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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

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↗
DOE OSTI2019

Dependence of Lamellar Eutectic Growth with Convection on Boundary Conditions and Geometric Confinement: A Phase-Field Lattice-Boltzmann Study

Simulating eutectic growth with convection is challenging because of the enormous computing demand resulting from the required domain size compared with the eutectic scale. In this study, a phase-field lattice-Boltzmann approach was employed to reproduce the eutectic growth with convection (both natural and forced). To enable and accelerate large-scale simulations, a parallel-adaptive mesh refinement algorithm was developed to combine with this numerical approach. The effects of the boundary conditions and the geometric confinement on the eutectic growth with convection were systematically investigated in the Al-Cu eutectic alloy. Results showed that both boundary conditions and the geometric confinement altered the eutectic evolution by affecting the distributions of the solute and velocity ahead of the eutectic solid/liquid interface. As the first attempt to explore the two factors on the eutectic growth with convection, our thorough investigation lays a foundation for modeling the coupled convection–solute eutectic evolution.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Effect of Eutectic Characteristics on Hot Tearing of Cast Superalloys

The occurrence of hot cracks in the blades of Ni-based superalloy turbocharger wheels is thought to be closely related to eutectic characteristics. Different alloys that are susceptible to hot tearing, namely K418, K419 and K424, were studied. SEM was used to obtain the microstructure of the alloys. DSC, isothermal solidification quenching process and EPMA were conducted to determine the relationship between the eutectic characteristics and solidification process, segregation behavior and dendrite coalescence. The results show that a large volume fraction of γ/γ′ eutectic indicates a wide-temperature solidification range and severe segregation. A large γ/γ′ eutectic size is a result of element segregation and poor dendrite coalescence. Ti is thought to promote the formation of a large isolated residual liquid pool and lead to a large eutectic size, leading to the poor coalescence behavior of the dendrites. The volume fraction and size of the γ/γ′ eutectic were considered, and a eutectic influence factor (E) was defined to evaluate the effect of eutectic characteristics on hot tearing in cast superalloys. It was found that a high E corresponds to high hot-tearing susceptibility.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Assessment of binary eutectic Ni alloys for high-temperature applications via laser remelting

It has been recently demonstrated that eutectic alloys processed by additive manufacturing have excellent high-temperature mechanical properties. We suggest that nickel-base eutectic alloys may enable new combinations of structural and functional properties. To this end, we investigate the processability, microstructure, and thermal stability of five, binary near-eutectic Ni-X (X = B, Ce, La, Y, and Zr) alloys processed via surface laser-remelting. The microstructure of all alloys contain a two-phase lamellar eutectic microstructure consisting of γ-Ni and intermetallic phases; this microstructure is significantly finer (100–200 nm lamellar spacing) in the laser-remelted alloys than in the cast substrate (0.5–1.0 µm lamellar spacing). The microhardness of the laser-remelted alloys (550–770 HV) is 35–50% higher than that of the cast alloys (370–570 HV) due to this finer eutectic spacing. An anomalous eutectic microstructure appears at the meltpool boundaries, containing globular and lamellar γ-Ni phases. The alloys contain a high volume fraction (>50 vol%) of intermetallic phase which forms a continuous network, causing brittleness. Following laser-remelting trials, the alloys showed a high density of solid-state cracks, except for the Ni-Zr alloy which processed well. During thermal exposure at 700 and 900°C for up to 500 h, the eutectic microstructure coarsens. Coarsening occurs heterogeneously and initiates at the meltpool boundaries. This process occurs more slowly in the Ni-Zr and Ni-Y alloys, and more rapidly in the remaining alloys, resulting in greater microhardness retention in the Ni-Zr and Ni-Y alloys following thermal exposure at 700°C. Thus, among the five alloys, the Ni-Zr system exhibits a good combination of high-temperature mechanical properties and processability. Here, we conclude with recommendations for future work on designing additively manufactured alloys based on these eutectic Ni systems.

