Macroscopic Length Scales Research Articles

1200% enhancement of solar energy conversion by engineering three dimensional arrays of flexible biophotoelectrochemical cells in a fixed footprint encompassed by Johnson solid shaped optical well

Photosynthetic proteins carry out photochemical charge separation with a near-unity quantum efficiency and provide interesting materials for sustainable solar energy conversion in man-made photoelectrochemical devices. The three-dimensional architectures of natural photosynthesisers on both macroscopic and microscopic length scales contrast strikingly with the essentially two-dimensional architectures of commercial photovoltaic devices. In this work we fabricated flexible and semi-transparent bio-photoelectrochemical cells (BPEC) that showed excellent flexibility and durability in response to repeated mechanical deformation. A three-dimensional stack of five such BPECs connected in parallel produced a peak photocurrent of 2900 nA under simulated sunlight in the laboratory and 2400 nA when tested outdoors. Placement of the BPEC stack within either a regular solid reflective well or a Johnson solid reflective well further boosted these photocurrents, computational analysis indicating that the strongest boost that more than doubled output was the consequence of multiple reflections within the Johnson solid that increased the light intensity incident on the BPEC stack. These design features, inspired by natural structures for absorbing and reflecting sunlight, improved the relative performance of the BPECs under non-peak insolation, such that the photocurrent output under natural sunlight was relatively uniform between 10 a.m. and 5 p.m. We discuss how the flexibility, durability and partial transparency of the individual BPECs enable the fabrication of cell arrays with a range of three-dimensional architectures.

Nanostructure and Fracture Behavior of Carbon Nanofiber-Reinforced Cement Using Nanoscale Depth-Sensing Methods.

In recent years, carbon nanofibers have been investigated as a suitable reinforcement for cementitious composites to yield novel multifunctional materials with improved mechanical, electrical, magnetic, and self-sensing behavior. Despite several studies, the interactions between carbon nanofibers and Portland cement hydration products are not fully understood, with significant implications for the mechanical response and the durability at the macroscopic lengthscale. Thus, the research objective is to investigate the influence of carbon nanofibers on the nanostructure and on the distribution of hydration products within Portland cement paste. Portland cement w/c = 0.44 specimens reinforced with 0.0 wt%, 0.1 wt%, and 0.5 wt% CNF by mass fraction of cement are cast using a novel synthesis procedure. A uniform dispersion of carbon nanofibers (CNF) via a multi-step approach: after pre-dispersing carbon nanofibers using ultrasonic energy, the carbon nanofibers are further dispersed using un-hydrated cement particles in high shear mixing and mechanical stirring steps. High-resolution scanning electron microscopy analysis shows that carbon nanofibers fill nanopores and connect calcium–silicate hydrates (C–S–H) grains. Grid nano-indentation testing shows that Carbon nanofibers influence the probability distribution function of the local packing density by inducing a shift towards higher values, = 0.76–0.93. Statistical deconvolution analysis shows that carbon nanofibers result in an increase in the fraction of high-density C–S–H by 6.7% from plain cement to cement + 0.1 wt% CNF and by 10.7% from plain cement to cement + 0.5 wt% CNF. Moreover, CNF lead to an increase in the C–S–H gel porosity and a decrease in both the capillary porosity and the total porosity. Based on scratch testing, adding 0.1 wt% CNF yields a 4.5% increase in fracture toughness and adding 0.5 wt% CNF yields a 7.6% increase in fracture toughness. Finally, micromechanical modelling predicts an increase of respectively 5.97% and 21.78% in the average Young’s modulus following CNF modification at 0.1 wt% CNF and 0.5 wt% CNF levels.

Sponge-derived natural bioactive glass microspheres with self-assembled surface channel arrays opening into a hollow core for bone tissue and controlled drug release applications

