We present an approach to calculate the atomic bulk solubility in binary alloys based on the statistical-thermodynamic theory of dilute lattice gas. The model considers all the appropriate ground states of the alloy and results in a simple Arrhenius-type temperature dependence determined by a {\it "low-solubility formation enthalpy"}. This quantity, directly obtainable from first-principle calculations, is defined as the composition derivative of the compound formation enthalpy with respect to nearby ground states. We apply the framework and calculate the solubility of the A specie in A-Ti alloys (A=Ag,Au,Cd,Co,Cr,Ir,W,Zn). In addition to determining unknown low-temperature ground states for the eight alloys, we find qualitative agreements with solubility experimental results. The presented formalism, correct in the low-solubility limit, should be considered as an appropriate starting point for determining if more computationally expensive formalisms are otherwise needed.
We discuss hydrogen diffusion and solubility in aluminum alloyed Fe-Mn alloys. The systems of interest are subjected to tetragonal and isotropic deformations. Based on ab initio modelling, we calculate solution energies, then employ Oriani's theory which reflects the influence of Al alloying via trap site diffusion. This local equilibrium model is complemented by qualitative considerations of Einstein diffusion. Therefore, we apply the climbing image nudged elastic band method to compute the minimum energy paths and energy barriers for hydrogen diffusion. Both for diffusivity and solubility of…
We present a novel cluster-expansion (CE) approach for the first-principles modeling of temperature and concentration dependent alloy properties. While the standard CE method includes temperature effects only via the configurational entropy in Monte Carlo simulations, our strategy also covers the first-principles free energies of lattice vibrations. To this end, the effective cluster interactions of the CE have been rendered genuinely temperature dependent, so that they can include the vibrational free energies of the input structures. As a model system we use the phase-separating alloy Fe-Cu …
Multiphase titanium alloys are critical materials in high value engineering components, for instance in aero engines. Microstructural complexity is exploited through interface engineering during mechanical processing to realise significant improvements in fatigue and fracture resistance and strength. In this work, we explore the role of select interfaces using in-situ micromechanical testing with concurrent observations from high angular resolution electron backscatter diffraction (HR-EBSD). Our results are supported with post mortem transmission electron microscopy (TEM). Using micro-pillar c…
The integrity of irradiated zirconium based nuclear fuel cladding is related to the precipitation of hydrides which is closely connected with the solubility of hydrogen. A review on the development of measurement technologies is given and the resulting terminal solid solubilities are reflected with respect to the established model of hydrogen solubility in zirconium alloys. The results often allow for a different interpretation than the established model. An alternative qualitative approach is proposed in which the fixed TSSp for the precipitation of zirconium hydrides is replaced by a kinetic…
The most energetically favourable accommodation processes for common impurities and alloying elements in Be metal and Be-Fe-Al intermetallics were investigated using atomic scale simulations. Fe additions, combined with suitable heat treatments, may scavange Al and Si through their incorporation into the FeBe5 intermetallic. In the absence of Fe, Al and Si will not be associated with Be metal. Li and Mg are also not soluble, but may react with other impurities if present (such as Al or H). Mg may also form the MgBe13 intermetallic phase under certain conditions. He and H exhibit negligible sol…
We have developed a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti$_{1-x}$Al$_x$N alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy, corresponding to the true equilibrium state of the system. We demonstrate that the anharmonic contribution and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti$_{1-x}$Al$_x$N alloy, lowering the maximum temperat…
