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At least 73 records · Page 4

Kinetics and evolution of solid-state metal dealloying in thin films with multimodal analysis

Thin-film solid-state metal dealloying (thin-film SSMD) is an emerging technique that uses self-organization to design nanostructured thin films. The resulting 3D bicontinuous nanostructures are promising for a wide range of applications, such as catalysis and energy storage. In this work, we prepared thin films by SSMD using Ti-Cu as the parent alloy and Mg as the solvent. Using a multimodal approach, we combined synchrotron X-ray spectroscopy, diffraction, and high-resolution electron-based spectroscopy and imaging to study their morphological, structural, and chemical evolution. The processing-structure relationship was analyzed as a function of parent alloy composition and dealloying temperature and time. Morphological transitions from globular, to lamellar, to bicontinuous structures, in conjunction with a ligament size evolution, were identified as functions of the parent alloy composition. The dealloying rate increased with increasing concentration of interdiffusing elements (dissolving component) in the parent alloy. The parting limit, a dealloying compositional threshold, was systematically analyzed and determined to be 30%–40%. The order of crystalline phase formation is CuMg 2 , Cu 2 Mg, and Ti; the Ti phase first shows self-reorganization during dealloying, separate from the crystallization process. The coarsening in thin-film SSMD was identified and not entirely self-similar; in addition to the increase of ligament size over time, the formation of larger globular ligaments were also observed. This work furthers our fundamental understanding of thin-film SSMD and nanostructured thin-film design, where the thermodynamic and kinetic effects differ from the bulk counterparts. The fact that dealloying and diffusion outpaces the crystallization and new phase formation also offers opportunities to utilize thin-film SSMD in certain alloy systems in which deleterious intermetallic phases need to be suppressed, that may not be possible in the bulk geometry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structural and magnetic properties of magnetostrictive Fe-Ga-Zr nanocrystalline alloy

(Fe 1–x Ga x ) 92 Zr 8 amorphous and nanocrystalline alloys with x = 0.15 to x = 0.36 were investigated to improve the magnetic softness of Galfenol-type alloys and to evaluate their magnetostrictive properties. The samples were prepared by melt spinning of arc melted ingots. The rapidly solidified ribbons were annealed at 823 K for 1 h to produce a nanocrystalline structure. X-ray Diffraction data showed that after annealing, body-centered cubic (BCC) Fe-Ga phase crystallized for x = 0.15 to x = 0.26. When x exceeded 0.26, the ribbons crystallized into BCC and a ternary intermetallic phase (i.e., ZrFe 6 Ga 6 ) which has deteriorating effect on saturation magnetization, magnetic softness and magnetostriction coefficient. The annealed ribbons’ saturation magnetization value decreases from 126 Am 2 /kg to 54 Am 2 /kg as the Ga content increased from x = 0.15 to x = 0.36. The alloy with x = 0.26 annealed at 823 K for 1 h shows a peak magnetostriction of 10 ppm with saturation magnetization of 110 Am 2 /kg and coercivity of 260 A/m.

36 MATERIALS SCIENCE↗

Dissimilar metal joining of Ti-6Al-4V and Inconel 625

The dissimilar joining of Ti-6Al-4V and Inconel 625 by using a suitable interlayer shows potential design flexibility by avoiding the brittle intermetallic phases from direct welding. These phases include NiTi , NiTi 2 , and Ni 3 Ti . The objective of this work is to facilitate laser welding of Ti-6Al-4V and Inconel 625 through a vanadium interlayer to form an intermetallic free, strong, and corrosion resistant joint. Vanadium was chosen based on binary phase diagram solubilities, literature, and theoretical CalPhaD calculations in PanDat. Laser welding was systematically explored from based on beam mode, offset, power, and scan speed. Varied parameters include laser power from 325 to 650 watts, laser scan speed from 80 to 160 in/min, and beam offset up to a ¼ of the beam diameter. Parameters were chosen based on previous dissimilar joining research and those found in the literature. Metallography, including optical and scanning electron microscopy, was used to analyze the weld chemical composition, grain structure, and defects through both the fusion and heat affected zones. The results and discussion will examine the relationship between process parameters, microstructure, and observed weld defects. Our findings will not only assess the weldability of vanadium and Inconel 625 but also establish a transferable framework for studying other dissimilar material combinations, providing valuable insights for future research in this field.