Porous, bioactive microspheres have always been a dream material to biomedical scientists for bone regeneration and drug delivery applications due to their interconnectivity, unique pore geometry, encapsulation ability and porosity spanning macroscopic, microscopic and nanoscopic length scales. Extensive efforts have been made to produce such materials synthetically at a great cost of money, time and labor. Herein, naturally-assembled multifunctional, open-channeled and hollow bioactive micro silica spheres (diameter 209.4 ± 38.5 µm) were discovered in a marine sponge (Geodia macandrewii), by peeling the outer surface of the sterrasters using hydrogen fluoride. The obtained micro silica spheres exhibited valuable characteristics such as homogeneously distributed pores, a cavity in the center of the sphere, and channels (approx. 3000) opening from each pore into the central cavity. Simulated body fluid analysis demonstrated the bioactivity of the micro silica spheres; whereas, no bioactivity was recorded for the original untreated sterrasters. The non-cytotoxicity and osteogenic ability of the isolated microspheres were confirmed through osteoblast cell culture. Finally, these silica based porous microspheres were tested for controlled drug release capacity. The spheres showed excellent loading and release abilities for an anti-cancer drug, carboplatin, in simulated solutions and in human cancer cell culture, HeLa, through a real time cell analyzer system. The drug loading capacity of the porous beads was determined as 10.59%. Considering the unique biological and physicochemical properties, these novel bioactive silica spheres, which we name as giant macroporous silica (GMS), are promising materials for a range of applications including bone tissue engineering and drug delivery.

Constructional and functional anatomy of Ediacaran rangeomorphs

AbstractEdiacaran rangeomorphs were the first substantially macroscopic organisms to appear in the fossil record, but their underlying biology remains problematic. Although demonstrably heterotrophic, their current interpretation as osmotrophic consumers of dissolved organic carbon (DOC) is incompatible with the inertial (high Re) and advective (high Pe) fluid dynamics accompanying macroscopic length scales. The key to resolving rangeomorph feeding and physiology lies in their underlying construction. Taphonomic analysis of three-dimensionally preserved Charnia from the White Sea identifies the presence of large, originally water-filled compartments that served both as a hydrostatic exoskeleton and semi-isolated digestion chambers capable of processing recalcitrant substrates, most likely in conjunction with a resident microbiome. At the same time, the hydrodynamically exposed outer surface of macroscopic rangeomorphs would have dramatically enhanced both gas exchange and food delivery. A bag-like epithelium filled with transiently circulated seawater offers an exceptionally efficient means of constructing a simple, DOC-consuming, multicellular heterotroph. Such a body plan is broadly comparable to that of anthozoan cnidarians, minus such derived features as muscle, tentacles and a centralized mouth. Along with other early bag-like fossils, rangeomorphs can be reliably identified as total-group eumetazoans, potentially colonial stem-group cnidarians.

Proton Transport in [BMIM+][BF4-]/Water Mixtures Near the Percolation Threshold.

The incorporation of ionic liquids into existing proton exchange membrane (PEM) materials has been shown to enhance thermal stability and improve conductivity at reduced water content. Because proton transport is dictated by an interplay between vehicular diffusion and the Grotthuss mechanism, it is expected that the nanoscale structure of the resulting ionic liquid/water networks will sensitively influence transport properties. In this work, we study proton transport in [BMIM+][BF4-]/water mixtures of systematically varying water volume fraction, focusing on concentrations near the percolation threshold in which water networks are connected over macroscopic length scales. We utilize reactive molecular dynamics within the multistate empirical valence bond (MS-EVB) framework to explicitly model Grotthuss hopping processes. Excellent agreement with experimental conductivity data is obtained within the Nernst-Einstein approximation, indicating that proton transport proceeds in a largely uncorrelated manner even at pH <0. We additionally study the changing topology of the hydrogen-bonded water network in these mixtures using percolation and graph theory analysis. We find that the proton diffusion coefficient and forward hop rate increase linearly with water content at concentrations ranging from dilute through the percolation threshold; surprisingly, we find no deviation in this trend at the percolation transition. The high concentration of BF4- anions inherently alters the fraction of Eigen and Zundel proton states, producing a net detrimental effect on proton transport rates relative to bulk water. This mechanistic insight is useful for selecting ideal ionic liquid candidates and determining the optimal ionic liquid concentration to incorporate into PEM materials.