The thermodynamic properties of the Zr-Nb alloy are investigated at temperatures below 890 K with ab initio calculations. The solution energies of the bcc Nb-rich and hcp Zr-rich solid solutions obtained within the framework of density functional theory are in good agreement with experimental data, although insufficient for a quantitative description of the miscibility gap, for which non configurational entropy has to be accounted for. Whereas electronic free energies can be neglected, we show, using the harmonic approximation and the density functional perturbation theory, that both solution …
Effect of severe plastic deformation realized by rotary swaging on the mechanical properties and corrosion resistance of near-a-titanium alloy Ti-2.5Al-2.6Zr
Atom probe tomography (APT), electron probe microanalysis (EPMA) and nanoindentation were used to characterise the oxygen-rich layer on an in-service jet engine compressor disc, manufactured from the titanium alloy TIMETAL 834. Oxygen ingress was quantified and related to changes in mechanical properties through nanoindentation studies. The relationship between oxygen concentration, microstructure, crystal orientation and hardness has been explored through correlative hardness mapping, EPMA and electron backscatter diffraction (EBSD). The role of microstructure on oxygen ingress has been studi…
Kinetics of niobium and titanium carbide precipitates in iron has been simulated with cluster dynamics. The simulations, carried out in austenite and ferrite for niobium carbides, respectively in austenite for titanium carbide, were analyzed for dependency on temperature, solute concentration, and initial cluster distribution. The results are presented for different temperatures and solute concentrations and compared to available experimental data. They show little impact of initial cluster distribution beyond a certain relaxation time and that highly dilute alloys with only monomers present a…
Hot salt stress corrosion cracking in Ti 6246 alloy has been investigated to elucidate the chemical mechanisms that occur. Cracking was found to initiate beneath salt particles in the presence of oxidation. The observed transgranular fracture was suspected to be due to hydrogen charging; XRD and high-resolution transmission electron microscopy detected the presence of hydrides that were precipitated on cooling. SEM-EDS showed oxygen enrichment near salt particles, alongside chlorine and sodium. Aluminium and zirconium were also involved in the oxidation reactions. The role of intermediate corr…
We show that alloying with rare earth metals (REMs) can dramatically improve the machineability of a range of titanium alloys, even though the REM is not incorporated in the alloy matrix. The mechanism for this is that under cutting, shear bands are formed within which the nano-precipitates of REM are shear mixed. This lowers the melting point such that the mechanism of deformation changes from dislocation mechanism to localised amorphisation and shear softening. The material then fractures along the thin, amorphous shear-band. Outside the shear band, the REM remains as precipitates. The new a…
Dwell fatigue, the reduction in fatigue life experienced by titanium alloys due to holds at stresses as low as 60% of yield, has been implicated in several uncontained jet engine failures. Dislocation slip has long been observed to be an intermittent, scale-bridging phenomenon, similar to that seen in earthquakes but at the nanoscale, leading to the speculation that large stress bursts might promote the initial opening of a crack. Here we observe such stress bursts at the scale of individual grains in situ, using high energy X-ray diffraction microscopy in Ti-7Al-O alloys. This shows that the …
The alpha/beta interface in Ti-6Al-2Sn-4Zr-6Mo (Ti-6246) is investigated via centre of symmetry analysis, both as-grown and after 10% cold work. Semi-coherent interface steps are observed at a spacing of 4.5 +/-1.13 atoms in the as-grown condition, in good agreement with theory prediction (4.37 atoms). Lattice accommodation is observed, with elongation along [-1 2 -1 0]alpha and contraction along [1 0 -1 0]alpha . Deformed alpha exhibited larger, less coherent steps with slip bands lying in {110}beta. This indicates dislocation pile-up at the grain boundary, a precursor to globularisation, off…
The "titanium fire" as produced during high pressure and friction is the major failure scenario for aero-engines. To alleviate this issue, Ti-V-Cr and Ti-Cu-Al series burn resistant titanium alloys have been developed. However, which burn resistant alloy exhibit better property with reasonable cost needs to be evaluated. This work unveils the burning mechanisms of these alloys and discusses whether burn resistance of Cr and V can be replaced by Cu, on which thorough exploration is lacking. Two representative burn resistant alloys are considered, including Ti14(Ti-13Cu-1Al-0.2Si) and Ti40(Ti-25…
