FG Mikrostrukturelles Werkstoffdesign
Refine
Year of publication
Document Type
Way of publication
- Open Access (4)
Language
- English (146)
- Chinesisch (1)
- German (1)
Keywords
- Microstructure (2)
- Material alloying (1)
- Phase Transformation (1)
- Phase composition (1)
- Titanium Aluminide (1)
- Titanium Aluminides (1)
Institute
Stacking fault formation in perovskite Ti3AlC carbides in a TiAl based alloy during creep at 800°C
(2023)
Recent research on Co-based and CoNi-based alloys revealed that the Co–Al–W-system provides interesting properties, however, the high content of W addition triggers high mass density of alloys which limits its industrial application. Therefore, new high temperature superalloys based on the Co–Ni–Al–Ti-system with high content Cr and strengthened by γ′-(Ni,Co)3(Cr,Al,Ti) precipitates, have been developed, and the effect of different refractory element additions was investigated. STEM-EDS and HEXRD were employed to determine the elemental partitioning behavior and the lattice misfit between the γ and γ′ phases. Ta and Nb strongly concentrate within the γ′ phase, whereas Mo weakly partitions to the γ phase. W distributes equally between the γ and γ′ phases. These new superalloys have an unexpectedly high positive misfit compared with some conventional Ni-based superalloys and Co-based superalloys. Nb and Ta additions increase the lattice misfit further, while Mo and W decrease the lattice misfit. The effect of refractory elements alloying on the yield stress at room temperature was evaluated by analyzing the contributions of different strengthening mechanisms. Alloying with Nb or Ta significantly improves precipitation strengthening by increasing the antiphase boundary energy. Mo has the highest solid solution strengthening effect in the γ phase, followed by W. Compared with some conventional Ni-based superalloys, the investigated new CoNi-based superalloys exhibited better mechanical properties at high temperature, which indicates that these compositionally complex alloys are possible candidates for high temperature applications.
Due to the lack of independent slip systems and the difficulty in mechanical twinning, D019 ordered α2-Ti3Al phase is known to be of substantial mechanical anisotropy, which partly accounts for the low ductility of two-phase (α2+γ) TiAl alloys. However, recent studies have shown that in Al-rich α2 phase compression deformation twins can be activated, which could be beneficial for the ductility of the alloys. In the present study, for the first time, we have revealed a novel internal twinning mechanism of α2 phase in a TiAl alloy deformed at high temperature. Three twin generations of a common type {202¯1}[removed] were revealed: Secondary twins formed within the primary twin, and tertiary twins formed in the secondary twin. It is important to note that this internal twin structure can only be observed in the [removed] direction but not the commonly used [removed] direction. The shear plane P of all twin variants is of type {12¯10}. Due to the variation of the twinning elements between the twin variants, the twinning shear is blunted. The interfaces between the twin variants are characterized by high-resolution electron microscopy. Special attention was paid to the structure of the coherent and incoherent twin boundaries. The effect of chemical ordering is discussed. Our results also shed light on the complex twinning mechanisms in hexagonal structures.
The high-temperature oxidation behaviors of Co- and CoNi-base alloys with different Ni and Cr additions were investigated by isothermal oxidation in air at 900 and 1000 °C. The structure, composition, and element distribution in the three layers within the oxide scales in different alloys have been explored in detail by electron microscopy, especially with regard to the fine oxide particles in the intermediate layer. Based on the microstructure and phase constitution of the oxide scales, the synergetic effects of alloying elements on the oxidation mechanisms and resistance have been elucidated in detail with the aid of CALPHAD calculation.
