Experimental Observations Research Articles

The capacity of disclinated non-equilibrium GBs to accommodate point defects in tungsten

Experimental observations reveal that disclinated non-equilibrium grain boundaries (GBs) exist extensively in polycrystalline metals; however, the interaction between these GBs and irradiation-induced point defects is rarely reported. In the present work, Molecular statics simulation was used to evaluate the capacity of disclinated non-equilibrium GBs to accommodate point defects in tungsten. Simulation results showed that disclinated non-equilibrium GBs are more efficient sinks for point defects than their equilibrium counterparts because of long-range stress field around them. Continuous segregation of point defects will change the structure of the disclinated non-equilibrium GBs and leads to the GBs tending to relax to equilibrium state. According to theoretical calculation, the disclinated non-equilibrium GBs can absorb a large number of point defects before transforming into equilibrium state; therefore, disclinated non-equilibrium GBs have very strong capacity to accommodate point defects and can be used as strong defect sinks for developing radiation resistance materials.

Blind prediction and post-experimental analysis of RC core wall’s cyclic flexural response using MVLEM-FD

AbstractBlind prediction and post-experimental studies of the flexural cyclic response of a U-shaped core wall, tested at UCLouvain, Belgium, are presented. The tested specimen (referred to as UW1) was modelled using a relatively simple 3D force–displacement-based version of the beam–column multiple-vertical-line-element (MVLEM-FD), developed at the University of Ljubljana (UL), using standard element parameters. The blind prediction accurately identified critical failure points within the specimen. However, the predicted type of failure, attributed to the rupture of longitudinal bars in the boundary region of flanges was somewhat different from that observed in the experiment. These bars were indeed ruptured, but their rupture was preceded by their buckling and the spalling of the surrounding concrete core. Moreover, the predicted force–displacement hysteretic loop exhibited a slight shift compared to experimental observations. Post-experimental studies revealed that this discrepancy was primarily due to the modelling of the loading at the top of the wall rather than the modelling of the wall itself. Specifically, an additional bending moment induced by the eccentricity of the vertical load applied using three actuators, which was overlooked in the blind prediction. Upon correcting the loading, the agreement between the numerical studies and experiment was considerably improved in terms of both the global and local response quantities. Additionally, minor improvements in modelling the boundary regions of the wall’s flanges, considering the relatively large unconfined concrete cover, were introduced, leading to enhanced estimations of near-collapse response.

Refinement of the Drude Polarizable Force Field for Hexose Monosaccharides: Capturing Ring Conformational Dynamics with Enhanced Accuracy.

We present a revised version of the Drude polarizable carbohydrate force field (FF), focusing on refining the ring and exocyclic torsional parameters for hexopyranose monosaccharides. This refinement addresses the previously observed discrepancies between calculated and experimental NMR 3J coupling values, particularly in describing ring dynamics and exocyclic rotamer populations within major hexose monosaccharides and their anomers. Specifically, α-MAN, β-MAN, α-GLC, β-GLC, α-GAL, β-GAL, α-ALT, β-ALT, α-IDO, and β-IDO were targeted for optimization. The optimization process involved potential energy scans (PES) of the ring and exocyclic dihedral angles computed using quantum mechanical (QM) methods. The target data for the reoptimization included PES of the inner ring dihedrals (C1-C2-C3-C4, C2-C3-C4-C5, C5-O5-C1-C2, C4-C5-O5-C1, O5-C1-C2-C3, C3-C4-C5-O5) and the exocyclic torsions, other than the pseudo ring dihedrals (O1-C1-O5-C5, O2-C2-C1-O5, and O4-C4-C5-O5) and hydroxyl torsions used in the previous parametrization efforts. These parameters, in conjunction with previously developed Drude parameters for hexopyranose monosaccharides, were validated against experimental observations, including NMR data and conformational energetics, in aqueous environments. The resulting polarizable model is shown to be in good agreement with a range of QM data, experimental NMR data, and conformational energetics of monosaccharides in aqueous solutions. This offers a significant improvement of the Drude carbohydrate force field, wherein the refinement enhances the accuracy of accessing the conformational dynamics of carbohydrates in biomolecular simulations.

Assessment of Edge Modification of Nanographene.

