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Uncertainty Quantification for Equation of State using Heterogeneous Data Sources
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Separating Physically Distinct Mechanisms in Complex Infrared Plasmonic Nanostructures via Machine Learning Enhanced Electron Energy Loss Spectroscopy
Electron energy loss spectroscopy (EELS) enables direct exploration of plasmonic phenomena at the nanometer level. To isolate individual plasmon modes, linear unmixing methods can be used to separate different physical mechanisms, but in larger and more complex systems the interpretability of the components becomes uncertain. Here, infrared plasmonic resonances in self-assembled heterogeneous monolayer films of doped-semiconductor nanoparticles are examined beyond linear unmixing techniques, and both supervised and unsupervised machine-learning-based analyses of hyperspectral EELS datasets are demonstrated. Additionally, in the supervised approach, a human operator labels a small number of pixels in the hyperspectral dataset corresponding to features of interest which are then propagated across the entire dataset. In the unsupervised approach, non-linear autoencoders are used to create a highly-reduced latent-space representation of the dataset, within which insight into the relevant physics can be gleaned from straightforward distance metrics that do not depend on operator input and bias. The advantage of these approaches is that the labeling separates physical mechanisms without altering the data, enabling robust analyses of the influence of heterogeneities in mesoscale complex systems.
Modeling Microstructural Effects on Heterogeneous Temperature Fields within Polycrystalline Explosives
The paper addresses the role of crystal anisotropy on the evolution of heterogeneous temperature fields in plastic-bonded explosives (PBXs) under conditions of weak shock. The modeling approach is based on simplified idealizations of PBX microstructure including RDX grains and estane binder regions subjected to velocity boundary conditions representative of impact conditions in situ. The constitutive description of the microstructure constituents includes a dislocation-based, anisotropic, single crystal plasticity model for the explosive grains and a linear viscoelastic model to represent the estane binder. Large suites of simulations were used to systematically study the correlation in heating of the grains with local wave dynamics, crystal orientation, and the microstructural neighborhood. These correlations were identified through the selection of characteristics of crystal anisotropy including oriented wave speeds and Taylor factor. A key observation is that the wave dispersion within a certain distance from the impact interface plays a dominant role in the temperature field. Beyond this distance, individual crystal orientations play a more dominant role, but cannot entirely account for the observed heterogeneity without consideration of the local microstructure neighborhood.
Ramsey envelope modulation in NV diamond magnetometry
Nitrogen-vacancy (NV) spin ensembles in diamond provide an advanced magnetic sensing platform, with applications in both the physical and life sciences. The development of isotopically engineered 15 NV diamond offers advantages over naturally occurring 14 NV for magnetometry, due to its simpler hyperfine structure. However, for sensing modalities requiring a bias magnetic field not aligned with the sensing NV axis, the absence of a quadrupole moment in the 15 N nuclear spin leads to pronounced envelope modulation effects in time-dependent measurements of 15 NV spin evolution. While such behavior in spin echo experiments are well studied, analogous effects in Ramsey measurements and the implications for magnetometry remain underexplored. Here, we derive the modulated 15 NV Ramsey response to a misaligned bias field, using a simple vector description of the effective magnetic field on the nuclear spin. The predicted modulation properties are then compared to experimental results, revealing significant magnetic sensitivity loss if unaddressed. We demonstrate that double-quantum coherences of the NV S=1 electronic spin states dramatically suppress these envelope modulations, while additionally proving resilient to other parasitic effects such as strain heterogeneity and temperature shifts.
Activity of Silica-Alumina for the Conversion of Polyethylene into Tunable Aromatics Below Pyrolytic Temperatures
Plastic waste is a mounting problem that lacks global strategy, largely due to inadequate recycling capabilities. One alternative gaining traction in the heterogeneous catalysis community is the upcycling of polyolefins into value-added products, such as hydrogen-free conversion to alkylaromatic compounds over Pt/Al 2 O 3 . Here, we examined the activity of nominally metal-free, mesoporous silica-alumina mixed oxide materials (SiO 2 –Al 2 O 3 ) for the conversion of polyethylene into aromatic compounds at temperatures of and below 280 °C. Yields with the silica-alumina catalysts are comparable to those obtained over Pt(1 wt %)/Al 2 O 3 under identical conditions, and product selectivity can be tuned by altering reaction conditions or the acid site density of the SiO 2 –Al 2 O 3 . Notably, the fraction of polyaromatic products increases with the Brønsted acid site density of the catalyst, as does the degree of polymer deconstruction. These catalysts can be reused without regeneration, and their activity improves with each recycling event, producing soluble product yields up to 83%. Preliminary work on the mechanism of the reaction suggests that acid sites are responsible for initiating depolymerization and aromatization reactions, in analogy to previous work in the literature. Finally, this work showcases the activity of SiO 2 –Al 2 O 3 for polyolefin deconstruction/aromatization at subpyrolytic temperatures and lays the foundation for future studies involving solid acid and bifunctional catalysts.
