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At least 91 records · Page 5

Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering

We report hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow" bromide perovskites with general formula (FA) 1-x (en) x (Pb) 1-0.7x (Br) 3-0.4x (FA = formamidinium (FA + ), en = ethylenediammonium (en 2+ ), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr 3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x > 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric-field-assisted-sintering of rare-earth oxide dispersion strengthened Fe-Cr-Mo alloys

Oxide dispersion-strengthened (ODS) alloys are widely recognized for their exceptional high-temperature strength, creep resistance, and radiation tolerance, making them indispensable for advanced nuclear reactors, aerospace, and energy systems. Achieving a fine and stable dispersion of oxide nanoparticles is critical, as these particles act as strong barriers to dislocation motion and effective sinks for irradiation-induced defects, ensuring structural integrity under extreme conditions. Here, in this study, Fe–Cr–Mo-based ODS alloys were fabricated via mechanical alloying and consolidated using electric-field-assisted sintering (EFAS) with additions of Y 2 O 3 , La 2 O 3 , and CeO 2 . EFAS processing produced ultrafine-grained microstructures (average grain size <1 μm) with uniformly distributed oxide clusters (2–4 nm). Atom probe tomography revealed that La 2 O 3 -containing alloys exhibited the highest nanoparticle number density, resulting in superior tensile strength compared to yttria- and ceria-bearing counterparts. The combined effect of grain refinement and rare-earth oxide dispersion significantly enhanced mechanical performance, demonstrating the potential of EFAS for developing high-strength ferritic alloys for demanding environments such as nuclear systems.

36 - MATERIALS SCIENCE↗

Packing density optimization and recyclability of multi-modal SiC powder feedstocks in binder jet additive manufacturing

Achieving high powder packing density is critical in binder jet additive manufacturing (BJAM), as it directly influences the final part density, mechanical properties, and sintering behavior. Multi-modal powder blends, which combine particles of different sizes, have been explored as a strategy to optimize packing efficiency and minimize defects. In this study, bimodal and trimodal powder blends were obtained by mixing silicon carbide powder in three different sizes. These results show that increased powder density is achievable with bimodal powder blends but is reduced in trimodal blends, and it was found that a 13 % increase in the powder tap density was achieved using a bimodal blend of powder. The powder size distribution of the bimodal blend was measured at various stages during binder jet additive manufacturing and, no measurable powder separation occurred even after eight prints. Altogether, this study shows limited advantage to trimodal powder blends but good promise for bimodal blends for increasing printed density while maintaining reusability in the binder jet process.

Aguirre, Trevor G. [Oak Ridge National Laboratory ↗

Binder Jet Additive Manufacturing of Silicon Carbide Solar Reactor (CRADA Report)

Achieving high powder packing density is critical in binder jet additive manufacturing (BJAM), as it directly influences the final part density, mechanical properties, and sintering behavior. Multi-modal powder blends, which combine particles of different sizes, have been explored as a strategy to optimize packing efficiency and minimize defects. In this study, bimodal and trimodal powder blends were obtained by mixing silicon carbide powder in three different sizes. These results show that increased powder density is achievable with bimodal powder blends but is reduced in trimodal blends, and it was found that a 13% increase in the powder tap density was achieved using a bimodal blend of powder. The powder size distribution of the bimodal blend was measured at various stages during binder jet additive manufacturing and, no measurable powder separation occurred even after eight prints. Overall, this study shows limited advantage to trimodal powder blends but good promise for trimodal blends for increasing printed density while maintaining reusability in the binder jet process.

99 GENERAL AND MISCELLANEOUS↗

Binder jet additive manufacturing of silicon carbide solar reactor

Achieving high powder packing density is critical in binder jet additive manufacturing (BJAM), as it directly influences the final part density, mechanical properties, and sintering behavior. Multi-modal powder blends, which combine particles of different sizes, have been explored as a strategy to optimize packing efficiency and minimize defects. In this study, bimodal and trimodal powder blends were obtained by mixing silicon carbide powder in three different sizes. These results show that increased powder density is achievable with bimodal powder blends but is reduced in trimodal blends, and it was found that a 13% increase in the powder tap density was achieved using a bimodal blend of powder. The powder size distribution of the bimodal blend was measured at various stages during binder jet additive manufacturing and, no measurable powder separation occurred even after eight prints. Overall, this study shows limited advantage to trimodal powder blends but good promise for trimodal blends for increasing printed density while maintaining reusability in the binder jet process.