Additive manufacturing↗
DOE OSTI2020

Deformation behavior of nanoscale Al–Al 2 Cu eutectics studied by in situ micropillar compression

We report deformation behavior of nanoscale laser processed Al–Al 2 Cu eutectics at room temperature is characterized through in situ micro-pillar compression testing in a scanning transmission microscope. Interlamellar spacing of Al–Al 2 Cu eutectics varies from hundreds of nanometers to 20 nm. Three different sizes of micro-pillars are fabricated in order to study the deformation behaviors of single colony and multiple colonies, corresponding to the single crystal and polycrystal respectively. For single colonies, lamellar orientations parallel, normal or inclined to the loading direction were tested. The main findings are: 1) the plasticity mechanisms strongly depend on loading orientation: buckling and kinking in the parallel-loaded eutectics, planar sliding along Al–Al 2 Cu lamellar interfaces in the incline-loaded eutectics and localized shearing in the normal-loaded eutectics. 2) the incline-loaded eutectics exhibits the lowest compression flow strength, and the normal-loaded eutectics has the highest compression flow strength. 3) with decreasing inter-lamellar spacing, the strength increases and plasticity is uniformly distributed, as opposed to shear localization. Highest compressive plasticity is observed in polycrystalline eutectics with an ensemble of lamellar orientations with ~20 nm average spacing: 17.9% at flow stress of 1.63 GPa, and degenerate, bimodal morphology: 11.1% at flow stress of 1.36 GPa.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of Cooling Rate on Nano-Eutectic Formation in Laser Surface Remelted and Rare Earth Modified Hypereutectic Al-20Si Alloys

Laser Surface Remelting (LSR) was applied to arc-melted Al-20Si-0.2Sr, Al-20Si-0.2Ce, and Al-20Si hypereutectic alloys to refine microstructures. Experiments revealed that microstructures in the melt pool varied from fully eutectic to a mixture of Al dendrites and inter-dendritic eutectic. We calculated cooling rates using the Eagar-Tsai model and correlated cooling rates with characteristic microstructures, revealing that a cooling rate on the order of 104 K/s could lead to maximized fully eutectic microstructure morphology. Due to rapid solidification, the Si composition in the LSR eutectic was measured at 18.2 wt.%, higher than the equilibrium eutectic composition of 12.6 wt.%Si. Compared to Al-20Si, Ce addition had no significant effect on the volume fraction of the fully eutectic structure but refined Si fibers to approximately 30 nm in diameter. Sr addition did not further refine the diameter of eutectic Si fibers compared to Al-20Si but increased the volume fraction of the fully eutectic microstructure morphology. The refinement ratio (φ) of the Si fiber diameter from the bottom of the melt pool to the surface for the three alloys was similar, at around 28%. The established correlation between the cooling rate and the size and morphology of the microstructure within the melt pool will enable tailoring of the microstructure in laser-processed as well as deposited alloys for high strength and plasticity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Corrosion evaluation of metal foams in eutectic molten salts for high temperature latent heat energy storage application

