Effect of Cold Drawing and Annealing in Thermomechanical Treatment Route on the Microstructure and Functional Properties of Superelastic Ti-Zr-Nb Alloy.

In this study, a superelastic Ti-18Zr-15Nb (at. %) alloy was subjected to thermomechanical treatment, including cold rotary forging, intermediate annealing, cold drawing, post-deformation annealing, and additional low-temperature aging. As a result of intermediate annealing, two structures of ß-phase were obtained: a fine-grained structure (d ≈ 3 µm) and a coarse-grained structure (d ≈ 11 µm). Cold drawing promotes grain elongation in the drawing direction; in a fine-grained state, grains form with a size of 4 × 2 µm, and in a coarse-grained state, they grow with a size of 16 × 6 µm. Post-deformation annealing (PDA) at 550 °C for 30 min leads to grain sizes of 5 µm and 3 µm, respectively. After PDA at 550 °C (30 min) in the fine-grained state, the wire exhibits high tensile strength (UTS = 624 MPa), highest elongation to failure (δ ≥ 8%), and maximum difference between the dislocation and transformation yield stresses, as well as the highest superelastic recovery strain (εrSE ≥ 3.3%) and total elastic + superelastic recovery strain (εrel+SE ≥ 5.4%). Additional low-temperature aging at 300 °C for 30-180 min leads to ω-phase formation, alloy hardening, embrittlement, and a significant decrease in superelastic recovery strain.

Surface Modification of Biomedical Ti-18Zr-15Nb Alloy by Atomic Layer Deposition and Ag Nanoparticles Decoration.

Superelastic biocompatible alloys attract significant attention as novel materials for bone tissue replacement. These alloys are often composed of three or more components that lead to the formation of complex oxide films on their surfaces. For practical use, it is desirable to have a single-component oxide film with a controlled thickness on the surface of biocompatible material. Herein we investigate the applicability of the atomic layer deposition (ALD) technique for surface modification of Ti-18Zr-15Nb alloy with TiO2 oxide. It was found that a 10-15 nm thick, low-crystalline TiO2 oxide layer is formed by ALD method over the natural oxide film (~5 nm) of the Ti-18Zr-15Nb alloy. This surface consists of TiO2 exclusively without any additions of Zr or Nb oxides/suboxides. Further, the obtained coating is modified by Ag nanoparticles (NPs) with a surface concentration up to 1.6% in order to increase the material's antibacterial activity. The resulting surface exhibits enhanced antibacterial activity with an inhibition rate of more than 75% against E. coli bacteria.

Effect of High-Pressure Torsion and Annealing on the Structure, Phase Composition, and Microhardness of the Ti-18Zr-15Nb (at. %) Alloy.

The Ti-18Zr-15Nb shape memory alloys are a new material for medical implants. The regularities of phase transformations during heating of this alloy in the coarse-grained quenched state and the nanostructured state after high-pressure torsion have been studied. The specimens in quenched state (Q) and HPT state were annealed at 300-550 °C for 0.5, 3, and 12 h. The α-phase formation in Ti-18Zr-15Nb alloy occurs by C-shaped kinetics with a pronounced peak near 400-450 °C for Q state and near 350-450 °C for HPT state, and stops or slows down at higher and lower annealing temperatures. The formation of a nanostructured state in the Ti-18Zr-15Nb alloy as a result of HPT suppresses the ß→ω phase transformation during low-temperature annealing (300-350 °C), but activates the ß→α phase transformation. In the Q-state the α-phase during annealing at 450-500 °C is formed in the form of plates with a length of tens of microns. The α-phase formed during annealing of nanostructured specimens has the appearance of nanosized particle-grains of predominantly equiaxed shape, distributed between the nanograins of ß-phase. The changes in microhardness during annealing of Q-specimens correlate with changes in phase composition during aging.

Evolution of Structure and Properties of Nickel-Enriched NiTi Shape Memory Alloy Subjected to Bi-Axial Deformation.

