Phase evolution in driven alloys: An overview on compositional patterning
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Materials Science↗
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Results for “Phase evolution”
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Phase evolution in two-phase alloys during severe plastic deformation
Herein, phase evolution in FCC metals with strongly interacting alloy components during severe plastic deformation is investigated using molecular dynamics simulations. Specifically, we study the alloy microstructure in steady state, nucleation and growth of precipitates in supersaturated alloys, and the decomposition of precipitates in undersaturated alloys. The results are compared to a modified effective temperature model, providing a physical understanding for the atomic processes underlying the model and a perspective on its strengths and weaknesses. Key observations in this work are nucleation and growth of precipitates during SPD at a temperature of 100 K; Gibbs-Thomson-like behavior relating solubility to precipitate size under steady-state shearing; a direct relationship between the effective temperature and the shear modulus; and the importance of cluster agglomeration during precipitate growth. The study also reveals that the mechanisms of forced chemical mixing depends on precipitate size, adding complications for effective temperature models describing inhomogeneous systems. The simulations are shown to provide good semiquantitative agreement with experimental findings reported in the literature.
36 MATERIALS SCIENCE↗
Effect of Zn Addition on Phase Evolution in AlCrFeCoNiZn High–Entropy Alloy
The addition of Zn to AlCrFeCoNi high-entropy alloy (HEA) poses intriguing questions as to how it would affect phase evolution. Herein, the phase evolution in AlCrFeCoNiZn is studied using a combination of experimental techniques (X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential scanning calorimetry) and computational (density-functional theory [DFT], calculation of phase diagrams, and machine-learning) methods. Mechanically alloyed and spark-plasma-sintered AlCrFeCoNiZn assumes a metastable single-phase, body-centered-cubic (BCC) structure that undergoes diffusion-controlled phase separation upon subsequent heat treatment to form separate (Al, Cr)-rich, (Fe, Co)-rich, and (Zn, Ni)-rich phases. The formation of (Al, Cr)-rich phase, not reported previously in AlCrFeCoNi-based HEAs, is attributed to strong clustering tendency of Cr–Zn and Cr–Ni pairs, combined with the strong ordering of Zn–Ni pair, driving out Cr that in turn combines with Al to form a (Al, Cr)-rich phase. In the DFT results, the formation of thermodynamically stable L1 2 phase is shown wherein Cr–Fe–Zn [Al–Ni-Co] preferably occupy1a (000) [3c (0 ½ ½)] positions. Furthermore, the sluggish diffusional transformation to L1 2 phase from BCC precursors is attributed to the small stacking-fault energy of AlCrFeCoNiZn. The equilibrated HEA exhibits a high microhardness of 8.24 GPa with an elastic modulus of 184 GPa.
36 MATERIALS SCIENCE↗
Sigma phase evolution and nucleation mechanisms revealed by atom probe tomography in a 347H stainless steel
The size evolution and phase composition of sigma phases were investigated for a 347H stainless steel subject to isothermal aging at 750 °C for up to 10,000 h. Scanning electron microscopy reveals that sigma phases are present before 336 h aging and they continue to grow for all aging times studied. Atom probe tomography shows little variation in the sigma phase composition with aging time up to 10,000 h, and only the C content decreases with aging time. The comparison of C concentration suggests that the sigma phase does not nucleate within the C-depleted matrix or precipitate free grain boundaries, leaving dissolving metastable M 23 C 6 as the only possible nucleation site. Based on the experimental results and thermodynamic simulations, the desirable Nb concentration is discussed to reduce the kinetics of sigma phase growth, and possible design directions are suggested to improve 347H.