Carboxy groups on the edges of nanographene (NG) enable functionalization for realizing NG-organic hybrid materials. Therefore, assessment of the edge-functionalization of the electronic structures of NGs is valuable for the rational design of functional carbon materials. In this study, the structures of model NGs comprising 174 carbon atoms with armchair edges and various functional groups at the edges were computed. To achieve the greatest possible similarity between the computed structure and the real one, the carbon framework was designed based on experimental observations. The functional groups can be accessed via suitable chemical reactions. The computations predicted that although the conversion of carboxyl groups with electron-withdrawing/donating groups influences the orbital energies, the HOMO-LUMO (H-L) gap is not significantly affected, except in a few cases. Among the evaluated examples, π-extension had the greatest influence on the H-L gap. Interestingly, for the Pd2+-coordinated NG, the participation of the low-lying LUMO localized on Pd2+ in the surface-to-metal transitions seemingly narrowed the H-L gap, and a surface-to-ligand transition was observed.

Deciphering the Morphological Difference of Amyloid-β Fibrils in Familial and Sporadic Alzheimer's Diseases.

The aggregation of amyloid-β (Aβ) into amyloid fibrils is the major pathological hallmark of Alzheimer's disease (AD). Aβ fibrils can adopt a variety of morphologies, the relative populations of which are recently found to be associated with different AD subtypes such as familial and sporadic AD (fAD and sAD, respectively). The two AD subtypes differ in their ages of onset, AD-related genetic predispositions, and dominant Aβ fibril morphologies. We postulate that these disease subtype-dependent fibril morphology differences can be attributed to the intrinsic fibril properties and interacting molecules in the environment. Using atomistic discrete molecular dynamics simulations, we demonstrated that the fAD-dominant morphology exhibited a lower free-energy barrier for fibril growth but also a lower stability compared with the sAD-dominant fibril morphology, resulting in the time-dependent population change consistent with experimental observations. Additionally, we studied the effect of the Bri2 BRICHOS domain, an endogenous protein that has been reported to inhibit Aβ aggregation by preferential binding to fibrils, as one of the possible environmental factors. The Bri2 BRICHOS domain showed stronger binding to the fAD-dominant fibril than the sAD-dominant fibril in silico, suggesting a more effective suppression of fAD-dominant fibril formation. This result explains the high population of the sAD-dominant fibril morphology in sporadic cases with normal Bri2 functions. Genetic predisposition in fAD, on the other hand, might impair or overwhelm Bri2 functions, leading to a high population of fAD-associated fibril morphology. Together, our computational findings provide a theoretical framework for elucidating the AD subtypes entailed by distinct dominant amyloid fibril morphologies.

Study on reaction mechanism of CO2 electro-reduction to CO in organic medium: Revealed by experimental and spectroscopic Investigations

CO2 electrocatalytic reduction (CO2RR) to CO in organic electrolytes has received considerable attention due to its potential industrial application prospect. However, the reaction mechanism is not fully understood. In this study, we employed experimental observation, in-situ ATR-IRAS and Raman spectroscopy to elucidate the reaction mechanism of CO2 electro-reduction to CO in an organic medium. The reaction intermediates *CO2•-, *(CO2)2•- and *CO has been identified during CO2RR. Based on these results, the reaction mechanism has been discussed extensively. Density Functional Theory (DFT) analysis further indicates that the electrolytic CO2 reduction to CO in organic electrolyte is relatively more difficult than that in aqueous solutions.

Fast, Regioselective Aminolysis of Tetrasubstituted Cyclic Carbonates and Application to Recyclable Thermoplastics and Thermosets.

Herein, the long-standing challenge of the ring-opening aminolysis of CO2-derived tetrasubstituted cyclic carbonates at room temperature (r.T) is overcome under catalyst-free conditions. Molecular design of the cyclic carbonate by substitution of an alkyl group by a thioether unlocks quantitative conversion at r.T and ensures total regioselectivity toward highly substituted oxazolidone scaffolds. An in-depth rationalization of the high reactivity of these cyclic carbonate structures and of the aminolysis reaction mechanism is provided by a computational study supporting experimental observations. The high efficiency of the reaction is then translated to the deconstruction of high-performance thermoplastics containing tetrasubstituted cyclic carbonate linkages to deliver building blocks that are reused for designing recyclable thermosets bearing dynamic N,S-acetal linkages.