Ti has a high affinity for hydrogen and is a typical hydride formers. Ti-hydride are brittle phases which probably cause premature failure of Ti-alloys. Here, we used atom probe tomography and electron microscopy to investigate the hydrogen distribution in a set of specimens of commercially pure Ti, model and commercial Ti-alloys. Although likely partly introduced during specimen preparation with the focused-ion beam, we show formation of Ti-hydrides along α grain boundaries and α/\b{eta} phase boundaries in commercial pure Ti and α+\b{eta} binary model alloys. No hydrides are observed in the …
Based on first-principles calculations, we show that the maximum reachable concentration $x$ in the (Ga$_{1-x}$In$_x$)$_2$O$_3$ alloy in the low-$x$ regime (i.e. In solubility in $β$-Ga$_2$O$_3$) is around 10%. We then calculate the band alignment at the (100) interface between $β$-Ga$_2$O$_3$ and (Ga$_{1-x}$In$_x$)$_2$O$_3$ at 12%, the nearest computationally treatable concentration. The alignment is strongly strain-dependent: it is of type-B staggered when the alloy is epitaxial on Ga$_2$O$_3$, and type-A straddling in a free-standing superlattice. Our results suggest a limited range of appl…
Dislocation interactions at the crack nucleation site were investigated in near-alpha titanium alloy Ti-6242Si subjected to low cycle fatigue. Cyclic plastic strain in the alloy resulted in dislocation pile-ups in the primary alpha grains, nucleated at the boundaries between the primary alpha and the two-phase regions. These two phase regions provided a barrier to slip transfer between primary alpha grains. We suggest that crack nucleation occurred near the basal plane of primary alpha grains by the subsurface double-ended pile-up mechanism first conceived by Tanaka and Mura. Superjogs on the …
Ductile metals undergo a considerable amount of plastic deformation before failure. Void nucleation, growth and coalescence is the mechanism of failure in such metals. α/β titanium alloys are ductile in nature and are widely used for their unique set of properties like specific strength, fracture toughness, corrosion resistance and resistance to fatigue failures. Voids in these alloys were reported to nucleate on the phase boundaries between α and β phase. Based on the findings of crystal plasticity finite element method (CPFEM) based investigation of the void growth at the interface of α and …
Two phase titanium alloys are important for high performance engineering components, such as aeroengine discs. The microstructures of these alloys are tailored during thermomechanical processing to precisely control phase factions, morphology and crystallographic orientations. In bimodal two phase (α + β) Ti-6Al-2Sn-4Zr-2Mo (Ti-6242) alloys there are often three microstructural lengthscales to consider: large (~10 μm) equiaxed primary α; >200 nm thick plate α with a basketweave morphology; and very fine scaled (>50 nm plate thickness) secondary α that grows between the larger α plates surround…
Aiming at increasing the yield strength of transformation and twinning induced plasticity (TRIP and TWIP) titanium alloys, a dual-phase $α$/$β$ alloy is designed and studied. The composition Ti 7Cr 1.5Sn (wt.%) is proposed, based on an approach coupling Calphad calculations and classical Bo-Md design tool used in Ti-alloys. Its microstructure is made of 20% of $α$ precipitates in a $β$ matrix, the matrix having optimal Bo and Md parameters for deformation twinning and martensitic transformation. The alloy indeed displays a yield strength of 760 MPa, about 200 MPa above that of a Ti 8.5Cr 1.5Sn…
The methodology of single crystal growth of metastable $β$-Ti alloy TIMETAL LCB in an optical floating zone furnace is presented in this paper. Chemical compositions of both precursor material and single crystals were checked. It was found that the concentration of base alloying elements did not change significantly during the growth process, while the concentrations of interstitial elements O and N increased. DSC measurement determined that this concentration shift has a slight impact on ongoing phase transformations, as in the single-crystalline material peak associated with $α$ phase precip…