36 MATERIALS SCIENCE↗
Kinetic control of phase evolution and defect-mediated recombination in AACVD-grown copper antimony sulphide thin films
Copper antimony sulphide (CAS) is a multinary chalcogenide semiconductor in which small deviations from stoichiometry can drive phase competition and strong defect-mediated modulation of optoelectronic properties. However, the systematic roles of copper precursor fraction and deposition time in governing phase evolution, off-stoichiometry, and recombination dynamics in aerosol-assisted chemical vapour deposition (AACVD)-grown undoped CAS thin films remain insufficiently understood. In this work, undoped CAS thin films were deposited by AACVD using Cu(dedtc)2 and Sb(dedtc)3 single-source precursors at 550 °C and a carrier gas flow rate of 150 sccm, while the Cu(dedtc)2 mole fraction (x = 0.15 – 0.55) and deposition time (1 – 2 hours) were systematically varied to probe how growth kinetics influence phase composition, microstructure, and defect-mediated optical properties without post-deposition annealing or extrinsic doping. Increasing copper precursor content drives phase evolution toward tetrahedrite-dominant CAS films at intermediate Cu(dedtc)2 mole fractions, with the film deposited at x = 0.35 exhibiting the strongest tetrahedrite character within the parameter space examined. The films are also copper-rich, antimony-poor, and sulphur-deficient, consistent with off-stoichiometric growth and intrinsic defect formation, plausibly including copper interstitials, Cu-on-Sb antisites, and sulphur vacancies. These growth-dependent compositional deviations are accompanied by tunable indirect optical bandgaps of approximately 1.60 – 2.18 eV and weak visible photoluminescence governed by defect-mediated recombination. Time-resolved photoluminescence reveals bi-exponential decay behaviour with lifetimes of approximately 0.1 – 3.6 ns, with emission dominated by slower donor–acceptor pair recombination and a smaller contribution from faster trap-assisted pathways. Collectively, these results establish an explicit kinetic process–structure–defect–property relationship for AACVD-grown CAS thin films and provide a growth–structure–property framework relevant to future optimization of CAS-based optoelectronic and energy materials.
36 MATERIALS SCIENCE↗
Fast Charge Induced Phase Evolution and Element Contribution of Nickel-Rich Layered Cathode for Lithium-Ion Batteries
In nickel-rich layered cathode materials, three transition metals (TM = Ni, Co and Mn) play critical roles in Li storage performance. However, rate-dependent phase evolution and elemental contribution of nickel-rich cathode materials are not well understood, but very important for further design and development of these cathodes in high-power applications. Here, the rate-dependent phase evolution and elemental contribution of LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) cathode are investigated thoroughly by using time-resolved synchrotron-based in situ X-ray diffraction and absorption techniques. The increase of Ni content in NMC532 has been found to be the main cause of the complex structural changes, resulting in distortion of TM-O 6 octahedron and strong static vibration between TM and O coordination. It is revealed that the fast charge (10C and 30C) of NMC532 leads to intermediate Li-poor phases, shrinking of H2 phase region, and prolonged O1 phase. During high-rate charging, Co is oxidized easily in low voltage region, while Ni mainly dominates charge compensation in high voltage region. It is found that delithiation-induced local structure distortion transfers from Ni to Co sites in fast kinetic process. In conclusion, these findings provide in-depth understanding for the fast charge behavior of Ni-rich layered cathode materials and help to guide further development of advanced high-power lithium-ion batteries.
25 ENERGY STORAGE↗
Phase evolution and morphology in Cu-In-Ga sputtered precursors
The reaction of metallic precursors has become the primary method of industrial manufacturing for Cu(In,Ga)Se2. Commonly used Cu3Ga sputter targets have thus far dictated that the relative Ga composition of these precursors is Ga/(In+Ga) ≈ 0.25. Cu-In-Ga precursors are prepared with varying DC sputtering conditions and Ga compositions ranging from 0 ≤ Ga/(In+Ga) ≤ 0.75. The phase evolution and morphology of these precursors is characterized using x-ray diffraction (XRD) and scanning electron microscopy, including in situ annealing of precursors during XRD measurements. It is observed that the Ga composition of as-deposited precursors affects phase evolution with annealing. Consistent morphology changes were not observed with changing Ga, however, film morphology was controlled by adjusting In sputter conditions.