Electrochemistry at Back-Gated, Ultrathin ZnO Electrodes: Field-Effect Modulation of Heterogeneous Electron Transfer Rate Constants by 30× with Enhanced Gate Capacitance
We report steady-state voltammetry of outer-sphere redox species at back-gated ultrathin ZnO working electrodes in order to determine electron transfer rate constants k ET as a function of independently-controlled gate bias, V G . We demonstrate that k ET can be modulated as much as 30-fold by application of V G ≤ 8 V. Key to this demonstration was integrating the ultrathin (5 nm) ZnO on a high dielectric constant (k) insulator, HfO 2 (30 nm), which was grown on a Pd metal gate. The high-k HfO 2 dramatically decreased the required V G values and increased the gate-induced charge in ZnO compared to previous studies. Importantly, the enhanced gating power of the Pd/HfO 2 /ZnO stack meant it was possible to observe a non-monotonic dependence of k ET on V G , which reflects the inherent density of redox acceptor states in solution. Furthermore, this work adds to the growing body of literature demonstrating that electrochemical kinetics (i.e., rate constants and overpotentials) at ultrathin working electrodes can be tuned by V G , independent of the conventional electrochemical working electrode potential.
Investigation of breakaway corrosion observed during oxide growth in pure and low alloying element content Zr exposed in water at 360°C
The addition of small concentrations of alloying elements to pure zirconium can prevent nuclear fuel cladding material from undergoing unstable oxide growth in aqueous environments at light water reactor operating temperatures. The role of alloying elements in stabilizing the oxide growth is examined in this paper, to better understand the oxide growth stabilization mechanism. To this end, a set of initial, short-duration corrosion experiments were performed, followed by oxide layer characterization. Specifically, ten model Zr alloys were selected to test the effect of small alloying additions on the alloy corrosion rate and corrosion breakaway. Additionally, these alloys were corrosion tested in pure water in an autoclave at 360°C for up to 70 days. The alloys included crystal bar Zr, sponge Zr, and model alloys with small concentrations of Sn, Fe, and Cr. After testing, the alloys were characterized using scanning electron microscopy (SEM) and synchrotron µ-X-ray fluorescence (µXRF) to study how the structure of the oxide and alloying element distribution related to unstable oxide growth. Initial results in the 360°C water environment showed breakaway oxidation may be caused by unstable oxide growth due to heterogeneous distribution of the alloying elements. Heterogeneous distribution of alloying elements was correlated to the occurrence of unstable oxide growth (either nodule-like, grain boundary penetration, or differential grain-to-grain growth). It is possible that this heterogeneity, made possible by low alloying element content, can cause breakaway corrosion, but further study is warranted.
Mars Atmospheric Oxidant Sensor (MAOS): An In-Situ Heterogeneous Chemistry Analysis
We describe a chemometric array sensor, the Mars Atmospheric Oxidant Sensor (MAOS, pronounced "mouse '') that is designed measure the oxidation rate of thin films on the martian surface. We select films that are sensitive to particular types of oxidants, that represent key elements in the martian soil, or that emulate prebiotic materials. Concern that naturally arising martian oxidants may have destroyed evidence of ancient life on Mars was raised by the Viking mission in the 1970's. The possibility that oxidants may limit the viability of biologica1 habitats is particularly timely in light of recent suggestions of contemporary flowing water on Mars. By controlling the temperature of the films, as well as their exposure to dust and ultraviolet light, MAOS will discriminate among leading hypotheses for oxidant production. MAOS weighs 55 grams, fits in a 6 x 7 x 2 cm envelope, and uses 250 mW power. Much of the enabling technology was developed for the MOx experiment, lost on the Russian Mars '96 mission.
Thermal cycling-driven microstructural changes of eutectic Al–Si phase change materials in SS304 containers revealed by multi-modal imaging
Aluminum-based Al–Si alloys are widely used as phase change materials (PCMs) in thermal energy storage (TES) systems owing to their high volumetric latent heat and superior thermal conductivity. However, their long-term reliability is limited by degradation processes that remain insufficiently understood. In this work, we employ a multimodal, correlative characterization framework to systematically resolve the degradation behavior of eutectic Al–Si PCMs in contact with SS304 containers under repeated thermal cycling. By integrating high-resolution electron microscopy, three-dimensional X-ray fluorescence (3D XRF) imaging, and differential scanning calorimetry (DSC), we directly link spatially resolved compositional and microstructural evolution to changes in thermophysical properties. The correlative analysis reveals that elemental leaching of Fe, Cr, and Ni from the stainless-steel container into the PCM drives the formation of intermetallic compounds (IMCs) both at the interface and within the bulk PCM, leading to pronounced compositional heterogeneity. These interfacial reactions and diffusion-induced transformations progressively destabilize the Al–Si eutectic, reducing the effective phase-transforming fraction. Consistent with these observations, DSC measurements show a decrease in melting temperature and latent heat of fusion with thermal cycling. These results underscore the critical influence of interfacial reactions and material compatibility on the stability, durability, and overall performance of Al–Si-based TES systems.