36 MATERIALS SCIENCE↗

Characterization of Ternary NiTiPt High-Temperature Shape Memory Alloys

Pt additions substituted for Ni in NiTi alloys are known to increase the transformation temperature of the alloy but only at fairly high Pt levels. However, until now only ternary compositions with a very specific stoichiometry, Ni50-xPtxTi50, have been investigated and then only to very limited extent. In order to learn about this potential high-temperature shape memory alloy system, a series of over twenty alloys along and on either side of a line of constant stoichiometry between NiTi and TiPt were arc melted, homogenized, and characterized in terms of their microstructure, transformation temperatures, and hardness. The resulting microstructures were examined by scanning electron microscopy and the phase compositions quantified by energy dispersive spectroscopy."Stoichiometric" compositions along a line of constant stoichiometry between NiTi to TiPt were essentially single phase but by any deviations from a stoichiometry of (Ni,Pt)50Ti50 resulted in the presence of at least two different intermetallic phases, depending on the overall composition of the alloy. Essentially all alloys, whether single or two-phase, still under went a martensitic transformation. It was found that the transformation temperatures were depressed with initial Pt additions but at levels greater than 10 at.% the transformation temperature increased linearly with Pt content. Also, the transformation temperatures were relatively insensitive to alloy stoichiometry within the range of alloys examined. Finally, the dependence of hardness on Pt content for a series of Ni50-xPtxTi50 alloys showed solution softening at low Pt levels, while hardening was observed in ternary alloys containing more than about 10 at.% Pt. On either side of these "stoichiometric" compositions, hardness was also found to increase significantly.

Rios, Orlando↗

Heat storage in alloy transformations

The feasibility of using metal alloys as thermal energy storage media was determined. The following major elements were studied: (1) identification of congruently transforming alloys and thermochemical property measurements; (2) development of a precise and convenient method for measuring volume change during phase transformation and thermal expansion coefficients; (3) development of a numerical modeling routine for calculating heat flow in cylindrical heat exchangers containing phase change materials; and (4) identification of materials that could be used to contain the metal alloys. Several eutectic alloys and ternary intermetallic phases were determined. A method employing X-ray absorption techniques was developed to determine the coefficients of thermal expansion of both the solid and liquid phases and the volume change during phase transformation from data obtained during one continuous experimental test. The method and apparatus are discussed and the experimental results are presented. The development of the numerical modeling method is presented and results are discussed for both salt and metal alloy phase change media.

Birchenall, C. E.↗

Mechanistic FCCI model for BISON

In this report, multi-scale simulations to develop a mechanistic model of fuel-cladding chemical interaction (FCCI) conducted under the auspices of the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program in FY23 are described. The model assumes that cladding wastage is dominated by the intermetallic phase (Fe,Cr)$_{17}$Nd$_2$, and calculates production and diffusion of Nd in the fuel, diffusion into the cladding, and formation and growth of the intermetallic wastage layer. Atomistic simulations are used to calculate diffusivity of Nd in the (Fe,Cr) system. Mesoscale simulations, informed by previous atomistic calculations, are used to determine the effective diffusivity of Nd through the fuel, accounting for empty and sodium-filled porosity within the fuel. The BISON model incorporates this data and calculates the wastage layer thickness as a function of time, assuming parabolic growth kinetics based on the best available data. The results of the new mechanistic BISON model are compared to existing assessment cases for the X447 experiment in EBR-II, and show good agreement with experimental data and the existing BISON empirical model. To improve predictions of kinetics for future work, a phase-field model that includes fuel, wastage, and cladding phases is developed. Preliminary testing indicates that the kinetics may differ significantly from the assumed parabolic growth law, suggesting direction for future improvement of the model that will allow it to be applied to other fuel designs with greater confidence.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Repurposing the θ (Al 2 Cu) phase to simultaneously increase the strength and ductility of an additively manufactured Al–Cu alloy

