Length Scales Research Articles

Localized Ionic Reinforcement of Double Network Granular Hydrogels.

Nature produces soft materials with fascinating combinations of mechanical properties. For example, the mussel byssus embodies a combination of stiffness and toughness, a feature that is unmatched by synthetic hydrogels. Key to enabling these excellent mechanical properties are the well-defined structures of natural materials and their compositions controlled on lengths scales down to tens of nanometers. The composition of synthetic materials can be controlled on a micrometer length scale if processed into densely packed microgels. However, these microgels are typically soft. Microgels can be stiffened by enhancing interactions between particles, for example through the formation of covalent bonds between their surfaces or a second interpenetrating hydrogel network. Nonetheless, changes in the composition of these synthetic materials occur on a micrometer length scale. Here, 3D printable load-bearing granular hydrogels are introduced whose composition changes on the tens of nanometer length scale. The hydrogels are composed of jammed microgels encompassing tens of nm-sized ionically reinforced domains that increase the stiffness of double network granular hydrogels up to 18-fold. The printability of the ink and the local reinforcement of the resulting granular hydrogels are leveraged to 3D print a butterfly with composition and structural changes on a tens of nanometer length scale.

Roadmap on nanoscale magnetic resonance imaging.

The field of nanoscale magnetic resonance imaging (NanoMRI) was started 30 years ago. It was motivated by the desire to image single molecules and molecular assemblies, such as proteins and virus particles, with near-atomic spatial resolution and on a length scale of 100 nm. Over the years, the NanoMRI field has also expanded to include the goal of useful high-resolution nuclear magnetic resonance (NMR) spectroscopy of molecules under ambient conditions, including samples up to the micron-scale. The realization of these goals requires the development of spin detection techniques that are many orders of magnitude more sensitive than conventional NMR and MRI, capable of detecting and controlling nanoscale ensembles of spins. Over the years, a number of different technical approaches to NanoMRI have emerged, each possessing a distinct set of capabilities for basic and applied areas of science. The goal of this roadmap article is to report the current state of the art in NanoMRI technologies, outline the areas where they are poised to have impact, identify the challenges that lie ahead, and propose methods to meet these challenges. This roadmap also shows how developments in NanoMRI techniques can lead to breakthroughs in emerging quantum science and technology applications.&#xD.

Thiol Coordination Softens Liquid Metal Particles To Improve On-Demand Conductivity.

Achieving tunable rupturing of eutectic gallium indium (EGaIn) particles holds great significance in flexible electronic applications, particularly pressure sensors. We tune the mechanosensitivity of EGaIn particles by preparing them in toluene with thiol surfactants and demonstrate an improvement over typical preparations in ethanol. We observe, across multiple length scales, that thiol surfactants and the nonpolar solvent synergistically reduce the applied stress requirements for electromechanical actuation. At the nanoscale, dodecanethiol and propanethiol in toluene suppress gallium oxide growth, as characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Quantitative AFM imaging produces force-indentation curves and height images, while conductive AFM measures current while probing individual EGaIn particles. As the applied force increases, thiolated particles demonstrate intensified softening, rupturing, and stress-induced electrical activation at forces 40% lower than those for bare particles in ethanol. To confirm that thiolation facilitates rupturing at the macroscale, a laser is used to ablate samples of EGaIn particles. Scanning electron microscopy and resistance measurements across macroscopic samples confirm that thiolated EGaIn particles coalesce to exhibit electrical activation at 0.1 W. Particles prepared in ethanol, however, require 3 times higher laser power to demonstrate a similar behavior. This unique collection of advanced techniques demonstrates that our particle synthesis conditions can facilitate on-demand functionality to benefit electronic applications.

Unified scaling for the optimal path length in disordered lattices

Unified scaling for the optimal path length in disordered lattices

A comparison study of spatial and temporal schemes for flow and transport problems in fractured media with large parameter contrasts on small length scales

AbstractIn this work, various high-accuracy numerical schemes for transport problems in fractured media are further developed and compared. Specifically, to capture sharp gradients and abrupt changes in time, schemes with low order of accuracy are not always sufficient. To this end, discontinuous Galerkin up to order two, Streamline Upwind Petrov-Galerkin, and finite differences, are formulated. The resulting schemes are solved with sparse direct numerical solvers. Moreover, time discontinuous Galerkin methods of order one and two are solved monolithically and in a decoupled fashion, respectively, employing finite elements in space on locally refined meshes. Our algorithmic developments are substantiated with one regular fracture network and several further configurations in fractured media with large parameter contrasts on small length scales. Therein, the evaluation of the numerical schemes and implementations focuses on three key aspects, namely accuracy, monotonicity, and computational costs.