The effect of a promising method of performing a thermomechanical treatment which provides the nanocrystalline structure formation in bulk NiTi shape memory alloy samples and a corresponding improvement to their properties was studied in the present work. The bi-axial severe plastic deformation of Ti-50.7at.%Ni alloy was carried out on the MaxStrain module of the Gleeble system at 350 and 330 °C with accumulated true strains of e = 6.6-9.5. The obtained structure and its mechanical and functional properties and martensitic transformations were studied using DSC, X-ray diffractometry, and TEM. A nanocrystalline structure with a grain/subgrain size of below 80 nm was formed in bulk nickel-enriched NiTi alloy after the MaxStrain deformation at 330 °C with e = 9.5. The application of MaxStrain leads to the formation of a nanocrystalline structure that is characterized by the appearance of a nano-sized grains and subgrains with equiaxed and elongated shapes and a high free dislocation density. After the MaxStrain deformation at 330 °C with e = 9.5 was performed, the completely nanocrystalline structure with the grain/subgrain size of below 80 nm was formed in bulk nickel-enriched NiTi alloy for the first time. The resulting structure provides a total recoverable strain of 12%, which exceeds the highest values that have been reported for bulk nickel-enriched NiTi samples.

Production, Mechanical and Functional Properties of Long-Length TiNiHf Rods with High-Temperature Shape Memory Effect.

In the present work, the possibility of manufacturing long-length TiNiHf rods with a lowered Hf content and a high-temperature shape memory effect in the range of 120-160 °C was studied. Initial ingots with 1.5, 3.0 and 5.0 at.% Hf were obtained by electron beam melting in a copper water-cooled stream-type mold. The obtained ingots were rotary forged at the temperature of 950 °C, with the relative strain from 5 to 10% per one pass. The obtained results revealed that the ingots with 3.0 and 5.0 at.% Hf demonstrated insufficient technological plasticity, presumably because of the excess precipitation of (Ti,Hf)2Ni-type particles. The premature destruction of ingots during the deformation process does not allow obtaining high-quality long-length rods. A long-length rod with a diameter of 3.5 mm and a length of 870 mm was produced by rotary forging from the ingot with 1.5 at.% Hf. The obtained TiNiHf rod had relatively high values of mechanical properties (a dislocation yield stress σy of 800 MPa, ultimate tensile strength σB of 1000 MPa, and elongation to fracture δ of 24%), functional properties (a completely recoverable strain of 5%), and a required finishing temperature of shape recovery of 125 °C in the as-forged state and of 155 °C after post-deformation annealing at 550 °C for 2 h.

Effect of Cooling and Annealing Conditions on the Microstructure, Mechanical and Superelastic Behavior of a Rotary Forged Ti-18Zr-15Nb (at. %) Bar Stock for Spinal Implants.

In this work, the microstructure, phase state, texture, superelastic and mechanical properties of a Ti-18Zr-15Nb (at. %) shape memory alloy subjected to a combined thermomechanical treatment, including hot rotary forging with either air cooling or water quenching and post-deformation annealing are studied. It was revealed that the main structural component of the deformed and annealed alloy is BCC ß-phase. With an increase in the forging temperature from 600 to 700 °C, the average grain size increases from 5.4 to 17.8 µm for the air-cooled specimens and from 3.4 to 14.7 µm for the water-quenched specimens. Annealing at 525 °C after forging at 700 °C with water quenching leads to the formation of a mixed statically and dynamically polygonized substructure of ß-phase. In this state, the alloy demonstrates the best combination of functional properties in this study: a Young's modulus of ~33 GPa, an ultimate tensile strength of ~600 MPa and a superelastic recovery strain of ~3.4%.

Surface modification and antibacterial properties of superelastic Ti-Zr-based alloys for medical application.

To date, significant progress has been achieved in the development of biomedical superelastic Ti-based alloys with high mechanical properties. In view of the high probability of implant-associated infection, an urgent task is to impart bactericidal properties to the material. Herein, advanced superelastic Ti-18Zr-15Nb alloys were surface-etched in a piranha solution, and then Ag nanoparticles were deposited on their surface using a polyol process. This led to the formation of a porous surface layer with a thickness of approximately 100 nm and pore size of less than 20 nm, filled with metallic Ag nanoparticles with an average size of 14 nm. The surface-modified samples showed superior antibacterial activity against E.coli cells. The enhanced bactericidal efficiency is explained by the combination of a higher rate of Ag+ ions release and direct contact of E.coli cells with Ag nanoparticles.