Usually, Co-based superalloys contain a high fraction of W and/or Mo. The refractory elements stabilize the precipitate phase, but cause a high density. In this work, new L12-phase hardened, low-density CoNiCr-based superalloys were developed with the assistance of CALPHAD calculations. Several alloys were studied experimentally and their microstructures, elemental distributions, lattice parameters and the lattice misfit between the γ and γ′ phases were evaluated using scanning electron microscopy, transmission electron microscopy, atom probe tomography and high energy X-ray diffraction. The alloys exhibit a very high misfit, good phase stability and excellent mechanical strength. It was found by hardness tests that a two-step heat treatment improves the strength of the new alloys even further. In comparison with conventional Co-based superalloys, Co–Al–W based superalloys and Co–Ti based superalloys, as well as Ni-based superalloys, i.e. Udimet 720Li, they have a low mass density and high yield stress. They also overcome the problem of a generally low lattice misfit of previous L12-phase hardened CoNiCr-based superalloys with high Ni and Cr contents. As a result, they show cuboidal-shaped precipitates similar to Co–Al–W and Co–Al–Mo based superalloys.
In order to develop highly efficient aircraft engines, the use of alloys for turbine blades that combine high creep resistance and lower density brings substantial benefits. That may be achieved by the introduction of a reinforcing phase, such as a discontinuous reinforcement. So far, most researched particle-reinforced Ni-based superalloys made use of sub-micrometer particles, such as oxides and borides, often produced by in-situ reactions. These are proposed solely as dislocation immobilizers, in a role comparable to that carried out by γ’ precipitates, while metal matrix composites (MMCs) containing micro-scale particles offer a load-transfer potential. To combine both approaches, a recently designed polycrystalline Ni-based γ’-strengthened superalloy reinforced with TiC particles was produced by low energy mixing of powders, followed by pressure sintering. The composite, along with a non-reinforced reference, was submitted to compression creep tests at 973 K (700 °C), with stresses varying from 280 to 500 MPa. Selected specimens had their microstructure evaluated with techniques such as EBSD and XRD. When simulating a working turbine, the material density influences directly the centripetal forces acting on a section of a turbine blade, and consequently the creep rates. In the proposed composite, not only an increase in the threshold stress by a load-transfer component was obtained, but also the density reduction affected remarkably the creep rates. Moreover, the presented MMC not only presented a superior creep resistance in relation to the non-reinforced alloy, but also exhibited higher stability of primary and secondary γ’ volumes after 500 h in creep tests.
Ti-Al3Ti metal-intermetallic laminate (MIL) composites are known as promising structural materials due to the unique combination of their specific properties. However, their application is still limited due to the extremely high brittleness of the Al3Ti phase. In this study, we attempt to address this issue by changing the D022 crystal structure of Al3Ti to the more ductile L12 structure by alloying it with silver. To select the best fabrication regimes of Ti-Ti(Al1−xAgx)3 composites, in situ synchrotron X-ray diffraction analysis was performed to reveal the chemical reactions occurring upon heating the Ti-Al-Ag sample. The analysis showed that the highest amount of Ti(Al1−xAgx)3 phase with the L12 structure appears at 930 °C. This temperature was chosen for subsequent spark plasma sintering experiments. Scanning electron microscopy, energy dispersive X-ray analysis, and X-ray diffraction analysis revealed that the sintered sample consisted mainly of Ti, Ti(Al1−xAgx)3, and a minor fraction of the Ag-Al compound distributed in the central parts of the intermetallic layers and at the grain boundaries. Modification of the titanium trialuminide crystal structure positively affected the properties of the composite, providing a 60% increase in fracture toughness. The Ag-Al phase also contributed to toughening, causing an additional crack deflection effect.
In-situ synchrotron-based high energy X-ray diffraction (HEXRD) and ex-situ Gleeble tests were conducted to investigate the deformation behavior of the βo(ωo) phase in a Ti4Al3Nb alloy. In samples compressed at 600 and 800 °C, the brittle ωo phase deforms mostly elastically, resulting in the failure of the Ti4Al3Nb alloy by premature fracture. In a sample deformed at 900 °C, the ωo phase mostly transforms into the βo phase under uniaxial loading. Moreover, the ductility of a Ti4Al3Nb alloy is largely enhanced at this temperature. In a sample deformed at 1000 °C, dynamic recrystallization (DRX) of the βo phase extensively takes place. Direction 1 (D1) and Direction 2 (D2) deviating from the loading direction with an angle of 65° ± 5° and 15° ± 5° are selected to analyze the lattice strain evolution of (110)βo lattice planes. At the late stage of macro strain hardening, deformed[removed]βo//D1 oriented grains bear a higher load due to the occurrence of DRX in[removed]βo//D2 oriented grains. Subsequently, DRX continues in[removed]βo//D1 oriented βo grains. The coordinated deformation of βo grains ensures the good deformability of a Ti4Al3Nb alloy at 1000 °C.