Co-Assembled Supramolecular Organohydrogels of Amphiphilic Zwitterion and Polyoxometalate with Controlled Microstructures

The organization of modifiable and functional building components into various superstructures is of great interest due to their broad applications. Supramolecular self-assembly, based on rationally designed building blocks and appropriately utilized driving forces, is a promising and widely used strategy for constructing superstructures with well-defined nanostructures and diverse morphologies across multiple length scales. In this study, two homogeneous organohydrogels with distinct appearances were constructed by simply mixing polyoxometalate (phosphomolybdic acid, HPMo) and a double-tailed zwitterionic quaternary ammonium amphiphile in a binary solvent of water and dimethyl sulfoxide (DMSO). The delicate balance between electrostatic attraction and repulsion of anionic HPMo clusters and zwitterionic structures drove them to co-assemble into homogeneous organohydrogels with diverse microstructures. Notably, the morphologies of the organohydrogels, including unilamellar vesicles, onion-like vesicles, and spherical aggregates, can be controlled by adjusting the ionic interactions between the zwitterionic amphiphiles and phosphomolybdic acid clusters. Furthermore, we observed an organohydrogel fabricated with densely stacked onion-like structures (multilamellar vesicles) consisting of more than a dozen layers at certain proportions. Additionally, the relationships between the self-assembled architectures and the intermolecular interactions among the polyoxometalate, zwitterionic amphiphile, and solvent molecules were elucidated. This study offers valuable insights into the mechanisms of polyoxometalate-zwitterionic amphiphile co-assembly, which are essential for the development of materials with specific structures and emerging functionalities.

Decoupling Nucleation and Growth in Fast Crystallization of Phase Change Materials

AbstractDisentangling nucleation and growth in materials that crystallize on the nanosecond time scale is experimentally quite challenging since the relevant processes also take place on very small, i.e., sub‐micrometer length scales. Phase change materials are bad glass formers, which often crystallize rapidly. Here systematic changes in crystallization kinetics are shown in pseudo‐binary compounds of GeTe and Sb2Te3 and related solids subjected to short laser pulses. Upon systematic changes in stoichiometry, the speed of crystallization changes by three orders of magnitude concomitantly with pronounced changes in stochasticity. Resolving individual grains with electron backscatter diffraction (EBSD) permits to disentangle of the process of nucleation and growth. From these experiments, supported by multiphysics simulations of crystallization, it can be concluded that high crystallization speeds with small stochasticity characterize phase change materials with fast nucleation, while compounds that nucleate slowly crystallize much more stochastically.

Graphene–fullerene heterostructures as robust and flexible nanomechanical bits

Electrical computers have revolutionized society over the past several decades, but questions have remained about their ability to perform in extreme environments, such as their stability at high-temperature conditions. This has motivated the recent surge of interest in developing mechanical computing platforms at all length scales, including the nanoscale, in which traditional electrical computers are augmented with mechanical ones. However, the most proposed nanomechanical bits are volatile memory bits based on the dynamic response of nanomechanical resonators, and as such, there is a need to develop robust and reprogrammable entirely non-volatile nanomechanical bits. Here, we exploit the multiple quasi-stable configurations of the graphene/fullerene/graphene (GFG) van der Waals heterostructure to work as a novel nonvolatile nanomechanical bit. The GFG heterostructure is unique and robust in that it can return to its initial state without further mechanical input, it can be used for logic functions at relevant operating temperatures through simple application of uniaxial strain, it can exhibit reprogrammability between five basic logic gates (NOT, AND, NAND, OR, NOR) by varying the magnitude or direction of applied strain, and it can be used to represent combinatorial logic through full and half adders. These findings provide a new opportunity to develop mechanical computers based on the large class of nanomaterials.

Novel barostat implementation for molecular dynamics.