A novel mechanistic model for predicting shrinkage kinetics in plant-based foods by integrating solid matrix mobility and viscoelasticity

Deformation during drying is a major physical change influencing drying kinetics and final product quality. Therefore, accurate prediction of shrinkage kinetics is essential for determining the optimal drying conditions for these foods. Shrinkage kinetics is greatly influenced by their structural mobility (rubbery-glassy transition) and viscoelastic properties. The current deformation models lack a comprehensive integration of structural mobility and viscoelasticity concepts, resulting in limitation in attaining insights on physiochemical state variations and viscoelastic stresses developed during drying. In order to overcome this limitation, this study proposes a novel mechanistic shrinkage model that combines solid matrix mobility-based shrinkage velocity and viscoelasticity consideration, incorporating variable mechanical properties to simulate deformation arising from moisture loss and pressure gradient respectively. Comparison between predicted drying kinetics and shrinkage evolution with experimental observation yielded close agreement, achieving low mean absolute error values. As the drying process progressed, a distinct anisotropic shrinkage pattern emerged, which is attributed to varied structural mobility based on temperature and moisture distribution across the food sample. Notably, shrinkage driven by moisture loss significantly outweighed that induced by pressure, exerting a predominant influence on overall volume change. Furthermore, the model demonstrated heightened sensitivity to water transport parameters compared to mechanical factors, which indicates the significance of moisture dynamics in shaping the drying process. Combined consideration of physiochemical changes and viscoelastic concept in the developed deformation model extends new possibility towards optimizing the drying process as well as quality aspect evaluation.

‘Invisible’ Molecular Dynamics Revealed for a Conformationally Chiral π‐Stacked Perylene Bisimide Foldamer

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes ‘invisible’. Here we present an asymmetric perylene bisimide dimer (bis‐PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol–1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re‐fold, the transformation of one stereoisomer into others allowed us to ‘visualize’ the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

Exploring Emotional Responses of Design Styles using Electroencephalogram (EEG)

Emotion is a huge factor in creating immersive experience when playing a video game. It can be stimulated by visual design elements. In particular, different levels of realism have an effect over the human feelings. Referred to as the Design Style, it is a spectrum of mimicking the real world ranging from Abstract to Realistic. Between them is known as Stylized Design. While there have been many studies to understand the relationship between Design Styles and emotions, their experimental observations lack quantitative analysis and prone to misinterpretation. Electroencephalogram (EEG) technologies have made the possibilities to explore emotional responses directly from the brain. This research aims to understand the relationship between Design Styles and the emotional responses of the player. To analyse design styles for correlation with emotions, a working framework for machine learning classification using EEG is used. Subjects played video games of similar gameplay but of two different Design Styles – each game represents each end of the Design Styles spectrum. Analysis of the EEG data revealed distinction of emotional activity between Abstract and Realistic games. Higher intensity, larger data distribution, and abruptness of change in emotions are all associated with Abstract Design. Realism, on the other hand, is associated with a more sustained emotional state and therefore a good choice for maintaining a steady mood.

Mechanistic Analysis of Anodic Oxidation of Gold in KOH (0.1 M) Solution Using the Point Defect Model

The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using spectroscopic ellipsometry. The thickness of the oxide increases linearly with increasing applied voltage within this range. Mott-Schottky (MS) analysis showed that gold oxide formed in KOH (0.1 M) is an n-type semiconductor, and the dominant defect (Aui3+) density is calculated to be in the order of 1021–1022 (1/cm3). The steady-state current density of the oxide formation was independent of voltage, also in agreement with an n-type oxide. Reasonable agreement between PDM predictions and experimental observations of dominant defect density, steady-state current density, and thickness, demonstrates the value of the PDM in this system.

Influences of Zr and V Addition on the Crystal Chemistry of θ-Al13Fe4 and the Grain Refinement of α-Al in an Al-4Fe Alloy Based on Experiment and First-Principle Calculations

Fe-containing intermetallic compounds (IMCs) are among the most detrimental second phases in aluminum alloys. One particularly harmful type is θ-Al13Fe4, which exhibits a needle- or plate-like morphology, leading to greater degradation of mechanical properties compared to other Fe-IMCs with more compact structures, such as α-Al15(Fe,Mn)3Si2. The addition of alloying elements is a crucial strategy for modifying the microstructure during the solidification process of aluminum alloys. This study investigates the effects of adding vanadium (V) and zirconium (Zr) on the morphology and crystal chemistry of θ-Al13Fe4 in an Al-4Fe alloy, employing a combination of experimental observations, first-principle calculations, and thermodynamic analysis. Our findings indicate that zirconium significantly refines both the primary θ-Al13Fe4 particles and the α-Al grains. Additionally, a small amount of vanadium can be incorporated into one of the Wyckoff 4i Al sites in θ-Al13Fe4, rather than occupying any Fe sites, under casting conditions, in addition to the formation of binary Al-V phases.