36 MATERIALS SCIENCE↗

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO 2 /CH 4 selectivity and a 13% increase in CO 2 permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

CO2 separation↗

VPS45 is required for both diffuse and tip growth of Arabidopsis thaliana cells

Introduction VPS45 belongs to the Sec1/Munc18 family of proteins, which interact with and regulate Qa-SNARE function during membrane fusion. We have shown previously that Arabidopsis thaliana VPS45 interacts with the SYP61/SYP41/VTI12 SNARE complex, which locates on the trans -Golgi network (TGN). It is required for SYP41 stability, and it functions in cargo trafficking to the vacuole and in cell expansion. It is also required for correct auxin distribution during gravitropism and lateral root growth. Results As vps45 knockout mutation is lethal in Arabidopsis, we identified a mutant, vps45-3 , with a point mutation in the VPS45 gene causing a serine 284-to-phenylalanine substitution. The VPS45-3 protein is stable and maintains interaction with SYP61 and SYP41. However, vps45-3 plants display severe growth defects with significantly reduced organ and cell size, similar to vps45 RNAi transgenic lines that have reduced VPS45 protein levels. Root hair and pollen tube elongation, both processes of tip growth, are highly compromised in vps45-3 . Mutant root hairs are shorter and thicker than those of wild-type plants, and are wavy. These root hairs have vacuolar defects, containing many small vacuoles, compared with WT root hairs with a single large vacuole occupying much of the cell volume. Pollen tubes were also significantly shorter in vps45-3 compared to WT. Discussion We thus show that VPS45 is essential for proper tip growth and propose that the observed vacuolar defects lead to loss of the turgor pressure needed for tip growth.

59 BASIC BIOLOGICAL SCIENCES↗

Near-Surface Layer Perforations as Precursors to Fracture in Accumulative Roll Bonding of a Multilayered Metal Composite

We use micro-computed tomography (µ-CT) to characterize the sizes, shapes, and locations of layer perforation (LP) defects in laminates of copper (Cu) and tantalum (Ta) processed by accumulative roll bonding (ARB). One—termed Cu/Ta—was processed from an initial stacking of seven alternating Cu and Ta sheets, with the exterior sheets being Cu. In the other—termed Ta/Cu—the exterior sheets are Ta. Cu/Ta remained intact during processing and exhibits an approximately uniform spatial distribution of LPs. By contrast, Ta/Cu fractured by longitudinal splitting. LPs in this latter sample are concentrated near the sample surfaces. Moreover, their density increases with decreasing distance to the fracture surface. Furthermore, these findings show that materials undergoing ARB may remain intact, despite profuse formation of LPs, provided that the LPs are uniformly distributed. However, a non-uniform distribution of LPs is correlated with longitudinal splitting.

36 MATERIALS SCIENCE↗

Synergistic effect of microstructure and defects on the initiation of fatigue cracks in additively manufactured Inconel 718

Fatigue cracks in additively manufactured (AMed) Inconel 718 (IN-718) in machined surface condition often initiate from persistent slip bands (PSBs) unlike other popular AM alloys such as 17-4 PH stainless steel or Ti-6Al-4V, where fatigue crack initiation is exclusively from volumetric defects; therefore, a competition between PSB- vs. defect- mediated crack initiation clearly exists. To shed light on the factors governing the competition, this study investigates the characteristics of cyclic strain localization, PSB formation, and crack initiation via crystal plasticity (CP) modeling of cyclic loading on polycrystalline aggregates which are then validated by experiments. In this work, a physics-based, free slip distance (FSD) dependent slip strength evolution law is proposed, which is shown to enable the CP model to simulate the heterogeneous strain distribution in IN-718. Implementing a crack initiation criterion based on strain contrast, the locations and lives for crack initiation can also be calculated. It is shown that both FSD and resolve shear stress influence the strain localization and crack initiation behaviors. The distribution of a localization parameter calculated based on the multiplication of FSD and Schmid factor within a grain is found to correlate well with the locations of PSBs. The maximum values of the localization parameters within a microstructure are shown to correlate well with the experimentally obtained crack initiation lives. The presence of volumetric defects in IN-718 generally do not impact strain localization behavior unless their size is large compared to the grain size.