In modern β-solidified TiAl alloys, the decomposition of α2 phase is frequently observed during heat treatment or high-temperature deformation of the alloys. In this study, high-temperature deformation and decomposition mechanisms of α2 phase in a Ti-45Al-8.5Nb-0.2B-0.2W-0.02Y alloy are investigated. In a sample deformed at 800 °C, the precipitation of βo(ωo) phase is observed within the equiaxed α2 phase. The nucleation of ωo particles within the βo matrix indicates the α2→βo→ωo transformation. In addition, numerous γ phase precipitates form within the βo(ω) areas. The α2 lamellae decompose into ultrafine (α2+γ) lamellae and coarsened γ lamellae via α2→α2+γ and α2→γ transformation, respectively. Moreover, the ωo phase nucleates within the ultrafine lamellae via α2→ωo transformation. However, in a sample deformed at 1000 °C, the nucleation of βo particles is sluggish, which is caused by the efficient release of the internal stress via dynamic recrystallization (DRX). These results indicate that complex phase transformations can be introduced by the decomposition of α2 phase in TiAl alloys with a high amount of β-stabilizing elements.
Atomic site occupancy of alloying elements and Laves phase stability in γ-γ′ Co-base superalloys
(2022)
The atomic site occupancy of alloying elements in the ZrCo2 and HfCo2 based Laves phases formed in the Co-9Al-9W-2Zr and Co-9Al-9W-2Hf alloys was experimentally determined by the combined techniques of energy-dispersive X-ray spectroscopy mapping with atomic resolution and the atom location by channeling enhanced microanalysis (ALCHEMI) method. The results show that both Al and W occupy the Zr site in the C15 and the Hf site in the C36 crystal structure. The atomic locations of Al and W were further confirmed by comparing calculated inelastic cross-sections with experimental ALCHEMI results. Using the determined atomic site occupancies of alloying elements, special quasirandom structure solid solution models with 192 atoms were constructed and employed in first-principles calculations. It is found theoretically that the energy of formation of the C15 structure is always lower than that of the C36 structure at 0 K in both ZrCo2 and HfCo2 phases, no matter whether Al and W are incorporated or not. However, further ab initio molecular dynamics simulations suggest that lattice vibration at finite temperature contributes significantly to the phase stability, stabilizing the C36 structure compared to the C15 type for the (Hf, Al, W)Co2 phase at finite temperature, which fits well with the experimental findings.
The β titanium alloys are key materials in lightweight and biomedical applications, due to the combination of excellent biocompatibility and mechanical properties. However, the Binder-based Powder Technologies such as Metal-Injection-Molding (MIM), Binder-Jetting and Fused-Filament-Fabrication, normally introduce three major processing-related defects in the as-sintered Ti-parts: (i) residual porosity, (ii) high impurity level and (iii) coarse-grained structure. The previous studies revealed that these processing defects invariably tend to be even more severe in β titanium alloys than in α/β Ti-6Al-4V alloy, all fabricated by powder metallurgical route. In this work, these processing defects and their likely origins in MIM β titanium alloys are analysed. Furthermore, the influence of these defects on damage tolerance and fracture mechanisms of MIM β titanium alloys under either static or dynamic loading is investigated. Based on the studies, strategic technical improvements in the processing to improve the reliability of MIM β titanium alloys products are proposed.