The Al–Cu–Mn–Zr (ACMZ) cast family of alloys offers unique properties and value propositions for higher strength, higher temperature lightweight components of future vehicles. Earlier research has demonstrated trade-offs in the selection of the alloy chemistry in which an increase in Cu content from 6 up to 9 wt% improves hot tear resistance but lowers ductility. However, a recent study has demonstrated that higher-Cu (9Cu) ACMZ fabricated with laser powder bed fusion additive manufacturing (AM) results in an increase in both ductility and strength when compared to as-aged microstructure of cast 9Cu alloys. The mechanisms of differing mechanical performance of the cast and AM ACMZ alloys are elucidated in the current paper through the utilization of in situ high energy x-ray diffraction (HEXRD) tensile testing wherein lattice strains of different phases are calculated and correlated to their stresses. The ACMZ alloys consisted of theta (θ) and theta prime (θ') phases (both Al 2 Cu in nominal composition) within an aluminum matrix. The larger micron-size θ phase which decorated the grain boundaries in 9Cu ACMZ cast alloys recorded small lattice strains, while the submicron, homogeneously distributed θ phase in the 9Cu ACMZ AM alloy recorded considerably higher lattice strains. The maximum stress reached in the θ phase for the cast 9Cu alloy was found to be ~280 MPa, which was lower than the AM 9Cu alloy which registered a maximum stress of ~1.4 GPa. These measurements indicate that delayed fracture of the finer intermetallic phases simultaneously improves the ductility and strength of AM 9Cu alloy relative to the cast 9Cu alloy, which exhibits early fracture of the larger intermetallic particles.

36 MATERIALS SCIENCE↗

Enhanced Tensile and Tear Toughness Properties of Thin-Wall Vacuum-Assisted High-Pressure Die-Cast Aural-5 Alloy by Friction Stir Processing

Steadily rising demand for glider weight reduction has driven the development of vacuum-assisted high-pressure die-cast (HPDC) Al-alloys for automotive structural components. Aural-5 is a strontium-modified HPDC alloy utilizing manganese (Mn) to reduce die soldering, eliminating detrimental needle-shaped Fe-bearing ß-phase intermetallic and improving ductility. HPDC Aural-5 contains shrinkage porosity, dendrites with Al-Si eutectic colonies, externally solidified crystals (ESCs), shear-band structure, and large second-phase particulates. Porosity, ESCs and large second-phase particles work as crack initiation sites, negatively impacting tensile properties. In this study, friction stir processing (FSP) is employed for microstructural modification of a thin-walled HPDC Aural-5 by eliminating porosity and breaking down dendrites, second-phase particles, eutectic colonies, ESCs and shear-band structures to create wrought microstructure with homogenized particle distribution. Mechanical property characterization indicates ~30% and ~35% enhancement in yield strength and ductility and associated marked effects on ~69% improvement in tear toughness according to the ASTM B871 test.

Friction stir processing, Aural-5, Strength, Tear ↗

CALPHAD-based Bayesian optimization to accelerate alloy discovery for high-temperature applications

Two crucial properties influencing the performance of high-temperature alloys are coefficient of thermal expansion (CTE) and phase constitution. It is desirable to have alloys with low CTE, which reduces CTE mismatch with the surface oxide and the likelihood of oxide spallation. Reducing the amount of brittle intermetallic phases such as Sigma (σ) enhances alloy ductility and processability. Here, we propose a multi-objective Bayesian Optimization (BO) model to simultaneously minimize CTE (at an operational temperature of 1150 °C) and T σ (temperature when the Sigma phase completely dissolves in the metal matrix), properties which are obtained from high-throughput CALculation of PHAse Diagrams (CALPHAD). The model successfully identifies several alloys with CTE ≤ 2 × 10 –5 /K and T σ ≤ 500 °C by exploring just 7% of the nickel–chromium–cobalt–aluminum–iron (Ni–Cr–Co–Al–Fe) composition space. Such multi-objective alloy design frameworks can be used to inform additive manufacturing experiments and accelerate alloy discovery for high-temperature energy applications.