The mechanism of AgCl-induced stress corrosion cracking of Ti-6246 was examined at \SI{500}{\mega\pascal} and \SI{380}{\celsius} for \SI{24}{\hour} exposures. SEM and STEM-EDX examination of a FIB-sectioned blister and crack showed that metallic Ag was formed and migrated along the crack. TEM analysis also revealed the presence of \ce{SnO2} and \ce{Al2O3} corrosion products mixed into \ce{TiO2}. The fracture surface has a transgranular nature with a brittle appearance in the primary $α$ phase. Long, straight and non-interacting dislocations were observed in a cleavage-fractured primary $α$ gra…
Effect of annealing on the corrosion-fatigue strength and hot salt corrosion resistance of fine-grained titanium near-α alloy Ti-5Al-2V obtained by Rotary Swaging
The near equiatomic NiTi alloy is the most successful shape memory alloy by a large margin. It is widely and increasingly used in biomedical devices. Yet, despite having a repeatable superelastic effect and excellent shape-memory, NiTi is very far from satisfying the conditions that characterize the most reversible phase transforming materials. Thus, the scientific reasons underlying its vast success present an enigma. In this work, we perform rigorous mathematical derivation and accurate DFT calculation of transformation mechanisms to seek previously unrecognized twin-like defects that we ter…
A new $β$-metastable Ti-alloy is designed with the aim to obtain a TWIP alloy but positioned at the limit between the TRIP/TWIP and the TWIP dominated regime. The designed alloy exhibits a large ductility combined with an elevated and stable work-hardening rate. Deformation occurring by formation and multiplication of {332}<113> twins is evidenced and followed by in-situ electron microscopy, and no primary stress induced martensite is observed. Since microstructural investigations of the deformation mechanisms show a highly heterogeneous deformation, the reason of the large ductility is then i…
Titanium alloys can suffer from halide-associated stress corrosion cracking at elevated temperatures e.g., in jet engines, where chlorides and Ti-oxide promote the cracking of water vapour in the gas stream, depositing embrittling species at the crack tip. Here we report, using isotopically-labelled experiments, that crack tips in an industrial Ti-6Al-2Sn-4Zr-6Mo alloy are strongly enriched (>5 at.%) in oxygen from the water vapour, far greater than the amounts (0.25 at.%) required to embrittle the material. Surprisingly, relatively little hydrogen (deuterium) is measured, despite careful prep…
Basal slip acts as a secondary deformation mode in hexagonal close-packed titanium and becomes one of the primary mechanisms in titanium alloyed with simple metals. As these solute elements also lead to a pronounced reduction of the energy of the basal stacking fault, one can hypothesize that they promote basal dissociation of dislocations which can then easily glide in the basal planes. Here, we verify the validity of this hypothesis using ab initio calculations to model the interaction of a screw dislocation with indium (In) and tin (Sn). These calculations confirm that these simple metals a…
A method for crystallographic mapping of an alpha-beta titanium alloy with nanometre resolution using scanning precession electron diffraction and open-source software libraries
The solubility and diffusivity of hydrogen in disordered Pd1-xCux alloys are investigated using a combination of first-principles calculations, a composition-dependent local cluster expansion (CDLCE) technique, and kinetic Monte Carlo simulations. We demonstrate that a linear CDCLE model can already accurately describe interstitial H in Pd1-xCux alloys over the entire composition range (0\leqx\leq1) with accuracy comparable to that of direct first-principles calculations. Our predicted H solubility and permeability results are in reasonable agreement with experimental measurements. The propose…
Additive manufacturing has been adopted to process nickel-titanium shape memory alloys due to its advantages of flexibility and minimal defects. The current layer-by-layer method is accompanied by a complex temperature history, which is not beneficial to the final characteristics of shape memory alloys. In this study, a continuous directed energy deposition method has been proposed to improve microstructure uniformity. The spatial characterization of nickel-titanium shape memory alloy fabricated by continuous directed energy deposition is investigated to study the temperature history, phase co…
