skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Complexity and evolution of a three-phase eutectic during coarsening uncovered by 4D nano-imaging
We investigate the coarsening dynamics of the three-phase eutectic Al-Ag2Al-Al2Cu at 723 K via in situ transmission X-ray nano-tomography. Unlike previous investigations that compared observations between different samples annealed for different times, our three-dimensional measurement shows at nanoscale resolution the microstructural changes occurring in the same field-of-view, enabling new insight on the capillary-driven evolution of a ladder-like pattern. With the aid of a new reconstruction algorithm and machine learning segmentation, we trace the interfaces of the eutectic and observe significant structural changes within 4 hr. of aging. Even though the average length-scales of the eutectic solids follow a temporal power law, the microstructure is not self-similar. Instead, it evolves (in part) through the coalescence of neighboring Ag2Al solids at the expense of the intervening Al2Cu. By combining our X-ray data with electron diffraction to identify the common planes at the interphase boundaries, we show that coalescence leads to a decrease in lattice misfit, and hence, interfacial energy. At longer times, the interphase boundaries with low misfit compete for surface area, resulting in a ‘locking’ of the interfacial shape.  more » « less
Award ID(s):
2203378
PAR ID:
10529572
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Acta Materialia
Volume:
266
ISSN:
1359-6454
Page Range / eLocation ID:
119684
Subject(s) / Keyword(s):
Coarsening Ostwald ripening Solid-state transformation Multi-phase eutectics Real-time imaging X-ray nano-tomography Crystallography
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Investigating how solid matter behaves at enormous pressures, such as those found in the deep interiors of giant planets, is a great experimental challenge. Over the past decade, computational predictions have revealed that compression to terapascal pressures may bring about counter-intuitive changes in the structure and bonding of solids as quantum mechanical forces grow in influence 1–6 . Although this behaviour has been observed at modest pressures in the highly compressible light alkali metals 7,8 , it has not been established whether it is commonplace among high-pressure solids more broadly. We used shaped laser pulses at the National Ignition Facility to compress elemental Mg up to 1.3 TPa, which is approximately four times the pressure at the Earth’s core. By directly probing the crystal structure using nanosecond-duration X-ray diffraction, we found that Mg changes its crystal structure several times with non-close-packed phases emerging at the highest pressures. Our results demonstrate that phase transformations of extremely condensed matter, previously only accessible through theoretical calculations, can now be experimentally explored. 
    more » « less
  2. Abstract Geopolymers, as a potentially environmentally friendly alternative to Portland cement, are increasingly attracting attention in the construction industry. Various methods have been applied for customizing the properties of geopolymers and improving their commercial viability. One of the promising methods for refining the properties of geopolymers such as their toughness is the use of short fibers. The effectiveness of a high‐strength short fiber in the geopolymer matrix is largely dependent on the interfacial bonding between the fiber and its surrounding matrix. While the importance of this interfacial chemistry is highlighted in the literature, the characteristics of this bonding structure have not been fully understood. In this paper, we aim to investigate the bonding mechanism between the carbon fiber and metakaolin‐based geopolymer matrix. For the first time, the existence and nature of the chemical bonding at the interfacial region (interphase) between carbon fiber and geopolymer matrix has been revealed. X‐ray pair distribution function computed tomography (PDF‐CT), field emission‐scanning electron microscopy imaging, and nanoindentation techniques are employed to discern the chemo‐mechanical properties of the interphase. PDF‐CT results show the emergence of a new atom–atom correlation at the interfacial region (around 1.82 Å). This correlation is a characteristic of interfacial bonding between the fiber and its surrounding matrix, where the existence of chemical linkages (potentiallyVAl‐O‐C) between fibers and the matrix contributes to the adhesion between the two constituents making up the composite. Due to such chemical bonding, the nanomechanical properties of the interfacial region fall between that of the carbon fiber and geopolymer. The combination of advanced techniques is proved useful for enhancing our understanding of the interfacial chemistry between fibers and the binding matrix. This level of knowledge facilitates the engineering of composite systems through the manipulation of their nanostructure. 