36 MATERIALS SCIENCE↗

Intermediate Yb valence in the Zintl phases Yb 14 MSb 11 (M=Zn,Mn,Mg): XANES, magnetism, and heat capacity

Yb 14 Mn Sb 11 is a magnetic Zintl compound as well as being one of the best high temperature p -type thermoelectric materials. According to the Zintl formalism, which defines intermetallic phases where cations and anions are valence satisfied, this structure type is nominally made up of 14 Yb 2 + , 1 MnSb 4 9 - , 1 Sb 3 7 - , and 4 Sb 3 - atoms. When Mn is replaced by Mg or Zn, the Zintl defined motifs become 13 Yb 2 + , 1 Yb 3 + , 1 (Mg, Zn) Sb 4 10 - , 1 Sb 3 7 - , and 4 Sb 3 - . The predicted existence of Yb 3 + based on simple electron counting rules of the Zintl formalism calls the Yb valence of these compounds into question. X-ray absorption near-edge structure, magnetic susceptibility, and specific heat measurements on single crystals of the three analogs show signatures of intermediate valence Yb behavior and in particular, reveal the heavy fermion nature of Yb 14 MgSb 11 . In these isostructural compounds, Yb can exhibit a variety of electronic configurations from intermediate ( M = Zn ), mostly 2+ ( M = Mn ), to 3+ ( M = Mg ). In all cases, there is a small amount of intermediate valency at the lowest temperatures. The amount of intermediate valency is constant for M = Mn , Mg and temperature dependent for M = Zn . The evolution of the Yb valence correlated to the transport properties of these phases is highlighted. The presence of Yb in this structure type allows for fine tuning of the carrier concentration and thereby the possibility of optimized thermoelectric properties along with unique magnetic phenomena.

36 MATERIALS SCIENCE↗

Lightweight High-Temperature Alloys Based on the AlFeSi System

Automotive applications need low-cost, lightweight, high-temperature alloys to enhance efficiencies in systems such as internal combustion engines. The aluminum-iron-silicon (Al-Fe-Si) system provides an opportunity to develop such a material, as it comprises three of the lowest cost elements abundant in nature. Specifically, the $τ_{11}$-Al 4 Fe 1.7 Si (historically called $τ_{10}$) ternary intermetallic phase is a lightweight and low-cost phase with promising mechanical properties at high temperatures. However, the $τ_{11}$-Al 4 Fe 1.7 Si phase has a narrow compositional range, which should be expanded to use this alloy at a commercial scale. To increase this compositional range, equilibrium phase boundaries were expanded using alloy design strategies.

36 MATERIALS SCIENCE↗

Bulk Stoichiometry-Controlled Surface Reconstruction of Nanosized Ni−In Intermetallic Catalysts Steers Methanol Selectivity in CO2 Hydrogenation

Intermetallic compounds (IMCs) are attractive platforms for elucidating structure−catalysis relationships due to their ordered atomic structure and well-defined bulk composition. Yet, how their surfaces reconstruct under reaction conditions and how such reconstruction is governed by bulk stoichiometry remain poorly understood. Here, we show that SiO2-supported Ni−In IMCs undergo reaction-driven surface reconstruction during CO2 hydrogenation and that bulk stoichiometry can be used to steer this evolution toward methanol formation. Among the compositions examined (Ni2In1, Ni1In1, Ni2In3, and Ni1In2), Ni2In3/SiO2 exhibits the highest methanol selectivity (∼70%) and a methanol space-time yield of 652 mg·gmetal−1·h−1 at 250 °C and 30 bar. Combined structural, surface characterization, and kinetic analyses suggest that the intermetallic bulk remains largely preserved, whereas the surface departs from the stoichiometric bulk and evolves toward InOx-enriched surface domains coupled to an electron-rich Ni−In intermetallic phase. The extent of this evolution depends strongly on the bulk Ni:In stoichiometry and is most pronounced for Ni2In3/SiO2. These findings identify bulk stoichiometry as a handle for tuning the working-state surface of intermetallic catalysts and provide a basis for designing methanol synthesis catalysts through controlled surface reconstruction.