High-temperature Thermal Energy Storage (TES) has drawn great attention as a technology that can increase the role and profitability of micro nuclear reactors in the decentralized clean energy market. Various research needs have been proposed by Idaho National Laboratory (INL) in "the Integrated Energy Systems: 2020 Roadmap" with the goal of utilizing the high temperature of 550 degrees or more generated in the 4th generation reactor to industrial purposes from the standpoint of integrated energy systems [1]. With the recent development of the 4th generation nuclear power plant, including micro nuclear reactor, there is a great deal of interest in researching how to efficiently couple a heat source to an industrial process through thermal processing. Texas A&M University (TAMU) and INL are currently collaborating to develop a novel latent heat storage design called HITB (Heat pipe-Integrated Thermal Battery). As part of the small-scale experimental demonstration research for HITB, a study for storage medium selection was conducted at TAMU. Eutectic salts have attracted interest as high-temperature heat storage medium for HITB. Especially, chloride molten salts and fluoride molten salts are considered promising candidates due to their high melting temperature, thermal stability, and high latent heat of fusion. Since eutectic salts have poor thermal conductivity in general, it is critical to distribute materials with high thermal conductivity evenly to facilitate the charging and discharging of heat. In this study, metal foam was considered in the HITB system to overcome the poor heat transfer characteristics of eutectic salts. In order to improve heat transfer, it is necessary to study materials with high thermal conductivity, corrosion resistant to molten salts, such as fins, extended surfaces, particles, microcapsulation, or foam structure. Porous structure of copper or aluminum can increase heat transfer area, form a thermal transfer network, and increase the effective thermal conductivity of thermal storage medium [2]. Since the melting temperature is required to be at least 450? in the current HITB design, various eutectic salts are being considered. FLiNaK and FLiBe, which are famous for fluoride salts, are good candidates, but due to the sharp rise in the price of LiF recently, they are excluded for economic reasons to be applied to large-capacity thermal energy storage. On the other hand, chloride salts are very cheap and easy to obtain, have a high melting temperature, and have a high latent heat of fusion, so they are recently in the spotlight as a phase change material. However, because of the hygroscopic nature of chloride salts, HCl gas due to impurity is easy to be released and is particularly vulnerable to corrosion. Chloride eutectic salts have been tested and suggested for metal alloys that are particularly resistant to corrosion, such as SS304, SS316, Hastelloy, Inconel 625, Incoloy 800H, which has low thermal conductivity, and is very expensive [3-6]. Porous materials with high thermal conductivity such as copper and aluminum have been tested for stability in fluids such as paraffin or water as metal foam or metal fin structures, but high temperature corrosion tests were not performed on various eutectic salts yet. Therefore, this study investigated the high temperature corrosion characteristics of metal alloys, such as C10100 foam, C10100 plate, 6101 alloy foam, and SS316 plate, while immersed in the candidate eutectic salts. A total of 20 tests for SS316 coupons and 10 tests for C10100 coupons were performed to ensure the repeatability of the present measurements. Since it is difficult to completely remove the salt inside metal foam due to the complex inner structure of the metal foam, only the surface condition was observed with a microscopy and scanning electron microscopy (SEM) image, except for measuring the corrosion rate and average mass loss.

25 ENERGY STORAGE↗
DOE OSTI2023

Plastic homogeneity in nanoscale heterostructured binary and multicomponent metallic eutectics: An overview

Heterostructured materials comprised of relatively soft/hard disparate phases typically exhibit composite strengthening but lack plastic deformability at ambient temperatures. However, heterostructured systems comprised of nanoscale phases can simultaneously enhance yield strength and strain hardening, thereby promoting uniform distribution of plastic flow. In this review, the atomic-scale deformation mechanisms in model systems of eutectic alloys, Al-Al 2 Cu and Al-Si, refined to nanoscales via laser rapid solidification are discussed, and compared with literature on multi-component (high entropy) eutectics such as Ni-Al-Fe-based with Cr and/or Co additions. The nano-lamellar Al-Al 2 Cu structures exhibit unit defect mechanisms not reported in monolithic Al 2 Cu intermetallic: localized shear on {0 1 1} and shear-induced faults on {1 2 1} planes, constrained by closely-spaced dislocation arrays in Al confined by Al/Al 2 Cu interfaces. The unexpected plasticity mechanisms are enabled by slip continuity in nanoscale Al-Al 2 Cu eutectics associated with the orientation relationship and interface habit planes. In nano-fibrous Al-Si eutectic, tensile ductility at strength approaching 600 MPa is observed resulting from dislocation plasticity in the nano-Al channels and cracking in Si nanofibers. Molecular dynamics simulations show that Al dislocations easily cross-slip (screw) or climb (edge) along Al-Si interfaces, making slip transmission difficult. The propagation of nano-cracks is suppressed by surrounding strain hardening Al, retaining good ductility of the sample, in spite of lack of direct slip transmission. Finally, the critical unit mechanisms of slip transmission and interface-enabled plasticity observed in nanoscale eutectic binary systems can also explain the strength-ductility relationship in multi-component eutectics and homogeneously distributed plastic flow with increasing microstructural heterogeneity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Salt Hydrate Eutectic Mixtures for Near-ambient Thermal Energy Storage Applications

In this work, we synthesized and characterized Na2SO4.10H2O – Na2CO3.10H2O eutectic salt hydrate phase change material (PCM) using Differential Scanning Calorimetry (DSC), Attenuated total reflectance infrared spectroscopy (ATR-IR), and X-ray Diffraction (XRD) techniques. The eutectic point of the PCM mixture was predicted based on binary eutectic effect and ion exchange theory. The XRD and ATR-IR results indicate that the eutectic PCM mixture was formed based on only physical mixing without chemical interaction. Moreover, DSC results showed that the eutectic concentration is 50wt% Na2SO4.10H2O – 50wt% Na2CO3.10H2O with melting temperature of 25.18°C and melting enthalpy of 187.46 J/g. Also, 78% of melting enthalpy was recoverable after 10 melt/freeze cycles. This eutectic mixture has the potential to be used in building thermal comfort applications.