Precise knowledge of the phase equilibria in the Ti-Al-Nb system between 700 and 900 °C is of crucial importance for the urgently needed improvement of TiAl-based turbine materials already in industrial use to achieve further energy savings. As a result of the occurrence of the two ternary intermetallic phases ωo (“Ti4NbAl3”) and O (“Ti2NbAl”), which form in the solid state just in the range of the application-relevant temperatures, the phase relations are very complex and not well studied. In the present investigation, isothermal sections of the Ti-rich part of the Ti-Al-Nb system at 700, 800, and 900 °C were determined by a systematic study of 15 ternary alloys, one solid-solid diffusion couple, and three liquid-solid diffusion couples. Using scanning electron microscopy, electron probe microanalysis (EPMA), x-ray diffraction (XRD), high-energy XRD (HEXRD), differential thermal analysis (DTA), and transmission electron microscopy (TEM) investigations, type and composition of phases as well as phase transitions were determined. With these results, the phase equilibria were established. A focus of the investigations is on the homogeneity ranges of the two ternary phases ωo and O, which both are stable up to temperatures above 900 °C. Based on the compositions measured for the ωo phase and its crystal structure type, a new formula (Ti,Nb)2Al is suggested. The results also indicate that the phase field of the ωo phase is split into two parts at 900 °C because of the growing phase field of the ordered (βTi,Nb)o phase.
The knowledge of phase equilibria in the Ti-Al-Nb system above 1000 °C is of importance for the manufacturing of TiAl-based parts for high-temperature structural applications. Especially the extended homogeneity range of the cubic (βTi,Nb) phase, which is determined by its Al solubility, and the position and extension of the high-temperature (αTi) phase is of crucial importance for the hot-workability and microstructure control of these alloys. However, the phase diagrams reported in the literature are very contradicting especially regarding these aspects. For this reason, a systematic reinvestigation of the phase equilibria in this part of the system was carried out. A total of 17 ternary alloys were synthesized, heat-treated at 1000-1300 °C, and analyzed by electron probe microanalysis (EPMA), x-ray diffraction (XRD), high-energy XRD (HEXRD), and differential thermal analysis (DTA) to determine composition and type of equilibrium phases as well as transition temperatures. With this information, isothermal sections of the Ti-rich part of the Ti-Al-Nb system at 1000, 1100, 1200, and 1300 °C were established. An isolated (βTi,Nb)o phase field is found to be stable at 1000 and 1100 °C. Furthermore, the formation and homogeneity range of (αTi) at high temperatures as well as the presence of Ti3Al at 1200 °C is experimentally investigated and discussed. Based on the observed phase equilibria and transition temperatures, an improved reaction scheme for the entire Ti-Al-Nb system is proposed.
Intermetallic alloys such as FeTi have attracted ever-growing attention as a safe and efficient hydrogen storage medium. However, the utilization of high-purity metals for the synthesis of such materials poses considerable concerns over the environmental sustainability of their large-scale production. Here, we report an approach for synthesizing FeTi from industrial scraps of iron (steels C45 and 316 L) and titanium (Ti alloy Grade 2) to reduce the carbon footprint associated with FeTi alloy synthesis, without compromising their hydrogen storage properties. At 50 °C and a pressure of 0 to 100 bar, the alloys obtained by using C45-Ti Grade 2 and 316L-Ti Grade 2 can absorb a maximum amount of hydrogen of 1.61 wt.% and 1.50 wt.%, respectively. Moreover, depending on the type of steel utilized, the thermodynamic properties can be modified. Our findings pave a pathway for developing high-performance, environmentally-sustainable FeTi alloys for hydrogen storage purposes using industrial metal wastes.