We propose a novel implementation of the extended-dynamics equations for isothermal-isobaric ensemble in molecular dynamics, as the Martyna-Tobias-Klein thermostat and barostat. This method is suitable for systems with constraints and the Verlet-family integrators. Instead of iterations or the Trotter-expansion-based methods, both velocities and box sizes (scaling of bond lengths) are predicted. The algorithm begins with force calculation, requiring neither quarter nor half time steps, and necessitating iterations only inside SHAKE. Several tests demonstrate that the quality is comparable to other implementations. It is found that the formula relating the extended barostat mass to the characteristic time of volume fluctuations is inaccurate for condensed systems, which has consequences for the parameter setup. Emphasis is also put on the verification of the precise isothermal-isobaric ensemble and finite-size effects.

Overcoming strength-ductility tradeoff with high pressure thermal treatment

Conventional material processing approaches often achieve strengthening of materials at the cost of reduced ductility. Here, we show that high-pressure and high-temperature (HPHT) treatment can help overcome the strength-ductility trade-off in structural materials. We report an initially strong-yet-brittle eutectic high entropy alloy simultaneously doubling its strength to 1150 MPa and its tensile ductility to 36% after the HPHT treatment. Such strength-ductility synergy is attributed to the HPHT-induced formation of a hierarchically patterned microstructure with coherent interfaces, which promotes multiple deformation mechanisms, including dislocations, stacking faults, microbands and deformation twins, at multiple length scales. More importantly, the HPHT-induced microstructure helps relieve stress concentration at the interfaces, thereby arresting interfacial cracking commonly observed in traditional eutectic high entropy alloys. These findings suggest a new direction of research in employing HPHT techniques to help develop next generation structural materials.

Dark dimension, the swampland, and the dark matter fraction composed of primordial near-extremal black holes

In a recent publication we studied the decay rate of primordial black holes perceiving the dark dimension, an innovative five-dimensional (5D) scenario that has a compact space with characteristic length scale in the micron range. We demonstrated that the rate of Hawking radiation of 5D black holes slows down compared to 4D black holes of the same mass. Armed with our findings we showed that for a species scale of O(1010 GeV), an all-dark-matter interpretation in terms of primordial black holes should be feasible for black hole masses in the range 1014≲M/g≲1021. As a natural outgrowth of our recent study, herein we calculate the Hawking evaporation of near-extremal 5D black holes. Using generic entropy arguments we demonstrate that Hawking evaporation of higher-dimensional near-extremal black holes proceeds at a slower rate than the corresponding Schwarzschild black holes of the same mass. Assisted by this result we show that if there were 5D primordial near-extremal black holes in nature, then a primordial black hole all-dark-matter interpretation would be possible in the mass range 105β≲M/g≲1021, where β is a parameter that controls the difference between mass and charge of the associated near-extremal black hole. Published by the American Physical Society 2024

Study on the flame radiative heat transfer and near-field radiation heat flux predictive model of vehicle fires in a tunnel

As a major form of heat transfer, flame thermal radiation has an important effect on the ignition of adjacent energy, fire spread and environmental damage. Forecasting the flame radiation heat flux can provide theoretical basis for fire hazard assessment, fire extinguishing and salvation. Meanwhile, the distinctive structure of the arc tunnel can result in significant variations in the local heat and mass transfer processes during tunnel fires compared to those in rectangular tunnels, leading to different fire characteristics parameters. In this study, experiments and theoretical analyses were conducted to investigate the flame length scale and near-field radiation heat flux on the lower surface of an arc-shaped ceiling induced by vehicle fires in a tunnel. The findings reveal that the flame length scale in the transverse direction beneath the arc-shaped ceiling decreases with an increasing burner aspect ratio and increases with the increasing heat release rate. A dimensionless model of the flame length scale under the arced ceiling with various burner aspect ratios was proposed based on the amount of remaining unburned fuel after flame impingement and the buoyancy component along the arc-shaped ceiling. Simultaneously, radiative heat fluxes on the lower surface also increase with rising heat release rate. The flame geometry beneath the arc-shaped ceiling is assumed to be a combination of a cuboid and an arc plate model based on the actual flame length scale. Subsequently, the view factor, radiative fraction, and flame surface area are analyzed to predict the radiative heat fluxes on the lower surface. The predictions of the cuboid and arc plate flame model show good agreement with the current experimental data. This work presents a dimensionless correlation of the flame length scale and calculates the view factor between the target and the arc plate to predict the near-field radiative heat flux more accurately. This approach also facilitates the understanding of flame spreading behavior and thermal hazards impacted by arced ceiling.