Effect of Thermomechanical Treatment on Structure and Functional Fatigue Characteristics of Biodegradable Fe-30Mn-5Si (wt %) Shape Memory Alloy.

The Fe-Mn-Si shape memory alloys are considered promising materials for the biodegradable bone implant application since their functional properties can be optimized to combine bioresorbability with biomechanical and biochemical compatibility with bone tissue. The present study focuses on the fatigue and corrosion fatigue behavior of the thermomechanically treated Fe-30Mn-5Si (wt %) alloy compared to the conventionally quenched alloy because this important functionality aspect has not been previously studied. Hot-rolled and water-cooled, cold-rolled and annealed, and conventionally quenched alloy samples were characterized by X-ray diffraction, transmission electron microscopy, tensile fatigue testing in air atmosphere, and bending corrosion fatigue testing in Hanks' solution. It is shown that hot rolling at 800 °C results in the longest fatigue life of the alloy both in air and in Hanks' solution. This advantage results from the formation of a dynamically recrystallized γ-phase grain structure with a well-developed dislocation substructure. Another important finding is the experimental verification of Young's modulus anomalous temperature dependence for the studied alloy system, its minimum at a human body temperature, and corresponding improvement of the biomechanical compatibility. The idea was realized by lowering Ms temperature down to the body temperature after hot rolling at 800 °C.

Structural, physical, chemical, and biological surface characterization of thermomechanically treated Ti-Nb-based alloys for bone implants.

Metastable near-beta Ti-21.8Nb-6Zr and Ti-19.7Nb-5.8Ta (at%) alloys were subjected to a thermomechanical treatment comprising cold rolling (CR) with a true strain of e = 0.3 and post-deformation annealing (PDA) in the 500-900°C temperature range to ensure the superelastic behavior which is important for bone implants. It was found that PDA resulted in formation of about 1-2 µm-thick oxide layer on the Ti-Nb-Zr and Ti-Nb-Ta alloy samples; the layer was mainly composed of TiO2 , in rutile and anatase modifications. The structure, the phase and chemical compositions, and some surface-sensitive properties of the alloys were compared to those of Ti-50.7Ni and Ti-Grade2 reference materials. These surface layers (especially that of the Ti-Nb-Zr alloy) demonstrated a promising combination of high cohesion strength (load causing surface layer fracture is over 25 N), hardness (∼12 GPa), and hydrophilicity (contact angle ∼40°). Surface modification by controlled oxidation during air annealing increases corrosion resistance and enhances in vivo osteoinductive properties of Ti-Nb-Zr alloys by changing the surface microrelief, increasing the surface wettability, and improving the mechanical characteristics, thus laying the foundation for the development of medical implants with prolonged service life. So, it was confirmed that the same thermomechanical treatment, which creates conditions for the superelastic behavior of the bulk metal (CR: e = 0.3 + PDA = 500-700°C for 1 hr), would also create a strong, protective and biocompatible layer on the implant surface.

The Electrochemical and Mechanical Behavior of Bulk and Porous Superelastic Ti‒Zr-Based Alloys for Biomedical Applications.

Titanium alloys are well recognized as appropriate materials for biomedical implants. These devices are designed to operate in quite aggressive human body media, so it is important to study the corrosion and electrochemical behavior of the novel materials alongside the underlying chemical and structural features. In the present study, the prospective Ti‒Zr-based superelastic alloys (Ti-18Zr-14Nb, Ti-18Zr-15Nb, Ti-18Zr-13Nb-1Ta, atom %) were analyzed in terms of their phase composition, functional mechanical properties, the composition and structure of surface oxide films, and the corresponding corrosion and electrochemical behavior in Hanks' simulated biological solution. The electrochemical parameters of the Ti-18Zr-14Nb material in bulk and foam states were also compared. The results show a significant difference in the functional performance of the studied materials, with different composition and structure states. In particular, the positive effect of the thermomechanical treatment regime, leading to the formation of a favorable microstructure on the corrosion resistance, has been revealed. In general, the Ti-18Zr-15Nb alloy exhibits the optimum combination of functional characteristics in Hanks' solution, while the Ti-18Zr-13Nb-1Ta alloy shows the highest resistance to the corrosion environment. The Ti-18Zr-14Nb-based foam material exhibits slightly lower passivation kinetics as compared to its bulk equivalent.