'Invisible' Molecular Dynamics Revealed for a Conformationally Chiral π-Stacked Perylene Bisimide Foldamer.

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes 'invisible'. Here we present an asymmetric perylene bisimide dimer (bis-PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol-1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re-fold, the transformation of one stereoisomer into others allowed us to 'visualize' the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

Sedimentary processes and patterns in deposits corresponding to freshwater lake-facies of hyperpycnal flow – An experimental study based on flume depositional simulations

Abstract The article establishes a depositional model for lacustrine hyperpycnal flow by examining dynamics, transport factors, and laminae formation. The results show that several typical experimental phenomena such as fluid front mixing, double flow division, underwater leap, water skiing, and “new head” can be observed in the flume experiment. Based on the experimental observation of the flow process, three modes of transport of hyperpycnal flow in freshwater lake basins are summarized: bottom-bed loading, suspended loading, and uplift loading. Further, the change of fluid properties in hyperpycnal flow is summarized in three stages: a high-concentration stage, a low-concentration stage, and an uplifting stage. There are two main factors affecting the long-range transport of hyperpycnal flow: (1) the concentration difference between the head deposits and the ambient water body and (2) shear force of turbulence in the upper part of hyperpycnal flow. The simulation experiments of hyperpycnites laminae show that the laminae change from continuous to intermittent with the increase of the transportation distance. It is clear that the mode of transport of the hyperpycnal flow has a controlling effect on the degree of development of the laminae. Eventually, a depositional model of lake-facies hyperpycnal flow under experimental conditions was constructed.

Strain-modulated antiferromagnetic Chern insulator in NiOsCl$_6$ monolayer

Abstract Recently, Chern insulators in an antiferromagnetic (AFM) phase have been suggested theoretically and predicted in a few materials. However, the experimental observation of two-dimensional AFM quantum anomalous Hall effect is still a challenge to date. In this work, we propose that an AFM Chern insulator can be realized in a two-dimensional monolayer of NiOsCl$_6$ modulated by a compressive strain. Strain modulation is accessible experimentally and used widely in predicting and tuning topological nontrivial phases. With first-principles calculations, we have investigated the structural, magnetic and electronic properties of NiOsCl$_6$. Its stability has been confirmed through molecular dynamical simulations, elasticity constant and phonon spectrum. It has a collinear AFM order, with opposite magnetic moments of 1.3 $\mu_B$ on each Ni/Os atom, respectively, and the Néel temperature is estimated to be 93 $K$. In the absence of strain, it functions as an AFM insulator with a direct gap with spin-orbital coupling included. Compressive strain will induce a transition from a normal insulator to a Chern insulator characterized by a Chern number $C = 1$, with a band gap of about 30 meV. This transition is accompanied by a structural distortion. Remarkably, the Chern insulator phase persists within the 3$\%$-10$\%$ compressive strain range, offering an alternative platform for the utilization of AFM materials in spintronic devices.

The origin of broadband blue emission in zero-dimensional organic lead iodine perovskites: A first-principles study.

Broadband blue emission in zero-dimensional perovskites has received considerable attention, which is very important for the realization of stable blue-light emitters; however, the underlying formation mechanism remains unclear. Based on first-principles calculations, we have systematically studied the self-trapped excitons (STEs) behavior and luminescence properties in 0D-(DMA)4PbI6 perovskite. Our calculations show that there is a significant difference between the intrinsic STE luminescence mechanism (∼2.51eV) and experimental observations (∼2.70eV). In contrast, we found that the iodine vacancy (VI) is energetically accessible and exhibits a shallow charge transition level at ∼2.69eV (0/+1) above the valence band maximum, which provides the initial local well for the STEs formation. Moreover, the low electronic dimension synergistic Jahn-Teller distortion facilitates the formation of extrinsic excitons self-trapping. Further excited state electronic structure analysis and configuration coordinate diagram calculations confirmed that the broadband blue emission in 0D-(DMA)4PbI6 is the origin of VI-induced extrinsic STEs instead of intrinsic STEs. Therefore, our simulation results rationalize the experimental phenomena and provide important insights into the formation mechanism of STEs in low-dimensional perovskite systems.