Probing quantum decoherence at Belle II and LHCb

With the advent of Belle II and the LHCb upgrade, the precision measurements of various B-Physics observables are on cards. This holds significant potential for delving into physics beyond the standard model of electroweak interactions. These measurements can also serve as means to establish limits on phenomena occurring at much finer length scales, such as quantum decoherence, which may arise due to potential discreteness in space-time or non-trivial topological effects. In this work, we set up the formalism to investigate the impact of quantum decoherence on several potential observables in B meson systems. The approach employs the trace-preserving Kraus operator formalism, extending unitary evolution to non-unitary dynamics while maintaining complete positivity. In this formalism, the decoherence effects are parametrized in terms of a single parameter. Through the analysis of purely leptonic, semileptonic, and non-leptonic decays of B mesons, we identify observables that could, in principle, be influenced by decoherence. The theoretical expressions are provided without neglecting the impact of decay width difference (∆Γ) and CP violation in mixing. Considering that many of these observables can be measured with high precision using the abundant data collected by LHCb and Belle II, our formalism can be applied to establish constraints on the decoherence parameter through multiple decay channels. This offers an alternative set-up for such studies, which, at present, are predominantly conducted in the neutrino sector.

Photoresponsive Biomimetic Functions by Light-Driven Molecular Motors in Three Dimensionally Printed Liquid Crystal Elastomers.

Despite the fascinating developments in design and synthesis of artificial molecular machines operating at the nanoscales, translating molecular motion along multiple length scales and inducing mechanical motion of a three-dimensional macroscopic entity remains an important challenge. The key to addressing this amplification of motion relies on the effective organization of molecular machines in a well-defined environment. By taking advantage of long-range orientational order and hierarchical structures of liquid crystals and unidirectional rotation of light-driven molecular motors, we report here photoresponsive biomimetic functions of liquid crystal elastomers (LCEs) by the repetitive unidirectional rotation of molecular motors using 3D printing. Molecular motors were built in the main chain of liquid crystals oligomers to serve as photoactuators. The oligomers were then used as the ink, and liquid crystal elastomers with different morphologies were printed. The obtained LCEs are able to conduct multiple types of motions including bending, helical coiling, closing of petals, and flipping of wings of a butterfly upon UV illumination, which paves the way for future design of responsive materials with enhanced complex actuating functions.

An assessment of effective slope as a parameter for turbulent drag prediction over multi-scaled roughness

The streamwise effective slope (ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document}), which is the mean absolute streamwise gradient of the roughness, is considered to be a key parameter in predicting the drag penalty of rough-wall turbulent boundary-layers. However, many real-world rough surfaces are multi-scaled. For such surfaces, ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document} can be unbounded and its value can be dominated by scales of the topography that are invisible to the flow. To illustrate this, a campaign of drag balance measurements was conducted with a set of machined surfaces. A baseline surface is prepared with fine machining parameters. By coarsening the machining precision, artefacts called ‘scallops’ are introduced which increases the ‘measured’ ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document} without changing other geometrical statistics. The drag of the ‘scalloped’ surfaces is higher than the baseline surface, with the relative drag increase scaling with the viscous scaled scallop height, but only when their height exceeds 2∼3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$2\\sim 3$$\\end{document} times the viscous length scale. Further, the drag of one of the ‘scalloped’ cases, even when the scallop height is O(10)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathcal {O}(10)$$\\end{document} viscous units, is seen to be much lower (∼28\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim 28$$\\end{document}%) than a case with matched ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document}, but where the ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document} results from larger scale features. These findings confirm that for multi-scaled surfaces, ESx\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm ES}_x$$\\end{document} may be a misleading topographical metric for drag (or ks\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$k_s$$\\end{document}) prediction and one must consider which scales contribute to the average slope of a surface.

Upgrading event driven Monte Carlo simulations for molecule‐based morphological control for battery and sensor applications

AbstractMultiphase polymeric materials and applications play a prominent role in our society. One of the key challenges is the design and modification of their macromolecules so that the composition and structuring of the phases as well as the interactions between them can be controlled from the molecular scale onwards. In the present contribution, it is highlighted that more recently developed event driven (kinetic) Monte Carlo models provide an interesting framework to grasp molecular variations over various length scales. The strength lies in the tracking of individual molecules per phase of interest so that interphase transfer events can be sampled based on the distributed nature of the (macro)molecules present. Hence, the micro‐scale of local concentrations and temperatures can be connected to the meso‐scale defining interphase transport and morphological variations, with an additional connection to the macro‐ or application scale within reach by adding macro‐scale transfer events to the overall sampling scheme. Starting from a benchmark coupled matrix based Monte Carlo (CMMC) study on the multiphase formation of engineering composites which explicitly acknowledges the type of (macro)molecules present in each phase, it is showcased that the CMMC framework can support the general field of energy and electronics applications. This is highlighted through (i) a case study devoted to the design of polymer electrolytes for batteries, and (ii) a case study on blend design for the regulated stretching of piezoresistive sensors.This article is protected by copyright. All rights reserved.

