In this paper, phase transitions and microstructure evolution in titanium Ti-6Al-4V alloy parts produced by electron beam melting (EBM) under hydrogenation was investigated. Hydrogenation was carried out at the temperature of 650 °C to the absolute hydrogen concentrations in the samples of 0.29, 0.58, and 0.90 wt. %. Comparative analysis of microstructure changes in Ti-6Al-4V alloy parts was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). Furthermore, in-situ XRD was used to investigate the phase transitions in the samples during hydrogenation. The structure of Ti-6Al-4V parts produced by EBM is represented by the α phase plates with the transverse length of 0.2 μm, the β phase both in the form of plates and globular grains, and metastable α″ and ω phases. Hydrogenation to the concentration of 0.29 wt. % leads to the formation of intermetallic Ti₃Al phase. The dimensions of intermetallic Ti₃Al plates and their volume fraction increase significantly with hydrogen concentration up to 0.58 wt. % along with precipitation of nano-sized crystals of titanium δ hydrides. Individual Ti₃Al plates decay into nanocrystals with increasing hydrogen concentration up to 0.9 wt. % accompanied by the increase of proportion and size of hydride plates. Hardness of EBM Ti-6Al-4V alloy decreases with hydrogen content.

In the present study, the methods of optical, scanning electron, and transmission electron microscopy as well as X-ray diffraction analysis gained insights into the mechanisms of surface finish and microstructure formation of Ti–6Al–4V parts during an EBF³-process. It was found that the slip band propagation within the outermost surface layer provided dissipation of the stored strain energy associated with martensitic transformations. The latter caused the lath fragmentation as well as precipitation of nanosized β grains and an orthorhombic martensite α″ phase at the secondary α lath boundaries of as-built Ti–6Al–4V parts. The effect of continuous electron beam post-treatment on the surface finish, microstructure, and mechanical properties of EBF³-fabricated Ti–6Al–4V parts was revealed. The brittle outermost surface layer of the EBF³-fabricated samples was melted upon the treatment, resulting in the formation of equiaxial prior β grains of 20 to 30 μm in size with the fragmented acicular α′ phase. Electron-beam irradiation induced transformations within the 70 μm thick molten surface layer and 500 μm thick heat affected zone significantly increased the Vickers microhardness and tensile strength of the EBF³-fabricated Ti–6Al–4V samples.

The inferior mechanical properties of EBAM Ti-6Al-4V samples are due to the coarse columnar grains containing coarse lamellar structures. One can expect that water cooling of the build platform will increase the cooling rate of the molten pool during the build-up process, causing microstructure refinement. In the present work, the substrate cooling effects on the microstructure and phase composition of EBAM Ti-6Al-4V samples are studied using optical, scanning electron, and scanning transmission microscopy, as well as X-ray diffraction analysis. It is shown that the microstructure of the EBAM Ti-6Al-4V samples built on the substrate without water cooling consists predominantly of columnar prior β grains with lateral sizes ranging up to 2000 µm, while cooling of the build platform causes the appearance of equiaxed prior β grains measuring 1000 µm. Moreover, the refinement of the martensite structure and the precipitation of α′′ martensite platelets within α laths occur in the EBAM Ti-6Al-4V samples built on the water-cooled build platform. An explanation of the mechanisms underlying the α′→α + β and α′→α + α′′ + β transformations during the building process is provided based upon ab initio calculations. The fragmentation of the α laths under the residual compressive stresses is discussed.

Experimental and theoretical studies enabled the reveal of patterns of the microstructure formation in the surface layer of Ti-6Al-4V titanium alloy subjected to ultrasonic impact treatment. The mixed amorphous and nanocrystalline structure of the 200 nm thick uppermost surface layer of titanium dioxide TiO₂ was demonstrated using transmission electron microscopy. The 5 µm thick intermediate layer containing nanocrystalline α grains, and the 50–60 µm thick lower layer containing fragmented α-Ti grains with retained β phase were also observed. The refinement of the β-Ti phase during ultrasonic impact treatment was accompanied by the formation of the orthorhombic (α″) martensitic phase. Molecular dynamics simulation of strains of a vanadium-doped titanium crystallite subjected to ultrasonic impact treatment revealed the formation of striped dislocation substructures as well as the development of reversible β→α phase transformations. Ab initio calculations of the atomic structure of V-doped Ti crystallites containing α, β or α″ phases of titanium were carried out. On the basis of the results of the experimental observations, a molecular dynamics simulation and ab initio calculations a mechanism was proposed, which associated the development of the strain-induced β→α″ phase transformations in Ti-6Al-4V alloy with the presence of oxygen. The role of the electronic subsystem in the development of the strain-induced phase transformations was discussed.

Experimental and theoretical studies helped to reveal patterns of surface roughening and the microstructure refinement in the surface layer of commercial pure titanium during ultrasonic impact treatment. Applying transmission electron microscopy technique, a gradient microstructure in the surface layer of the ultrasonically treated sample, where the grain size is varied from nano- to micrometers was revealed. It was shown that the surface plastic strains of the titanium sample proceeded according to the plastic ploughing mechanism, which was accompanied by dislocation sliding, twinning, and the transformations of the microstructure and phase composition. The molecular dynamics method was applied to demonstrate the mechanism of the phase transformations associated with the formation of stacking faults, as well as the reversible displacement of atoms from their sites in the hcp lattice, causing a change in coordination numbers. The role of the electronic subsystem in the development of the strain-induced phase transformations during ultrasonic impact treatment was discussed.