    more » « less
  3. Hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) has recently been shown to be a promising solid state organic ionic plastic crystal with potential application in advanced alkali metal batteries. This study provides a detailed exploration of the structural and dynamic behavior of [HMG][FSI] mixtures with the sodium salt NaFSI across the whole composition range from 0 to 100 mol%. All mixtures are solids at room temperature. A combination of differential scanning calorimetry (DSC), synchrotron X-ray diffraction (SXRD) and multinuclear solid state NMR spectroscopy is employed to identify a partial phase diagram. The 25 mol% NaFSI/75 mol% [HMG][FSI] composition presents as the eutectic composition with the eutectic transition temperature at 44 °C. Both DSC and SXRD strongly support the formation of a new compound near 50 mol% NaFSI. Interestingly, the 53 mol% NaFSI [HMG][FSI] composition was consistently found to display features of a pure compound whereas the 50 mol% materials always showed a second phase. Many of the compositions examined showed unusual metastable behaviour. Moreover, the ion dynamics as determined by NMR, indicate that the Na + and FSI − anions are signifcantly more mobile than the HMG cation in the liquid state (including the metastable state) for these materials. 
    more » « less
  4. Abstract Two commonly used ice models that are constructed using glacial isostatic adjustment (GIA) modeling are the ICE‐6G and ANU ice models. In this study, we examined the relationships among mantle viscosity, ice models and relative sea level (RSL) data through an analytic GIA model. In general, almost all the pairs of RSL data sets and ice models we considered appear to be consistent with a mantle viscosity structure with a factor of 10–20 viscosity increase from the upper to lower mantles. By using the GIA model with the viscosity structure that produces a minimum model‐data misfit, we constructed the temporal and spatial distributions of misfit (i.e., misfit maps) to different RSL data sets, for both the ICE‐6G and ANU ice models. While the misfit maps at different times clearly show that more observations are desired to constrain ice models, we propose that the spatial and temporal misfit maps should be used to revise the existing ice models to further improve the fit to RSL data. In our initial proof of concept attempts to modify ICE‐6G by adding more ice to it, the three modified ICE‐6G ice models we considered all significantly improve the fit to the far‐field RSL data, although additional effort is needed to reduce misfit to near field RSL data. Finally, we emphasize that RSL at different far‐field sites may differ by up to ∼25 m at the Last Glacial Maximum (LGM) (∼26 ka), suggesting the need for a sufficiently large number of far‐field RSL data in determining the total melt ice volume since the LGM. 
    more » « less
  5. Interphases formed at battery electrodes are key to enabling energy dense charge storage by acting as protection layers and gatekeeping ion flux into and out of the electrodes. However, our current understanding of these structures and how to control their properties is still limited due to their heterogenous structure, dynamic nature, and lack of analytical techniques to probe their electronic and ionic properties in situ . In this study, we used a multi-functional scanning electrochemical microscopy (SECM) technique based on an amperometric ion-selective mercury disc-well (HgDW) probe for spatially-resolving changes in interfacial Li + during solid electrolyte interphase (SEI) formation and for tracking its relationship to the electronic passivation of the interphase. We focused on multi-layer graphene (MLG) as a model graphitic system and developed a method for ion-flux mapping based on pulsing the substrate at multiple potentials with distinct behavior ( e.g. insertion–deinsertion). By using a pulsed protocol, we captured the localized uptake of Li + at the forming SEI and during intercalation, creating activity maps along the edge of the MLG electrode. On the other hand, a redox probe showed passivation by the interphase at the same locations, thus enabling correlations between ion and electron transfer. Our analytical method provided direct insight into the interphase formation process and could be used for evaluating dynamic interfacial phenomena and improving future energy storage technologies. 
    more » « less