Lam, Isaac K. (ORCID:0000000198002765)↗
Resolving local structural motifs across the phase evolution of zinc titanates with computational x-ray absorption spectroscopy
Resolving the local structure motifs that characterize phase evolution as a function of composition is a key challenge in structure characterization of complex materials. Here, in this study, we combine first-principles simulations and x-ray absorption near-edge structures (XANES) analysis to gain insights into the structure evolution revealed by measurements across a combinatorial zinc titanate thin film, which was grown with smoothly varying composition over a wide range of the Ti:Zn ratio. Specifically, we propose a cluster blind-signal-separation (cBSS) method for XANES spectral analysis based on a library of the structures and spectra of representative local motifs. In addition to motifs from zinc titanate crystals, two types of Ti-defect models constructed in this study are key to the understanding of the structure characteristics in the Zn-rich region. The cBSS method makes use of both spectral clustering of the simulated site-XANES spectra library and the BSS procedure to construct high-fidelity spectral basis functions from an experimental spectral sequence. The method provides a rigorous measure of the spectral sensitivity and basis completeness. The results of the XANES analysis are corroborated with other experimental modalities, including x-ray diffraction and spectroscopic ellipsometry, to validate the cBSS method. The calculated motif weights resulting from fitting the XANES spectra with the cBSS basis probe the atomic structure characteristics of both crystalline and amorphous phases as a function of the Ti/Zn composition. The insights of the local structure motif evolution are pivotal to the understanding of the nonmonotonic trend in the optical gap, which may lead to potential applications through tuning the optical properties of zinc titanate. The workflow of the XANES spectral analysis developed in this work can be generalized to construct the structure-property relationship in a broad material space.
36 MATERIALS SCIENCE↗
Phase evolution of U-Zr system in a thermal cycling neutron diffraction experiment: as-cast U-35Zr and U-50Zr
Here, phase evolution of as-cast U-35 wt% Zr and U-50 wt% Zr alloys during thermal cycling (303–1073 K) was investigated using in-situ neutron diffraction. Analysis was performed using Rietveld crystal and microstructure refinements from time-of-flight neutron diffraction data, with a focus on evolution of lattice parameter, atom ordering, unit cell volume, and weight fractions during the thermal cycling. Disordered δ-UZr 2 and residual γ-(U,Zr) phase are retained in the field of δ of the U-Zr equilibrium phase diagram for the U-50Zr sample, and in the field between δ and α-U for the U-35Zr sample. The α phase that is present in the reported phase diagrams of U-Zr was not observed in the diffraction patterns. The evolutions of lattice parameter and unit cell volume of δ and γ are affected by both thermal expansion and chemistry.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Phase evolution and mechanical performance of an ettringite-based binder during hydrothermal aging
Little is known about the performance of ettringite-based binders in hydrothermal conditions. This investigation aims to gain insights into the phase evolution and corresponding mechanical performance of an ettringite-based binder considering crystallization pressure caused by late-reaction products. Additionally, the role of fiber reinforcement on the strength retention of the binder was investigated. When aged at an elevated temperature under water-saturated conditions, hard-burned MgO hydrated to form brucite. The precipitation and growth of the brucite crystals led to a crystallization pressure of approximately 200 MPa calculated using thermodynamic modelling. Damage was observed after 4 months of aging with cracks in the microstructure and eventually a failure at the macro scale. Ettringite remained stable at 60 °C due to the water-saturated conditions. Polypropylene fiber delayed crack propagation and thus reduced the damage caused by crystallization pressure. The fiber improved the flexural performance of composite attaining deflection-hardening behavior regardless of aging conditions.
36 MATERIALS SCIENCE↗
Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution
The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.
Brown, Paul D.↗
In-situ synchrotron X-ray investigation of phase evolution in gas atomized powder enabling manufacturing of nanoscale oxide-dispersion strengthened ferritic steels
Here, we present an investigation of Fe-14Cr-3W-0.4Y-0.4Zr-0.18Ti (wt.%) as a reduced-activation oxide-dispersion strengthened (ODS) ferritic steel, an alternative to the “14YWT” structural alloys designed for nuclear energy applications. Gas atomization reaction synthesis (GARS) was used to produce these Zr-modified powders with a non-equilibrium (metastable) phase that enable a heat treatment (delayed) route for producing nanoscale oxide-dispersion strengthening. In situ synchrotron X-ray diffraction and transmission electron microscopy were used to analyze phase evolution as a function of temperature and time, revealing formation of highly dispersed oxide nanoprecipitate phases at temperatures above those needed for powder consolidation and shaping of components. This would allow fabrication of net-shape parts using conventional powder-processing methods prior to thermal activation of a reaction producing nanocrystalline Y-(Ti, Zr)-O particles, with a size of 20 ± 7 nm. These results can inform processing of tubes, cladding, sheets, and plates for use in advanced fission and fusion reactors.