42 ENGINEERING↗

Nanoscale Strain and Octahedral Tilting Removes Structural and Nonradiative Defects in 2D-Templated FAPbI 3

The halide perovskite formamidinium lead iodide (FAPbI 3 ) is a prime candidate for photovoltaics due to its excellent optoelectronic properties, but its application has been limited due to its structural instability. The large size of the FA cation results in metastability of the photoactive cubic phase and a facile degradation into thermodynamically stable hexagonal phases at room temperature. Recently, the incorporation of two-dimensional (2D) Ruddlesden-Popper halide perovskite seeds into a FAPbI 3 precursor solution was shown to template the growth of and stabilize cubic FAPbI 3 . Here, in this study, we investigate the nanoscale structural and optoelectronic mechanisms behind the observed bulk stabilization using synchrotron-based X-ray microscopies. Nanoprobe X-ray diffraction reveals 2D-templated FAPbI 3 films exhibit an average compressive strain normal to the substrate of -3.3%, 2-fold larger than that of MACl-stabilized FAPbI 3 . This compression creates locally templated regions composed of tetragonal-phase FAPbI 3 distributed nonuniformly throughout the film with fewer crystalline defects than purely cubic regions. Scanning X-ray excited optical luminescence (X-ray analog of photoluminescence) reveals that this local templating results in increased radiative recombination and red-shifted band edge and emission. Our results provide insight into the microscopic mechanism for the phase stabilization of FAPbI 3 using 2D perovskites as templates.

X-ray diffraction↗

Porosity evolution under increasing tension in wire-arc additively manufactured aluminum using in-situ micro-computed tomography and convolutional neural network

Internal defects such as porosities are often formed in additively manufactured metal components. The pores nucleate, grow, and coalesce to form cracks under loads, leading to eventual catastrophic failure. Here, in this paper, the full-field porosity evolution, including pore growth and coalescence in a wire-arc additively manufactured (WAAM) aluminum alloy cylinder under tension is observed with in-situ X-ray micro-computed tomography (μCT). The pore size distribution, density, and tensile stress are calculated from the volumetric images analyzed by a convolutional neural network (CNN) algorithm, which provides rapid analysis of 12,950 slice images from μCT volumetric images at the reference state and 13 tensile strains. The results show the quantitative evolution of the growth and coalescence of macropores under tension. A strong correlation is found between the local pore volume fraction and the true tensile stress when the tensile strain is larger than 5%.

36 MATERIALS SCIENCE↗

Microstructure and hardness evolution induced by annealing of ion irradiated LiTaO 3

We report the evolution of the microstructure and mechanical properties of low-energy heavy-ion-irradiated LiTaO 3 crystals annealed at various temperatures was investigated by transmission electron microscopy (TEM) observations and nanoindentation tests to extend the applications of irradiated LiTaO 3 crystals. Before annealing, randomly distributed voids formed in an approximately 200 nm thick region at the end of the ion irradiation range, which was attributed to preferential absorption of interstitials by the amorphous-crystalline interface. After annealing, a new directional diffusion path of defects was identified, resulting in a void string. Furthermore, void string diffusion to the free surface was also found during the annealing temperature increase process, which offers a potential application in designing custom sized-thickness exfoliation at the nanoscale. Meanwhile, two competing processes were identified during the annealing process: epitaxial recrystallization from the amorphous-crystalline interface and grain nucleation process in the amorphous region, which formed phases different from the matrix crystal structure, resulting in an interaction between them. Furthermore, the hardness of irradiated samples was also found to be affected by the annealing process; in particular, a hardness decrease induced by the interstitial Fe ions in the recrystallized region was also confirmed, which can improve the processability of samples for further application.

