB wetting) was successfully studied and confirmed. Notably, complete GB wetting was observed at temperatures near the liquidus point of the alloy. However, at lower temperatures, a coexistence of a nano-scaled precipitate film and bulk particles with nonzero contact angles within the same GB was observed. This insight into the wetting transition characteristics holds potential to expand the range of applications for the present alloy in the industry. By understanding and controlling GB wetting phenomena, the alloy’s mechanical properties and structural integrity can be enhanced, paving the way for its wider utilization in various industrial applications.

The study focused on a 21.99 at.%Ti–22.49 at.%Zr–20.35 at.%Hf–17.45 at.%Mo–17.73 at.%Cr). Analytical techniques such as X-ray diffraction, scanning electron microscopy as well as X-ray absorption spectroscopy were employed to investigate the alloy’s structure, phase transformations, and properties. The alloy in the as-cast state contained three phases, namely the body-centred cubic (A2) phase, hexagonal Laves phase (C14), and cubic Laves phase (C15). The alloy has been annealed for a long time at different temperatures. It led to the disappearance of the hexagonal Laves phase, leaving behind two primary phases, namely the cubic Laves phase (C15) and the body-centered cubic phase (A2). At 1200 °C, the A2 phase almost disappeared, resulting in a practically single-phase sample. After a high-pressure torsion (HPT) treatment, the hexagonal Laves phase disappeared entirely, while the A2 and C15 phases remained. The grain size of the A2 and C15 phases was refined after HPT and grains were elongated, and their configuration resembled a layered structure. The high hardness of the A2 and C15 + C14 phases accounted for this behavior. The lattice parameters in the A2 and C15 phases after HPT treatment approached those observed after prolonged annealing at 1000 °C, indicating that the composition of these phases after short-term high-pressure torsion at ambient temperature is equivalent to the composition of these phases after long tempering at 1000 °C. The rate of diffusion-like mass transfer during severe plastic deformation was estimated to be many orders of magnitude higher than that for conventional bulk diffusion at the HPT treatment temperature and similar to that at elevated temperatures above 1000 °C. X-ray absorption spectroscopy results obtained at K-edges of Ti, Cr, Zr, and Mo as well as at the L3-edge of Hf indicated that the local environment around metal atoms before HPT was similar to that after HPT. However, the static disorder increased after HPT, which could be attributed to an increased specific amount of metal atoms in the disordered grain boundary layers after HPT-driven grain refinement.

In this work the high-entropy alloy studied contained six components, Ti/Zr/Hf/Mo/Cr/Co, and three phases, namely one phase with body-centered cubic lattice (BCC) and two Laves phases C14 and C15. A series of annealings in the temperature range from 600 to 1000 °C demonstrated not only a change in the microstructure of the TiZrHfMoCrCo alloy, but also the modification of phase composition. After annealing at 1000 °C the BCC phase almost fully disappeared. The annealing at 600 and 800 °C leads to the formation of new Laves phases. After high-pressure torsion (HPT) of the as-cast TiZrHfMoCrCo alloy, the grains become very small, the BCC phase prevails, and C14 Laves phase completely disappears. This state is similar to the state after annealing at high effective temperature T_eff. The additional annealing at 1000 °C after HPT returns the phase composition back to the state similar to that of the as-cast alloy after annealing at 1000 °C. At 1000 °C the BCC phase completely wets the C15/C15 grain boundaries (GBs). At 600 and 800 °C the GB wetting is incomplete. The big spread of nanohardness and Young’s modulus for the BCC phase and (C15 + C14) Laves phases is observed.