Gluesenkamp, Kyle↗
DOE OSTI2024

Highly Ordered Eutectic Mesostructures via Template‐Directed Solidification within Thermally Engineered Templates

Template-directed self-assembly of solidifying eutectics results in emergence of unique microstructures due to diffusion constraints and thermal gradients imposed by the template. Here, the importance of selecting the template material based on its conductivity to control heat transfer between the template and the solidifying eutectic, and thus the thermal gradients near the solidification front, is demonstrated. Simulations elucidate the relationship between the thermal properties of the eutectic and template and the resultant microstructure. The overarching finding is that templates with low thermal conductivities are generally advantageous for forming highly organized microstructures. When electrochemically porosified silicon pillars (thermal conductivity < 0.3 Wm −1 K −1 ) are used as the template into which an AgCl-KCl eutectic is solidified, 99% of the unit cells in the solidified structure exhibit the same pattern. In contrast, when higher thermal conductivity crystalline silicon pillars (≈100 Wm −1 K −1 ) are utilized, the expected pattern is only present in 50% of the unit cells. The thermally engineered template results in mesostructures with tunable optical properties and reflectances nearly identical to the simulated reflectances of perfect structures, indicating highly ordered patterns are formed over large areas. This work highlights the importance of controlling heat flows in template-directed self-assembly of eutectics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

An additively manufactured near-eutectic Al-Ce-Ni-Mn-Zr alloy with high creep resistance

A new additively manufactured (AM) Al-7.5Ce-4.5Ni-0.4Mn-0.7Zr (wt.%) near-eutectic alloy is reported, which shows unprecedented creep resistance up to 400 °C (a homologous temperature of 0.72). The eutectic solidification microstructure comprises ~ 27 vol% of coarsening-resistant second phase network with an ultrafine (<100 nm) inter-phase spacing. Both Mn and Zr contribute to creep resistance of the alloy. Small amount of Mn addition promotes selection of coarsening resistant phases without compromising the alloy processability. Zr not only improves hot-tearing resistance, but further enhances the second phase coarsening resistance resulting in improved creep resistance. Neutron diffraction performed during creep deformation reveals that the underlying mechanism for creep resistance in this alloy is impedance to dislocation motion stemming from the ultrafine eutectic solidification microstructure, whereas load transfer strengthening becomes less effective as the creep temperature increases. The second phase forms a continuous network in the as-fabricated condition, which is maintained during long-term creep at 300 °C. However, this network is fragmented into fine dispersoids at higher temperatures. It is proposed that the rate-limiting deformation mechanism at 300–400 °C is (i) dislocation climb for the alloy with fragmented second phase dispersoids and (ii) Orowan looping for the alloy with a continuous second phase network. In conclusion, the present design of an AM-processable multicomponent eutectic alloy with high creep resistance can be applied to other metallic systems exhibiting eutectic reactions, with expected extreme creep resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Emergence of complex-regular eutectic patterns in Al–Ge: Observations from correlative nano-imaging

Eutectic solidification exemplifies nonequilibrium pattern formation, making it a well-studied moving boundary problem. Yet the mechanisms behind the formation of complex-regular microstructures – particularly in highly anisotropic systems with a significant volume fraction of a faceted phase – remain poorly understood. Our understanding of such systems is made complicated by the nonlinear interface kinetics and unique growth dynamics characteristic of faceted phases. To address these challenges, we investigate a model Al–Ge eutectic system, where the faceted Ge phase constitutes a substantial volume fraction (~0.35) and where the two solid phases arrange into so-called “fishbone” or “feather” complex-regular patterns. Using synchrotron-based x-ray nano-imaging and nanotomography with high spatial resolution (22 nm per pixel), we capture in real-time the evolution of the solid–liquid interfaces and the resulting three-dimensional microstructures in this faceted/non-faceted eutectic system. By integrating these observations with electron backscattered diffraction, we elucidate the crystallographic biases on the solidification process and the mechanisms driving the formation of such complex-regular microstructures. These findings inform a new growth model for irregular eutectics in (near-)symmetrical phase diagrams, offering insight on advanced microstructural design and processing strategies. More broadly, we demonstrate how interfacial curvature is generated in irregular eutectic alloys and how it depends on the volume fraction of the faceted phase.