36 MATERIALS SCIENCE↗

Scalable Bottom-Up Synthesis of Nanoporous Hexagonal Boron Nitride ( h -BN) for Large-Area Atomically Thin Ceramic Membranes

Nanopores embedded within monolayer hexagonal boron nitride (h-BN) offer possibilities of creating atomically thin ceramic membranes with unique combinations of high permeance (atomic thinness), high selectivity (via molecular sieving), increased thermal stability, and superior chemical resistance. However, fabricating size-selective nanopores in monolayer h-BN via scalable top-down processes remains nontrivial due to its chemical inertness, and characterizing nanopore size distribution over a large area remains extremely challenging. Here, we demonstrate a facile and scalable approach of exploiting the chemical vapor deposition (CVD) process temperature to enable direct incorporation of subnanometer/nanoscale pores into the monolayer h-BN lattice, in combination with manufacturing compatible polymer casting to fabricate centimeter-scale nanoporous atomically thin ceramic membranes. We leverage diffusive transport of analytes including size-selective Ficoll sieving to characterize subnanometer-scale and nanoscale defects that manifest as pores in centimeter-scale h-BN membranes, overcoming previous limitations in large-area characterization of nanoscale defects in h-BN. Our approach opens a new frontier to advance atomically thin membranes to 2D ceramic materials, such as h-BN via facile and direct formation of nanopores, for size-selective separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗

Editorial: Functionalization of porous materials for sustainable energy applications

Global energy demands are shifting toward a more sustainable future, with the goal of achieving carbon neutrality by 2050. Emerging technologies are driving this transition. The industry, academia, government, non-profit organizations, and the broader community are collaboratively working to reduce greenhouse gas (GHG) emissions and address climate change to ensure a sustainable future. According to the International Energy Agency, in 2022, the production, transportation, and processing of oil and gas resulted in 5.1 billion tons of CO 2 -equivalent emissions, representing nearly 15% of all energy-related GHG emissions. Moreover, the end-use of oil and gas accounted for an additional 40% of emissions. The IEA’s Net Zero Emissions by 2050 Scenario calls for immediate, collective action from the industry, transportation and other stakeholders to mitigate these emissions. In this effort, the development of energy materials will play a critical role in reducing emissions. Among these, porous materials offer an innovative solution, leveraging their high surface area, adjustable pore sizes, and chemical versatility to address these pressing challenges effectively. By carefully designing their nanostructures, the architecture and properties of these materials can be tailored for specific applications. Key factors such as chemical composition, particle size, pore distribution, and surface area optimization enhance the reactivity and energy conversion efficiency. Additionally, pre- and post-functionalization processes can introduce targeted chemical properties, further improving their performance. This Research Topic explores recent advancements in energy and materials science through four scholarly papers, showcasing innovative solutions for sustainable energy technologies while providing valuable insights into the unique properties and structure of porous materials (Figure 1). Li et al. present their work on highly defective NiFeV layered triple hydroxides, highlighting enhanced electrocatalytic activity and stability for oxygen evolution reactions (OER). Kovalskii et al. contribute a mini-review on hydrogen storage using hexagonal boron nitride (h-BN) and BN-based materials, offering an insightful overview of these promising materials. Chava et al. discuss their recent achievements in ceramic electrolytes used for improvement of performance of solid-state batteries. Lastly, Li et al. review the properties of porous materials with a focus on shrinkage behavior during the drying process, shedding light on key considerations for material design.

36 MATERIALS SCIENCE↗

Algorithms for coordinate reconstruction in position-sensitive virtual Frisch-grid detectors