Subdiffusion of heavy quarks in hot QCD matter by the fractional Langevin equation

The subdiffusion phenomena are studied for heavy quarks dynamics in the hot QCD matter. Our approach aims to provide a more realistic description of heavy quark dynamics through detailed theoretical analyses and numerical simulations, utilizing the fractional Langevin equation framework with the Caputo fractional derivative. I present numerical schemes for the fractional Langevin equation for subdiffusion and calculate the time evolution mean squared displacement and mean squared momentum of the heavy quarks. My results indicate that the mean squared displacements of the heavy quarks for the subdiffusion process deviate from a linear relationship with time. Further, I calculate the normalized momentum correlation function, kinetic energy, and momentum spread. Finally, I show the effect of subdiffusion on experimental observables, the nuclear modification factor. Published by the American Physical Society 2024

Multi-physics modeling of phase change memory operations in Ge-rich Ge2Sb2Te5 alloys

One of the most widely used active materials for phase-change memories (PCM), the ternary stoichiometric compound Ge2Sb2Te5 (GST), has a low crystallization temperature of around 150°C. One solution to achieve higher operating temperatures is to enrich GST with additional germanium. This alloy crystallizes into a polycrystalline mixture of two phases, GST and almost pure germanium. In a previous work [R. Bayle et al., J. Appl. Phys. 128, 185 101 (2020)], this crystallization process was studied using a multi-phase field model (MPFM) with a simplified thermal field calculated by a separate solver. Here, we combine the MPFM and a phase-aware electrothermal solver to achieve a consistent multi-physics model for device operations in PCM. Simulations of memory operations are performed to demonstrate its ability to reproduce experimental observations and the most important calibration curves that are used to assess the performance of a PCM cell.

Real-Time Simulation of the Reaction Kinetics of Supported Metal Nanoparticles.

A common issue with supported metal catalysts is the sintering of metal nanoparticles, resulting in catalyst deactivation. In this study, we propose a theoretical framework for realizing a real-time simulation of the reactivity of supported metal nanoparticles during the sintering process, combining density functional theory calculations, microkinetic modeling, Wulff-Kaichew construction, and sintering kinetic simulations. To validate our approach, we demonstrate its feasibility on α-Al2O3(0001)-supported Ag nanoparticles, where the simulated sintering behavior and ethylene epoxidation reaction rate as a function of time show qualitative agreement with experimental observation. Our proposed theoretical approach can be employed to screen out the promising microstructure feature of α-Al2O3 for stable supported Ag NPs, including the surface orientation and promoter species modified on it. The outlined approach of this work may be applied to a range of different thermocatalytic reactions other than ethylene epoxidation and provide guidance for the development of supported metal catalysts with long-term stability.

Conversion of a piston–cylinder dimensional dataset to the effective area of a mechanical pressure generator

Recent developments in diameter metrology at NIST have improved the dimensional characterization of piston-cylinder assemblies (PCAs) to unprecedented precision. For the newest generation of PCAs, the standard uncertainty in the measurement of the outer diameter is 12 nm, while uncertainty in the measurement of the inner diameter is 14 nm. With a high-accuracy dimensional dataset in hand, the task of determining the pressure generated by a specific PCA is reduced to converting the diameter (and straightness and roundness) to an effective area (and distortion coefficient). The details on how this was performed for the artifact PCA2062 are described. PCA2062 was dimensioned in 2017 and 2020; the area repeated within . The calculation produced estimates of fall rate and rotation decay that agreed with experimental observations within 12 %. The fall rate is proportional to the square of the gap width; therefore, the agreement between calculation and measurement validates the dimensional estimate of the gap width within (36 ± 42) nm, where the 42 nm standard uncertainty is governed by the present state of flow theory. The piston gage model is buttressed by three comparison tests against a laser barometer, which support a view that PCA2062 is linear and reproducible within 0.2 μPa Pa-1. Finally, an estimate of uncertainty in the effective area of a dimensioned artifact is provided: as expected, the diameter measurement is the main culprit, but there are open questions regarding the flow model that preclude an accurate evaluation of the distortion coefficient. For the 530 kPa operating range of PCA2062, distortion is not a significant problem, but the effect would be dominant in assemblies operating at 1 MPa and above.