36 MATERIALS SCIENCE↗
DOE OSTI2023

3D Printed eutectic aluminum alloy has facility for site-specific properties

Additive manufacturing (AM) has the ability to print structures with site-specific properties. Existing AM approaches for site-specific properties are, however, based on complex processing-microstructure relationships in conventional alloys that were not designed for this purpose. Here, in this work, we report a straightforward approach for achieving site-specific properties that takes advantage of eutectic solidification characteristics. We demonstrate that the yield strength of a eutectic Al-Cu-Ce-Zr alloy can be tuned by varying the laser scan speed in concert with hatch spacing in laser powder bed fusion AM. A faster speed increases solidification rate resulting in finer eutectic spacing and higher strength. The hatch spacing is reduced at faster speeds to ensure overlap between melt pools which become smaller with increasing scan speed. The yield strength and its anisotropy relative to build direction are further tunable with a heat treatment. The scan speed-eutectic spacing-strength relationship is successfully applied to print a complex pattern of site-specific hardness in the alloy. The generalized principle of using AM for a eutectic alloy to create site-specific properties and anisotropy in properties is demonstrated.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modulating solvation interactions of deep eutectic solvents formed by ammonium salts and carboxylic acids through varying the molar ratio of hydrogen bond donor and acceptor

Deep eutectic solvents (DESs) have gained increasing popularity in separation science due to the fact that their physico-chemical properties can be easily fine-tuned by varying the type or ratio of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). While it is well-known that the molar ratio of HBA/HBD affects the melting point of a eutectic mixture, much less is understood regarding its effect on the magnitude of individual solvation interactions. This is largely due to the fact that established solvatochromic dye methods lack sensitivity when the HBA/HBD ratio is varied slightly in a eutectic mixture. Herein, this study is the first to measure the variation of DES solvation interactions with small changes in the molar ratio of HBA/HBD using inverse gas chromatography (IGC). Solute-solvent interactions of three different DES systems comprised of ammonium salts and organic acids were examined. The probe molecules were studied for 18 eutectic mixtures of varied HBA and HBD composition. We report DES hydrogen bond basicity, hydrogen bond acidity, and dispersive-type interactions exhibited the greatest change when the molar ratio of HBA/HBD was varied in the eutectic mixture. Results from this study demonstrate that the HBA/HBD ratio can be used to modulate the solvation characteristics for this class of DESs in separations and that the stoichiometric ratio of the HBA/HBD is important in ensuring their reproducible preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tuning and high throughput experimental screening of eutectic electrolytes with co-solvents for redox flow batteries

Eutectic solvents, with high salt concentrations and suppressed volatility, are promising alternatives to aqueous and volatile organic electrolytes for grid-scale energy storage devices such as redox flow batteries (RFBs). However, it is not known a priori which hydrogen bond acceptors and donors would form a eutectic solvent and at which compositions of these mixtures would yield desirable properties for RFBs. Specifically, the known deep eutectic solvents generally have high viscosities and low ionic conductivities, especially in the landscape of RFB electrolytes. We report a high throughput experimental (HTE) study was carried out to assess the properties of eutectic solvents based on choline chloride as the hydrogen bond acceptor and ethylene glycol and aniline as the hydrogen bond donors. In addition, water, acetonitrile, and dimethyl sulfoxide as co-solvents were examined in terms of tuning the viscosity, conductivity, and solubility of two redox-active species: methyl viologen dichloride hydrate (MVCl 2 ·H 2 O, or MV for simplicity) and 2,1,3-benzothiadiazole (BTZ) that are relevant to RFBs. The HTE framework enabled the development of a rapid and comprehensive understanding of the design of new eutectic electrolytes incorporating co-solvents to improve the physicochemical and electrochemical properties for RFBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Systematic discovery of new nano-scale metastable intermetallic eutectic phases in laser rapid solidified Aluminum-Germanium alloy