Wang, Caiqi [ORNL] (ORCID:0000000198849990)↗

Microstructure and creep properties of cast near-eutectic Al–Ce–Ni alloys

This study investigates the as-cast and aged microstructures, thermal stability, ambient temperature strengthening, and creep resistance of three ternary Al–Ce–Ni alloys (wt%): near-eutectic Al–10Ce–5Ni (with both eutectic and hypoeutectic regions), hypoeutectic Al-7.5Ce-3.75Ni (with numerous primary Al dendrites), and hypereutectic Al-12.5Ce-6.25Ni (with coarse, blocky primary Al3Ni and Al11Ce3 precipitates and some primary Al dendrites). Depending on the alloy composition and local solidification conditions, the following eutectic morphologies are found: (i) coarse Al–Ce eutectic colonies where Al 11 Ce 3 is in the form of “Chinese script”, (ii) intermingled regions of binary Al–Ce and Al–Ni eutectic colonies, with finer Al 3 Ni and Al 11 Ce 3 fibers, (iii) large ternary eutectic colonies, where the binary Al 3 Ni and Al 11 Ce 3 phases are alternating or intertwining within the individual, fine fibers (diameters of ~60–170 nm, depending on solidification rates), and (iv) ternary eutectic zones (between primary Al dendrites), where fine Al 3 Ni and Al 11 Ce 3 build up a 3D-interconnected network. The high volume fraction of intermetallic phases and extremely fine eutectic spacing/fiber diameter both contribute to high ambient strengthening (higher as-cast microhardness than binary Al–Ce or Al–Ni), and also provide enhanced creep resistance at 300 and 350 °C. Additionally, the alloys are coarsening-resistant up to 425 °C for extended periods, with a gradual decrease in microhardness. The alloys aged at 400 °C to 1050 h show fiber fragmentation and coarsening of the resulting particles, with the faster-diffusing Ni driving more rapid coarsening of the Al 3 Ni particles which engulf finer, more stable Al 11 Ce 3 particles. Severe overaging (performed at 590 °C for 24 h) leads to Al 3 Ni and Al 11 Ce 3 spheroids which remain submicron-sized in eutectic colonies, but micron-sized at colony boundary and at Al dendrite-eutectic interface. Creep resistance at 300 °C of overaged Al–10Ce–5Ni remains substantial, consistent with load-transfer based composite strengthening being an important strengthening mechanism in these alloys, making them excellent candidates for replacement of heavier steel or titanium parts operating under stress up to 300 °C.

36 MATERIALS SCIENCE↗

Microstructures in rapidly solidified niobium aluminides

The microstructures of niobium aluminides produced by chill block melt spinning were compared to those of niobium aluminides produced by conventional casting. The rapidly solidified alloys were rapidly solidified by melt spinning in an argon atmosphere, and the melt-spun ribbons were examined by optical, X-ray, and TEM techniques. Microstructures were found to range from single-phase for Nb-75 at. pct Al (NbAl3) to two phase for Nb-46 at. pct Al (NbAl3 + Nb2Al). It was found that the melt spinning of Nb-aluminides produced finer grained microstructures than those produced in induction-melted ingots or in powders produced by the rotating electrode process. Ternary additions such as Cr, Ti, and Si tended to form intermetallic phases along the grain boundaries.

Hebsur, Mohan G.↗

Phase Selection During Solidification and Solid-State Phase Transformations in an Al-10Ce-8Mn (wt pct) Alloy

In multicomponent Al-Ce alloys, and especially after additive manufacturing (AM), complex and metastable solidification microstructures are frequently observed. Here, in this research, the relationship between solidification conditions and phase selection are explored for an Al-10Ce-8Mn (wt pct) alloy using a systematic study of laser melting conditions. Three solidification modes were observed: primary Al 10 Mn 2 Ce; primary Al 20 Mn 2 Ce; and eutectic FCC Al + Al 20 Mn 2 Ce. These solidification modes were correlated to specific liquid-solid interface velocities using a simple thermal model, showing the change in primary solidification phase for low (< 6.8 × 10 −4 m/s), moderate (between 8.2 × 10 −4 and 5.9 × 10 −2 m/s) and high solidification velocities (> 6.2 x 10 −2 m/s) for the above three solidification microstructures, respectively. These results were rationalized by using interface response function (IRF) theory to describe the solidification undercooling for the possible primary intermetallic phases. The implication of the local phase selection from differing solidification conditions is summarized by a comparison of hardness which demonstrates the potential variance of Vickers hardness from 101 to 242 (VHV) by changing the laser velocity from 1 to 83 mm/s. Interestingly, on heat treatment at 400°C, the decomposition pathways of the solidification microstructure and hardness were also found to be different, thereby opening multiple pathways for spatial microstructure and property control within AM components.