In Situ Nanoscale Dynamics Imaging in a Proton‐Conducting Solid Oxide for Protonic Ceramic Fuel Cells
Abstract Hydrogen fuel cells and electrolyzers operating below 600 °C, ideally below 400 °C, are essential components in the clean energy transition. Yttrium‐doped barium zirconate BaZr 0.8 Y 0.2 O 3‐d (BZY) has attracted a lot of attention as a proton‐conducting solid oxide for electrochemical devices due to its high chemical stability and proton conductivity in the desired temperature range. Grain interfaces and topological defects modulate bulk proton conductivity and hydration, especially at low temperatures. Therefore, understanding the nanoscale crystal structure dynamics in situ is crucial to achieving high proton transport, material stability, and extending the operating range of proton‐conducting solid oxides. Here, Bragg coherent X‐ray diffractive imaging is applied to investigate in situ and in 3D nanoscale dynamics in BZY during hydration over 40 h at 200 °C, in the low‐temperature range. An unexpected activity of topological defects and subsequent cracking is found on a nanoscale covered by the macroscale stability. The rearrangements in structure correlate with emergent regions of different lattice constants, suggesting heterogeneous hydration. The results highlight the extent and impact of nanoscale processes in proton‐conducting solid oxides, informing future development of low‐temperature protonic ceramic electrochemical cells.
Multi-Step Crystallization of Self-Organized Spiral Eutectics
A method for the solidification of metallic alloys involving spiral self-organization is presented as a new strategy for producing large-area chiral patterns with emergent structural and optical properties, with attention to the underlying mechanism and dynamics. This study reports the discovery of a new growth mode for metastable, two-phase spiral patterns from a liquid metal. Crystallization proceeds via a non-classical, two-step pathway consisting of the initial formation of a polytetrahedral seed crystal, followed by ordering of two solid phases that nucleate heterogeneously on the seed and grow in a strongly coupled fashion. Crystallographic defects within the seed provide a template for spiral self-organization. These observations demonstrate the ubiquity of defect-mediated growth in multi-phase materials and establish a pathway toward bottom-up synthesis of chiral materials with an inter-phase spacing comparable to the wavelength of infrared light. Given that liquids often possess polytetrahedral short-range order, our results are applicable to many systems undergoing multi-step crystallization.
Tailoring Cu-Zr gradient nanoglass structures: Influence of nanoparticle size and cooling rates on glass-glass interfaces
The study of gradient nanoglasses (GNGs) has gained attention due to their unique mechanical properties and potential applications in advanced materials. This study employs molecular dynamics simulations to synthesize a GNG using Cu-Zr metallic glass nanoparticles (NPs) sized from 3 to 15 nm. The NPs were produced by melting and quenching metallic clusters at a relatively slow quench rate of 10 9 K/s. The synthesis of GNG is elucidated along with the characterization of its heterogeneous metallic glass nanostructure. A seamless GNG structure is formed through cold compression of Cu 64 Zr 36 amorphous NPs of varying sizes. The influence of NP size on the GNG structure is investigated, utilizing deeply relaxed NPs, which exhibit a characteristic Cu segregation pattern on their surfaces. The results highlight an increase in structural heterogeneity due to heterogeneous mass transport and the development of local composition and density variations caused by Cu segregation at glass-glass interfaces (GGIs). A reduction in NP size is correlated with decreased Cu atomic displacements and local density at GGIs, suggesting that larger NPs may produce stronger GGIs. This research presents a novel methodology for synthesizing heterogeneous metallic glasses, demonstrating the capacity to control and customize nanostructure heterogeneity through the manipulation of NP sizes and cooling rates. Furthermore, these findings enhance our understanding of structural evolution during nanoglass synthesis and lay the foundation for further exploration in nanomaterial synthesis and characterization.