The effects of various heat treatments on the microstructure and hardness of new Ni56Ti41Hf3 and Ni56Ti36Hf8 (atomic %) alloys were studied to evaluate the suitability of these materials for tribological applications. A solid-solution strengthening effect due to Hf atoms was observed for the solution annealed (SA) Ni56Ti36Hf8 alloy (716 HV), resulting in a comparable hardness to the Ni56Ti41Hf3 alloy containing 54 vol.% of Ni4Ti3 precipitates (707 HV). In the Ni56Ti41Hf3 alloy, the maximum hardness (752 HV), achieved after aging at 300C for 12 h, was attributed to dense, semi-coherent precipit…
The dislocation structures appearing in highly mis-oriented soft/hard grain pairs in near-alpha titanium alloy Ti6242Si were examined with and without the application of load holds (dwell) during fatigue. Dislocation pile-up in a soft grain resulted in internal stresses in an adjacent hard grain which could be relaxed by dislocation multiplication at localized Frank-Read sources, a process assisted by the provision of a relaxation time during a load hold. The rate of this process is suggested to be controlled by <c+a> pyramidal cross-slip and <a> basal junction formation. A high density of <a>…
The tribological performance and underlying deformation behavior of Ni55Ti45, Ni54Ti45Hf1 and Ni56Ti36Hf8 alloys were studied using rolling contact fatigue (RCF) testing and transmission electron microscopy (TEM). TEM results of the as-machined RCF rods, prepared using focus ion beam, revealed some damage very close to the surface. TEM results after initial RCF cycling showed that additional damage was mainly confined to deformation bands that propagated several microns into the sample. These bands formed via localized dislocation slip, possibly on multiple slip systems, within the B2 matrix a…
The electrochemical frequency modulation (EFM) technique can consider as a new tool for electrochemical corrosion monitoring. The calculation of corrosion rate with a non-destructive and rapid technique is a necessity to study corrosion behavior of metals under loading and thermal cycling. NiTi shape memory alloy (SMA) is characterized by differential scanning calorimetry (DSC) and uniaxial tensile testing. The corrosion behavior and reliability of technique have been examined for NiTi sample in artificial physiological solution. The results show the sensitivity of EFM technique to temperature…
Solid solubility (SS) is one of the most important features of alloys, which is usually difficult to be largely tuned in the entire alloy concentrations by external approaches. Some alloys that were supposed to have promising physical properties could turn out to be much less useful because of their poor SS, e.g., the case for monolayer BNC [(BN)1-x(C2)x] alloys. Until now, an effective approach on significantly enhancing SS of (BN)1-x(C2)x in the entire x is still lacking. In this article, a novel mechanism of selective orbital coupling between high energy wrong-bond states and surface states…
Zr and Mo macrosegregations were investigated in Ti6246 titanium alloy industrial-scale ingotby vacuum arc remelting. The formation mechanism of Zr and Mo macrosegregations was studied during the solidification process. Zr macrosegregation was characterized by low content in the equiaxed grain zone and high content in the hot top zone. Mo exhibits an opposite trend with Zr. The macrosegregations of Zr and Mo were the most pronounced, with a statistic segregation degree higher than Al and Sn. It could be concluded that temperature gradient and solidification rate dominated the macrosegregation …
Designing Homogeneous Ti-Nb-Fe-Sn $β$ Titanium Alloys by PBF-LB: A Pre-Alloyed Powder Blend Strategy
Universidade Estadual de Campinas (UNICAMP)（坎皮纳斯州立大学）；Charles University（查理大学）；Federal Institute of Education, Science and Technology of São Paulo (IFSP)（圣保罗联邦教育、科学和技术学院）；Institute of Thermomechanics, Czech Academy of Sciences（捷克科学院热力学研究所）
The corrosion potential of commercially pure titanium in NaCl solutions is dramatically affected by trace Fe additions, which cause the appearance of submicron pockets of \b{eta} phase at grain boundary triple points. Furthermore, the low solubility of hydrogen in hexagonal close-packed α-Ti makes titanium alloys prone to subsequent hydride-associated failures due to stress corrosion cracking. We analyzed α-α and α-\b{eta} sections of the abutting grain boundary of a \b{eta} pocket in a Grade 2 CP-Ti, and the α-\b{eta} phase boundary. Fe and H partition to \b{eta} and segregate at the grain bo…