Sisco, Kevin↗

Friction stir processing on a strontium modified, thin-wall, vacuum-assisted high-pressure die-cast Aural-5 alloy to improve tensile and fatigue performance

Here, this study explores the application of friction stir processing (FSP) to enhance the material properties of Sr-modified Aural-5 alloy, with a focus on improved tensile and fatigue properties. Aural-5 is a well-known vacuum-assisted high-pressure die-cast (HPDC) Al-Si7-Mg alloy used in the automotive industry to reduce vehicle weight, enhance fuel efficiency, and lower carbon emissions. This alloy modifies its material chemistry with Sr for fine fibrous networks of eutectic silicon and manganese (Mn) to reduce die soldering. It has significantly less iron (Fe) content resulting in the elimination of detrimental needle-shaped Fe-bearing ß-phase intermetallic and improving ductility. The initial microstructure of as-received HPDC Aural-5 exhibits shrinkage porosity in the middle section, a dendritic microstructure with fibrous Al-Si eutectic colonies, a shear-band structure beneath the die-wall, large dendritic externally solidified crystals (ESCs), needle-shaped Mg 2 Si phase and significant second-phase particulates. Some of those microstructural features, such as porosity, ESCs, needle-shaped Mg 2 Si phase, and large second-phase particles, serve as initiation sites for cracks under mechanical loading, resulting in adverse effects on tensile properties, particularly ductility. FSP effectively transforms the microstructure into a wrought configuration with uniform particle distribution by eliminating porosity and disintegrating dendrites, eutectic colonies, ESCs, second-phase particles, and shear-band structures. FSP-driven microstructure modification enhances yield strength and tensile ductility by ~30% and ~35%, respectively. The fatigue life of the material in a bending mode configuration (stress ratio R = 0.1) after FSP exhibits enhancements ranging from 2.0 to 3.9 times that of the original HPDC Aural-5 alloy, depending on the applied stress level.

36 MATERIALS SCIENCE↗

Collaborative or competitive phase transformation processes in an additively manufactured-maraging steel M300

Although retained austenite is present in minor amounts in as-built additively manufactured-maraging steels, its evolution during ageing is key to controlling the final microstructure. This study investigates the relationship between austenite reversion and precipitation evolution during ageing, particularly whether these processes compete or cooperate. Using Scanning/Transmission Electron Microscopy, Atom Probe Tomography and Thermo-Calc® PRISMA simulations, the presence and evolution of retained austenite, Ni 3 Ti and Fe 7 Mo 6 intermetallic phases was characterised across different ageing conditions. Experimental results revealed the presence of non-enriched austenite in the as-built condition. Nevertheless, with increasing ageing temperature, Ni and Mo segregation became evident. High-Resolution Transmission Electron Microscopy revealed that Ni 3 Ti precipitation primarily occurred within the martensitic matrix, while Fe 7 Mo 6 nucleated preferentially at the austenite-martensite interface. PRISMA simulations indicated early and rapid precipitation in solute-enriched areas (i.e., intercellular regions), with Ni 3 Ti forming prior to Fe 7 Mo 6 . Both experimental and simulation results suggested Ni diffusion controls retained austenite growth, while Ti and Mo drive Ni 3 Ti and Fe 7 Mo 6 precipitation, respectively. The evidence reported in this work supports a both collaborative and independent phase transformation mechanism, where austenite reversion and precipitation co-evolve.

42 ENGINEERING↗

Towards engineering the growth morphology of anisotropic bicrystals

Eutectic alloys, such as Pb-free Bi-Sn-Ag or Sn-Ag-Cu, are essential for their low melting points in solder joints but suffer from brittle intermetallic phases, reducing reliability. Traditional solder design relies on equilibrium phase diagrams, often neglecting the kinetic influence of crystalline anisotropy during solidification. This study hypothesizes that the energetics at the solid-solid-liquid trijunction dictate crystalline facet selection. Using the Al-Al 3 Ni alloy as a model, this project combines atomistic simulations and experimental methods to understand interfacial energies and develop predictive models. This approach aims to mitigate the negative effects of intermetallics, enhancing component reliability in electronic applications.

36 MATERIALS SCIENCE↗