Arrays of position-sensitive virtual Frisch-grid (VFG) CdZnTe (CZT) detectors provide a cost-effective solution for integrating large-area arrays for gamma-ray imaging and spectroscopy. These detectors employ high-aspect ratio CZT crystals (bars) with thicknesses up to 50 mm and cross-sections of up to 10 × 10 mm 2 . Despite the long drift distances of charge carriers in such crystals, the detectors have demonstrated excellent performance, achieving energy resolutions better than 1 % full width at half maximum (FWHM) at 662 keV and 3D position resolutions finer than 1 mm. The high spatial resolution is a critical feature of these detectors, as it enables correction of response non-uniformities caused by crystal defects, which remain present even in the highest-quality CZT material. Dislocations and dislocation walls are the primary defects responsible for variations in charge carrier losses as they drift from the interaction points toward the charge-collecting electrodes. The mechanism by which these defects affect carrier transport is generally well understood. Dislocations and sub-grain boundaries act as sinks for carrier-trapping centers, primarily impurities and secondary phases such as tellurium inclusions and precipitates. Here, these regions exhibit significantly higher carrier-trapping rates, leading to variations in the μτ-products. Because the locations of these micron-sized regions are fixed within the detector volume, fluctuations in the total collected charge arise from the random distribution of interaction sites. This results in non-uniform detector responses and degradation of energy resolution. However, by measuring the interaction-site locations with sufficient precision, charge-loss variations can be accurately corrected, allowing recovery of nearly intrinsic energy resolution.

47 OTHER INSTRUMENTATION↗

Role of Computational Parameters on Predicting Self-Consistent Residual Stress and Distortion during Wire Arc Additive Manufacturing

Production of three-dimensional metallic parts through integration of an articulated robot and gas metal arc welding, also known as wire arc additive manufacturing (WAAM), can produce large-scale components with moderate geometrical complexity. This technology is particularly appealing due to its high deposition rates, scalability, and cost-effective feedstock compared to other AM processes. Despite its advantages, WAAM adoption is hindered by challenges in ensuring geometric conformity without extensive distortion, defect-free structures, and consistent mechanical properties. Finite element analysis (FEA) is often used to address the challenge of geometrical conformity. As the size of parts increases, the best practices for mesh size and temporal resolution known in the literature become computationally unviable. This research examined the effects of mesh and time-step resolutions during transient FEA of a large-scale (248 layers) metallic part. The impact of computational parameters on the thermal history, displacement, and residual stress distributions were evaluated. The results showed that predicted distortion was consistent across resolutions, while time-step length significantly affected predicted thermal history, and mesh size influenced residual stress distributions. To investigate this relationship further, directionally biased meshes were considered and analyzed. The results indicated that increasing mesh resolution perpendicular to the welding path yielded stress predictions that aligned closely with higher-resolution models while offering substantial computational savings. In conclusion, the significances of this research are related to verification and validation of WAAM models for widespread industrial adoption and pragmatic guidelines for optimizing computation parameters for balancing computational efficiency and predictive accuracy of residual stress and distortion.

Solsbee, Brandon [Univ. of Tennessee, Knoxville, T↗

Time at Temperature Experiments on Neutron Irradiated Zircaloy-2 using Conventional & Flash DSC

Dryout events in Boiling Water Reactors (BWRs) are currently treated by NRC regulations as automatic disqualification for continued fuel rod operation, even though this criterion does not account for the rate or duration of power increases, associated changes in material behavior, or the possibility of rewetting. Operational history from Anticipated Operational Occurrences (AOOs) shows that short, transient power excursions often demand only modest heat removal, and industry experience suggests that fuel can briefly enter dryout yet return to safe, stable operation. The lack of detailed understanding of the material response during such events motivates the present series of experiments. This study uses unique and innovative methods to investigate microstructural evolution in irradiated Zircaloy-2 exposed to high temperatures in inert environments. Differential Scanning Calorimetry (DSC) and FlashDSC are combined to build a comprehensive experimental framework capable of identifying the a–ß phase transformation in zirconium and examining defect annealing under steep thermal gradients. FlashDSC enables rapid heating and cooling of Focused Ion Beam (FIB)–prepared large-area lift-outs (LALOs) of irradiated Zircaloy-2 at rates of 1,000 K/s to peak temperatures of 600°C, 750°C, and 900°C. The goal is to determine whether these conditions produce measurable microstructural changes that could influence cladding performance in typical BWR environments. Microstructural characterization includes quantifying dislocation density and assessing secondary phase particle (SPP) size and distribution using Transmission Electron Microscopy (TEM). Ongoing analysis, such as diffraction pattern indexing and 4D STEM processing, will further refine these observations.

36 - MATERIALS SCIENCE↗