In-situ synchrotron X-ray diffraction↗
Phase evolution during reactive flash sintering of Li 6.25 Al 0.25 La 3 Zr 2 O 12 starting from a chemically prepared powder
Here, reactive flash sintering (RFS) of a chemically prepared multiphase precursor powder was performed to fabricate Li 6.25 Al 0.25 La 3 Zr 2 O 12 (Al-LLZO) ceramics. This approach allowed for obtaining single-phase dense samples in a remarkably short processing time of 30 s, at a furnace temperature of 600 °C, with an electric field of 50 V cm -1 and a current limit of 150 mA mm -2 . The ceramics display high bulk conductivity of 0.18 mS cm -1 at room temperature. Furthermore, phase evolution is studied by in-situ X-ray diffraction during: i) conventional heating and ii) RFS under current rate mode. As expected, the intermediate phases progressively dissolved into the Al-LLZO matrix by conventional heating. On the other hand, RFS promoted the growth of the intermediate La 2 Zr 2 O 7 , an effect that was overcome by the thermally driven formation of Al-LLZO at higher temperatures. The observed different reaction pathway suggests that RFS can be used for stabilizing phases that are not thermodynamically favored upon conventional heating.
36 MATERIALS SCIENCE↗
Interplay of strain and phase evolution of laser powder bed fusion Ti–6Al–4V
While additive manufacturing (AM) provides a method of producing geometrically complex and highly detailed structures, the generation of residual strain in AM processes like laser powder bed fusion (L-PBF) can negatively impact performance-enabling properties. In applications such as orthopedic implants, specific performance windows require optimized microstructures in order to obtain desirable properties from multi-phase alloys like Ti–6Al–4V. This research aims to quantify the microscale origins of strain in L-PBF manufactured Ti–6Al–4V by understanding how strain is distributed at the grain and sub-grain scale, the interplay between phase evolution and strain, and examining post-processing strain relief strategies to control these features. Model spinal cage implants were manufactured from Ti–6Al–4V powder via L-PBF and then subjected to strain relieving heat treatment cycles above and below the Ti–6Al–4V β transus as a function of time and cooling rate. Residual strain was then studied via high resolution electron backscatter diffraction (HR-EBSD), and 2D strain maps with sub-micron resolution were generated for each post-processing state. It was found that macroscale thermal strains decreased with heat treatment time, but additional contributions from phase stabilizing residual strains retained primarily in the α' grains as lattice distortive strain remained. Additionally, the retention of β phase significantly changed the strain and dislocation distribution while reducing overall residual strain. In conclusion, these results were validated and reinforced with 3D mesoscopic micromechanical modeling of strain behavior across simulated microstructures, confirming that the local lattice dilation of α’ martensite is a primary contributor of microscale strain generation and retention in L-PBF Ti–6Al–4V.
36 MATERIALS SCIENCE↗
A thermochemical database from high-throughput first-principles calculations and its application to analyzing phase evolution in AM-fabricated IN718
A comprehensive thermochemical database is constructed based on high–throughput first-principles phonon calculations of over 3000 atomic structures in limited concentrations in Ni, Fe, and Co alloys involving a total of 26 elements including Al, B, C, Cr, Cu, Hf, La, Mn, Mo, N, Nb, O, P, Re, Ru, S, Si, Ta, Ti, V, W, Y, and Zr, providing thermochemical data largely unavailable from existing experiments. Here, the database can be employed to predict the equilibrium phase compositions and fractions directly from first-principles by minimizing the chemical potential of a multicomponent system with a fixed overall chemical composition and a fixed temperature. It is applied to the additively manufactured nickel-based IN718 superalloy to analyze the phase evolution with temperature. IN718 is known for its great performance in tensile, fatigue, creep, and rupture strength, combined with easy fabrication and corrosion resistance. In particular, we successfully predicted the formation of L1 0 -FeNi, γ’-Ni 3 (Fe,Al), α-Cr, δ-Ni 3 (Nb,Mo), γ”-Ni 3 Nb, and η-Ni 3 Ti at low temperatures (below 680 K), γ’-Ni 3 Al, δ-Ni 3 Nb, γ”-Ni 3 Nb, α-Cr, and γ-Ni(Fe,Cr,Mo) at intermediate temperatures (between 680 and 1140 K), and δ-Ni 3 Nb and γ-Ni(Fe,Cr,Mo) at high temperatures (above 1140 K) in IN718. These predictions are validated by EDS mapping of compositional distributions and corresponding identifications of phase distributions. The database is expected to be a valuable source for future thermodynamic analysis and microstructure prediction of alloys involving the 26 elements.