First-principles calculations were performed to investigate the elastic and thermodynamic properties for multi-component Co-based superalloy systems and explored the effect of alloying on stabilizing the γ′ phase. First, the comparisons were carried out for the γ′ phase in Co3(Al,TM) (TM being transition metals) and Ni3Al systems between the present computational results using the EMTO-CPA method and other available DFT calculations as well as experimental data. The lattice parameters, elastic constants, and Debye temperatures are consistent with experimental results and other calculations. The predicted thermodynamic properties, e.g., the Gibbs free energy, excess entropy, and linear thermal expansion coefficient, agree well with CALPHAD results, experimental results, and other available first-principles calculations. A combination of EMTO-CPA method and Debye–Grüneisen model is utilized in this work to ensure that the alloying effect on the stability of the γ′ phase in a multi-component Co-based system is captured efficiently. This could open the path for designing novel multi-component Co-based alloys based on first-principles calculation. To demonstrate this, predictions for the properties of multicomponent systems were undertaken. Our results show that Ni aids in the stabilization of the (CoNi)3(Al, Mo, Nb) phase.
The effect of grinding on static recrystallization and oxidation of a novel Co-based superalloy has been studied. The evolution of surface recrystallization after heat treating at 850 °C in air was revealed by comparing ground specimens with electropolished ones. The loss of Al and Ti from the bulk material leads to the formation of a γ′-free region and further promotes recrystallization at the surface.
The alloying elements Nb, Ta and Zr improve the creep properties of fully lamellar γ/α2 titanium aluminides significantly. Since high temperature deformation mainly occurs in the γ-phase of γ/α2 titanium aluminides, the diffusivity and the solid solution hardening effect of these three elements in the γ-phase is studied by analyzing the concentration gradients of the alloying elements and the resulting hardness across the interdiffusion zone of diffusion couples by energy dispersive X-ray diffraction and nanoindentation. The results reveal that Zr has the highest interdiffusion coefficient but also the largest solid solution hardening coefficient. The mechanical properties of single γ-phase Ti-54Al-5X alloys were investigated by strain rate jump tests. The addition of 5 at.% Nb or Ta lead to an increased strength compared to a binary γ-Ti-54Al alloy. The Zr-containing γ-TiAl alloy reveals the highest strength at 750°C and 900°C, which is discussed to be due to the strong solid solution hardening effect of Zr. However, in comparison to the other alloys, Ti-54Al-5Zr shows quite brittle behavior up to 900°C. The lower diffusivity of Ta compared to Nb leads to a higher strength of the Ta-modified alloy at 900◦C.
Titanium aluminide alloys (TiAl), especially alloys based on the intermetallic γ-phase, have attracted much attention as a substitute for Ni-based alloys as highly promising high temperature structural materials. This is due to their low density, high specific strength and specific elastic moduli as well as good corrosion resistance [1,2]. However, the processing of these alloys is still challenging and expensive, since for example the necessary temperatures for hot forming between 1100 °C and 1250 °C bring currently available die materials to their limits. Fortunately, by an appropriate tuning of the alloy composition it is possible to form phases and microstructures at the forming temperature which provide good deformation capabilities. The addition of alloying elements can not only lead to a shift of the transition temperatures of the phases but can also improve mechanical properties. For instance the addition of Zirconium (Zr), a β-stabilizing element, lowers the phase transformation temperatures of the ‘softer’ disordered α and β phases and has other additional beneficial effects e.g. solution strengthening on TiAl alloys [3]. While TiAl systems with addition of elements like Niobium and Molybdenum are well investigated so far, only a few studies on the effects of Zr additions in TiAl systems exist.
References
[1] F. Appel, J. Paul, M. Oehring (Eds.), Gamma Titamium Aluminde Alloys - science and technology, Wiley-VCH, Weinheim, 2011.
[2] F. Appel, H. Clemens, F.D. Fischer, Modeling concepts for intermetallic titanium aluminides, Progress in Materials Science 81 (2016) 55–124.
[3] X.J. Jiang, Y.K. Zhou, Z.H. Feng, C.Q. Xia, C.L. Tan, S.X. Liang, X.Y. Zhang et al., Influence of Zr content on β-phase stability in α-type Ti–Al alloys, Materials Science and Engineering: A 639 (2015) 407–411.