A review of natural circulation flow in integral effect test facilities

The proposed NCFM map was reviewed using natural circulation data identified in the PWR simulated integral effect test (IET) facility with a height (length) scale ratio of 1/1. Based on this, the characteristics of natural circulation flow in the ATLAS and FESTA facilities, which are major IET facilities in Korea, are compared. It was confirmed that the natural circulation flow characteristics were well maintained within the NCFM area even at the half-height test facility of ATLAS. It was also confirmed that the natural circulation flow characteristics were well maintained within the NCFM area at the full-height test facility of FESTA, and the natural circulation flow characteristics were also maintained outside the NCFM region for a relatively small amount of coolant inventories.

A Standardised Potentiometric Method for the Effective Parameterisation of Reversible Heating in a Lithium-Ion Cell

Abstract Lithium-ion batteries generate heat, degrading faster and becoming unsafe at high temperature. Yet many battery models do not consider the contribution of reversible, entropic heating when evaluating the rate of heat generation from a cell or battery pack. This leads to temperature prediction errors in battery management systems, increased safety risk, and reduced lifetime of the battery pack. Here, a standardised potentiometric method is proposed, allowing anyone with access to a typical battery lab to reliably and accurately extract the entropy coefficient for any electrochemical cell, the key parameter for the inclusion of reversible heating in a battery model. The proposed method takes 7.4 days to complete, representing a reduction of 90% compared to some methods proposed in the literature. Results highlight the importance of moving away from the multiple temperature steps, and the temperature step increases that dominate the existing literature. These arguments are justified through the observation and introduction of voltage relaxation following both kinetic and thermal excitation. These phenomena are termed post-kinetic-potentialisation and post-thermalisation-potentialisation. Post-thermalisation-potentialisation is not discussed in any published literature yet represents an important behavioural trait for any lithium-ion cell with a non-negligible length scale and thermal diffusivity.

Self-assembly of nanocrystal checkerboard patterns via non-specific interactions

Checkerboard lattices—where the resulting structure is open, porous, and highly symmetric—are difficult to create by self-assembly. Synthetic systems that adopt such structures typically rely on shape complementarity and site-specific chemical interactions that are only available to biomolecular systems (e.g., protein, DNA). Here we show the assembly of checkerboard lattices from colloidal nanocrystals that harness the effects of multiple, coupled physical forces at disparate length scales (interfacial, interparticle, and intermolecular) and that do not rely on chemical binding. Colloidal Ag nanocubes were bi-functionalized with mixtures of hydrophilic and hydrophobic surface ligands and subsequently assembled at an air–water interface. Using feedback between molecular dynamics simulations and interfacial assembly experiments, we achieve a periodic checkerboard mesostructure that represents a tiny fraction of the phase space associated with the polymer-grafted nanocrystals used in these experiments. In a broader context, this work expands our knowledge of non-specific nanocrystal interactions and presents a computation-guided strategy for designing self-assembling materials.

Correlating activities and defects in (photo)electrocatalysts using in-situ multi-modal microscopic imaging

Photo(electro)catalysts use sunlight to drive chemical reactions such as water splitting. A major factor limiting photocatalyst development is physicochemical heterogeneity which leads to spatially dependent reactivity. To link structure and function in such systems, simultaneous probing of the electrochemical environment at microscopic length scales and a broad range of timescales (ns to s) is required. Here, we address this challenge by developing and applying in-situ (optical) microscopies to map and correlate local electrochemical activity, with hole lifetimes, oxygen vacancy concentrations and photoelectrode crystal structure. Using this multi-modal approach, we study prototypical hematite (α-Fe2O3) photoelectrodes. We demonstrate that regions of α-Fe2O3, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxygen vacancy concentration, with the film thickness and extended light exposure also influencing local activity. Our work highlights the importance of microscopic mapping to understand activity, in even seemingly homogeneous photoelectrodes.