Laser surface remelting of as-cast Al-Ge eutectic alloy is shown to produce ultrafine lamellar eutectic morphology with interlamellar spacing refined up to ∼60 nm and composed of FCC Al solid solution and unusual Al x Ge y intermetallic phases that do not form during near-equilibrium solidification. The microstructures are characterized and analyzed using a combination of selected area electron diffraction, high-resolution scanning transmission electron microscopy, energy dispersive X-ray spectroscopy to obtain high-resolution elemental maps, and atomistic modeling using density functional theory followed by atomic-scale image simulation. Depending on the local solidification conditions, the crystallography of the Al x Ge y intermetallic phases in the eutectic microstructure is either monoclinic (C 2/c) or monoclinic (P 2 1 ), with high densities of defects in both cases. This is in sharp contrast to the as-cast alloys that showed nominally pure Al and Ge phases with significant solute partitioning and equilibrium FCC and diamond cubic crystal structures, respectively. Corresponding kinetic phase diagrams are proposed to interpret the evolution of nano-lamellar eutectic morphologies with equilibrium Al and metastable Al x Ge y phases, and to explain increased solid solubility in the Al phases manifested by precipitation of ultrafine clusters of Ge. Furthermore, the reasons for the formation of these metastable eutectics under laser rapid solidification are discussed from the perspective of the competitive growth criterion.

Al-Ge eutectic↗
DOE OSTI2022

Dynamics of the gold–silicon eutectic reaction studied at limited length scales using in situ $\mathrm{TEM}$ and $\mathrm{STEM}$

We report the dynamics of the gold–silicon eutectic reaction in limited dimensions were studied using in situ transmission electron microscopy and scanning transmission electron microscopy heating experiments. The phase transformation, viewed in both plan-view and cross-section of the film, occurs through a complex combination of dislocation and grain boundary motion and diffusion of silicon along gold grain boundaries, which results in a dramatic change in the microstructure of the film. The conversion observed in cross-section shows that the eutectic mixture forms at the Au–Si interface and proceeds into the Au film at a discontinuous growth rate. This complex process can lead to a variety of microstructures depending on sample geometry, heating temperature, and the ratio of gold to silicon which was found to have the largest impact on the eutectic microstructure. The eutectic morphology varied from dendrites to hollow rectangular structures to Au–Si eutectic agglomerates with increasing silicon to gold ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tuning Solvation Dynamics of Electrolytes at Their Eutectic Point Through Halide Identity

Deep eutectic solvents (DESs) are regarded as highly promising solvent systems for redox flow batteries. DESs, composed of choline halides (ChX, X = F − , Cl − , Br − , I − ) and ethylene glycol (EG), exhibit distinct physicochemical properties at their eutectic points, including halide-dependent phase behavior, viscosity, polarity, conductivity, and solvation dynamics. In this study, we investigate the effects of the halide identity on the solvation properties of ChX:EG mixtures at varying mol % of ChX salt content. The solvatochromic polarity based on ET(30) measurements indicates higher polarity for larger halides (I − > Br − ) than for smaller halides (Cl − > F − ), which exhibit larger compensating solvation shells. The ionic conductivity follows the trend of the solvent fluidity (the inverse of the viscosity), namely ChCl > ChBr > ChI > ChF, influenced by the ion mobility and solvodynamic radii. Measurements of the liquidus temperatures (T L ) reveal that the system with ChCl exhibits the deepest eutectic point (at ~20 mol % ChCl), while ChBr and ChI have shallower minima at ~10 mol % ChBr and ~3 mol % ChI, respectively. ChF does not display a eutectic transition but instead appears to readily supercool at salt concentrations above 30 mol % ChF. Consistent with the phase transition measurements, femtosecond transient absorption spectroscopy shows that in the ChCl system, the solvation dynamics become faster with an increasing salt concentration up to ~16.67 mol %, after which the dynamics slow down with further increases in the salt content. The ChF-based system exhibits similar behavior, though with slower dynamics. In contrast, the solvation dynamics of the systems containing ChBr and ChI monotonously slow down with an increasing salt concentration, in agreement with the phase transition measurements, which show that the eutectic points occur at low salt concentrations. These measurements suggest that the solvent composition and, in particular, the identity of the halide anion play a significant role in the solvation behavior of these ethylene-glycol-based DESs, offering a foundation for tuning the DES properties for specific applications.

Biochemistry & Molecular Biology↗