The mechanical properties of polycrystalline metals are governed by the interaction of defects that are generated by deformation within the 3D microstructure. In materials that deform by slip, the plasticity is usually highly heterogeneous within the microstructure. Many experimental tools can be used to observe the results of slip events at the free surface of a sample; however, there are only a few methods for imaging these events in the bulk. In this article, the imaging of bulk slip events within the 3D microstructure are enabled by the combined use of X-ray diffraction contrast tomography…
High-Pressure XRD Study of Ti-3Al-2.5V Titanium Alloy: Intermediate Transition Pressure and Composition Trends in Ti-Al-V Alloys
Universitat de València（瓦伦西亚大学）；Geosciences Barcelona (GEO3BCN-CSIC)（巴塞罗那地球科学研究所（GEO3BCN-CSIC））；CELLS-ALBA Synchrotron Light Facility（CELLS-ALBA同步辐射光源设施）；AWE（英国原子武器研究院）
The kinetics of primary alpha-Ti colony/Widmanstatten plate growth from the beta are examined, comparing model to experiment. The plate growth velocity depends sensitively both on the diffusivity D(T) of the rate-limiting species and on the supersaturation around the growing plate. These result in a maxima in growth velocity around 40 K below the transus, once sufficient supersaturation is available to drive plate growth. In Ti-6246, the plate growth velocity was found to be around 0.32 um min-1 at 850 oC, which was in good agreement with the model prediction of 0.36 um min-1 . The solute fiel…
In Ni-base superalloys with low Al and/or Ti content the precipitation and subsequent coarsening of gamma' particles at intermediate temperatures contribute to the degradation of the mechanical properties of the alloy. In the present paper the coarsening process is modelled and the change of the critical resolved shear stress of the alloy due to coarsening of the gamma' particles is calculated by means of statistical analysis of the depinning of a single gliding edge dislocation. It is found that the contribution of gamma' hardening to the critical resolved shear stress at 973 K reduces to mor…
We describe a dynamical phase transition occurring within a shear band at high temperature and under extremely high shear rates. With increasing temperature, dislocation deformation and grain boundary sliding is supplanted by amorphization in a highly localized nanoscale band, which allows massive strain and fracture. The mechanism is similar to shear melting and leads to liquid metal embrittlement at high temperature. From simulation, we find that the necessary conditions are, lack of dislocation slip systems, low thermal conduction and temperature near the melting point. The first two are ex…
Additive manufacturing has been vastly applied to fabricate various structures of nickel-titanium (NiTi) shape memory alloys due to its flexibility to create complex structures with minimal defects. However, the microstructure heterogeneity and secondary phase formation are two main problems that impede the further application of NiTi alloys. Although post-heat treatment is usually adopted to improve or manipulate NiTi alloy properties, it cannot realize the spatial control of thermal and/or mechanical properties of NiTi alloys. To overcome the limitations of uniform post-heat treatment, this …
It has been widely accepted that the introduction of titanium carbides into titanium-based alloys can significantly enhance the oxidation resistance due to their superior physicochemical stability at elevated temperatures. The present study reported for the first time that the ordered C vacancies within titanium carbides could lead to an uncommon phenomenon particularly at the very initial stage of oxidation. The intrinsic micro-to-macro oxidation mechanisms were systematically clarified with the aids of transmission electron microscope and ab-initio molecular dynamics simulation.
We have performed density functional calculations of the formation energies of substitutional transition metal (TM) defects, C vacancies, and C interstitial defects in TiC. In addition we have evaluated the migration energy barriers for C atoms in the presence of TM impurities. We find that the solubility of TM impurities taken from the 3d TM series is low and only Sc and V impurities can be dissolved into TiC at equilibrium. In addition, we find that the migration energy barriers of C in TiC are greatly affected by the presence of TM impurities: The migration barriers are generally lower in t…