Identifying multiple synergistic factors on the susceptibility to stress relaxation cracking in variously heat-treated weldments
The 347H austenitic stainless steel has been widely used for pressure vessels and pipeline (PVP) applications due to its excellent creep and corrosion resistance, which fit ideally to the harsh conditions in petrochemical industries, fossil fuel or nuclear power plants, and modern energy storages. However, a failure mode has been commonly observed with cracks emerging at the heat affected zone (HAZ) of weldments during post-weld heat treatment (PWHT) or under intermediate to high temperature service conditions. This phenomenon is termed as Stress Relaxation Cracking (SRC) since the purpose of PWHT is to relieve the welding-induced residual stress fields, or as Stress Age Cracking (SAC) if failure happens during service. A leading literature explanation of this failure suggests that the residual stress relaxation and the precipitation dissolution and/or re-precipitation occur in the same temperature range, which can lead to locally high strains and thus to crack at the grain boundaries. Since in situ spatial measurements of residual stress fields, microstructural evolution, and failure processes are nearly infeasible, this work recourses to a micromechanical finite element framework that models the high temperature failure as the nucleation and growth of grain boundary cavities, whereas various parameters such as thermomechanical loading history and its evolution, the competition of grain-interior dislocation creep and grain-boundary diffusion in failure lifetime, and microstructural heterogeneities (such as the precipitate free zone near grain boundaries) can be quantitatively incorporated. It can be concluded from these microstructure-explicit simulations that an accurate knowledge of residual stress evolution and a carefully calibrated set of material constitutive parameters are the essential prerequisites for lifetime predictions. The understanding of individual governing factors also leads to a mechanistic interpretation of the observed SRC susceptibility C-curves. In conclusion, these results suggest that the criticality of residual stress evolution, but not the precipitation-induced local strains, be the leading factor for SRC.
Heterogeneous field response of hierarchical polar laminates in relaxor ferroelectrics
Understanding the microscopic origin of the superior electromechanical response in relaxor ferroelectrics requires knowledge not only of the atomic-scale formation of polar nanodomains (PNDs) but also the rules governing the arrangements and stimulated response of PNDs over longer distances. Using x-ray coherent nanodiffraction, we show the staggered self-assembly of PNDs into unidirectional mesostructures that we refer to as polar laminates in the relaxor ferroelectric 0.68PbMg 1/3 Nb 2/3 O 3 -0.32PbTiO 3 (PMN-0.32PT). Here, we reveal the highly heterogeneous electric-field–driven responses of intra- and interlaminate PNDs and establish their correlation with the local strain and the nature of the PND walls. Our observations highlight the critical role of hierarchical lattice organizations on macroscopic material properties and provide guiding principles for the understanding and design of relaxors and a wide range of quantum and functional materials.
Simulation of emergent compaction banding fronts caused by frictional boundaries
This study examines the role of boundary friction in promoting heterogeneous compaction in soft rock specimens loaded at high confining pressure outside the domain of compaction localisation. An elastoplastic constitutive model characterised by tunable hardening/softening behaviour is used to conduct the analyses. Finite-element simulations suggest that material instability is a non-necessary condition for the emergence of compaction fronts. Such fronts propagated as a result of a severe deviation in the local responses induced by frictional constraints. Overall, these findings suggest that boundary effects can bias the assessment of the extent of the compaction localisation domain. Experimental countermeasures and informed model calibration procedures are therefore necessary to minimise such bias and enable more accurate predictions of soft rock compaction.
Nonlinear mesomechanics of composites with periodic microstructure
This work is concerned with modeling the mechanical deformation or constitutive behavior of composites comprised of a periodic microstructure under small displacement conditions at elevated temperature. A mesomechanics approach is adopted which relates the microimechanical behavior of the heterogeneous composite with its in-service macroscopic behavior. Two different methods, one based on a Fourier series approach and the other on a Green's function approach, are used in modeling the micromechanical behavior of the composite material. Although the constitutive formulations are based on a micromechanical approach, it should be stressed that the resulting equations are volume averaged to produce overall effective constitutive relations which relate the bulk, volume averaged, stress increment to the bulk, volume averaged, strain increment. As such, they are macromodels which can be used directly in nonlinear finite element programs such as MARC, ANSYS and ABAQUS or in boundary element programs such as BEST3D. In developing the volume averaged or efective macromodels from the micromechanical models, both approaches will require the evaluation of volume integrals containing the spatially varying strain distributions throughout the composite material. By assuming that the strain distributions are spatially constant within each constituent phase-or within a given subvolume within each constituent phase-of the composite material, the volume integrals can be obtained in closed form. This simplified micromodel can then be volume averaged to obtain an effective macromodel suitable for use in the MARC, ANSYS and ABAQUS nonlinear finite element programs via user constitutive subroutines such as HYPELA and CMUSER. This effective macromodel can be used in a nonlinear finite element structural analysis to obtain the strain-temperature history at those points in the structure where thermomechanical cracking and damage are expected to occur, the so called damage critical points of the structure.