36 MATERIALS SCIENCE↗
Deciphering phase evolution in complex metal oxide thin films via high-throughput materials synthesis and characterization
Discovery of structure-property relationships in thin film alloys of complex metal oxides enabled by high-throughput materials synthesis and characterization facilities is demonstrated here with a case-study. In this study, thin films of binary transition metal oxides (Ti–Zn) are prepared by pulsed laser deposition with continuously varying Ti:Zn ratio, creating combinatorial samples for exploration of the properties of this material family. The atomic structure and electronic properties are probed by spatially resolved techniques including x-ray absorption near edge structures (XANES) and x-ray fluorescence (XRF) at the Ti and Zn K-edge, x-ray diffraction, and spectroscopic ellipsometry. The observed properties as a function of Ti:Zn ratio are resolved into mixtures of five distinguishable phases by deploying multivariate curve resolution analysis on the XANES spectral series, under constraints set by results from the other characterization techniques. First-principles computations based on density function theory connect the observed properties of each distinct phase with structural and spectral characteristics of crystalline polymorphs of Ti–Zn oxide. Continuous tuning of the optical absorption edge as a function of Ti:Zn ratio, including the unusual observation of negative optical bowing, exemplifies a functional property of the film correlated to the phase evolution.
36 MATERIALS SCIENCE↗
Unveiling phase evolution of complex oxides toward precise solid-state synthesis
The precise synthesis of high-purity materials is crucial in accelerating materials discovery. However, the lack of theoretical understanding and practical guidance poses challenges, particularly for materials with compositional and structural complexity. Here, we propose a feasible principle toward synthesizing complex inorganic solids. This principle involves the introduction of an inducer that induces crucial intermediates, which in turn guide the synthesis pathway toward the target materials through structural templating, named inducer-facilitated assembly through structural templating (i-FAST). We validate this principle with three distinct oxides: garnet Li6.5La3Zr1.5Ta0.5O12, perovskite BaCo0.8Sn0.2O3, and pyrochlore Gd1.5La0.5Zr2O7. This structural templating approach enables synthesis along predesigned pathways, forming intermediates that are thermodynamically favored for prior formation and kinetically preferred for the final product, resulting in precisely synthesizing high-purity target materials. This study not only represents a substantial advancement in comprehending the interplay between thermodynamics/kinetics and phase evolution in complex solid synthesis but also provides an effective strategy for guiding exploratory solid-state synthesis.
Yang, Lin↗
Ultrafast and Controllable Phase Evolution by Flash Joule Heating
Flash Joule heating (FJH), an advanced material synthesis technique, has been used for the production of high-quality carbon materials. Direct current discharge through the precursors by large capacitors has successfully converted carbon-based starting materials into bulk quantities of turbostratic graphene by the FJH process. However, the formation of other carbon allotropes, such as nanodiamonds and concentric carbon materials, as well as the covalent functionalization of different carbon allotropes by the FJH process, remains challenging. Here, we report the solvent-free FJH synthesis of three different fluorinated carbon allotropes: fluorinated nanodiamonds, fluorinated turbostratic graphene and fluorinated concentric carbon. This is done by millisecond flashing of organic fluorine compounds and fluoride precursors. Spectroscopic analysis confirms the modification of the electronic states and the existence of various short-range and long-range orders in the different fluorinated carbon allotropes. As a result, the flash time-dependent relationship is further demonstrated to control the phase evolution and product compositions.
01 COAL, LIGNITE, AND PEAT↗