On the dynamics of Richtmyer–Meshkov bubbles in unstable three-dimensional interfacial coherent structures with time-dependent acceleration

Richtmyer–Meshkov instability (RMI) plays an important role in many areas of science and engineering, from supernovae and fusion to scramjets and nano-fabrication. Classical RMI is induced by a steady shock and impulsive acceleration, whereas in realistic environments, the acceleration is usually variable. We focus on RMI induced by acceleration with power-law time-dependence and apply group theory to study the dynamics of regular bubbles. For early time linear dynamics, we find the dependence of the growth rate on the initial conditions and show that it is independent of the acceleration parameters. For late-time nonlinear dynamics, we consider regular asymptotic solutions, find a continuous family of such solutions, including their curvature, velocity, Fourier amplitudes, and interfacial shear, and study their stability. For each solution, the interface dynamics is directly linked to the interfacial shear. The non-equilibrium velocity field has intense fluid motion near the interface and effectively no motion in the bulk. The quasi-invariance of the fastest stable solution suggests that the dynamics of nonlinear RM bubbles is characterized by two macroscopic length scales: the wavelength and the amplitude, in agreement with observations. The properties of a number of special solutions are outlined. These are the flat Atwood bubble, the curved Taylor bubble, the minimum shear bubble, the convergence limit bubble, and the critical bubble. We elaborate new theory benchmarks for future experiments and simulations.

Chiral Instabilities and the Onset of Chiral Turbulence in QED Plasmas.

We present a first principles study of chiral plasma instabilities and the onset of chiral turbulence in QED plasmas with strong gauge matter interaction (e^{2}N_{f}=64), far from equilibrium. By performing classical-statistical lattice simulations of the microscopic theory, we show that the generation of strong helical magnetic fields from a helicity imbalance in the fermion sector proceeds via three distinct phases. During the initial linear instability regime the helicity imbalance of the fermion sector causes an exponential growth (damping) of magnetic field modes with right- (left-) handed polarization, for which we extract the characteristic growth (damping) rates. Secondary growth of unstable modes accelerates the helicity transfer from fermions to gauge fields and ultimately leads to the emergence of a self-similar scaling regime characteristic of a decaying turbulence, where magnetic helicity is efficiently transferred to macroscopic length scales. Within this turbulent regime, the evolution of magnetic helicity spectrum can be described by an infrared power spectrum with spectral exponent κ=10.2±0.5 and dynamical scaling exponents α=1.14±0.50 and β=0.37±0.13.

Emergent quantum materials

Abstract

DEM modelling of mini-triaxial test based on one-to-one mapping of sand particles

This paper presents a discrete-element method simulation of mini-triaxial tests on a sand with realistically shaped grains. It compares the results with physical experiments at multiple length scales, including the macroscopic sample length scale and the particle scale. A series of image-processing techniques were utilised to binarise, segment and label the raw data in images obtained from the mini-triaxial test. The images were obtained using an X-ray synchrotron radiation scanner. A spherical harmonic analysis was used to filter the image data and to reconstruct the natural particle morphology. Two parameters, these being the radius ratio of the smallest to largest sphere [Formula: see text] and a characteristic distance [Formula: see text] within the multisphere clump method, were chosen to represent the realistic particle morphology, balancing accuracy against computational cost. A one-to-one discrete-element model, where every particle in the physical experiment has its own numerical twin, was constructed. The discrete-element model was contained by a numerically generated flexible membrane allowing free deformation of the specimen under a prescribed confining stress, as in a physical triaxial test. Finally, attention was given to particle scale properties and their influences on the mechanical response of the discrete-element model. For a given strain rate it was found that shear modulus and friction coefficient affect the initial stiffness, the peak load and the dilation significantly. This study, and the simulation results within it, demonstrate that the proposed modelling approach is capable of reproducing macroscopic (e.g. stiffness, deviatoric stress response and volumetric response) and particle-level (e.g. displacement, rotation and branch vector orientation) behaviours that are very similar to what occurs within physical experiments, validating the effectiveness of the proposed one-to-one mapping technique.

Microstructural evolution and failure in short fiber soft composites: Experiments and modeling

In this work, we systematically study the mechanics of short glass fiber composites with a soft, hyperelastic matrix (polydimethylsiloxane). The fiber orientation can be controlled by fabricating the materials with direct ink writing, an extrusion-based 3D printing method. We specifically characterize the damage evolution in these materials when subject to tensile and cyclic loading by developing a micromechanical model, a continuum model, and by performing experiments. The stress-stretch behavior and damage evolution are highly-dependent on both volume fraction and fiber orientation. We focus primarily on loading that is parallel with the fiber alignment, which shows rich complexities as a function of volume fraction, including variable softening and non-monotonic increase of the yield strength. Unlike most prior work, we use in situ optical measurements and digital image correlation during mechanical loading to quantify the highly-nonhomogeneous stretch field at macroscopic and microscopic length scales, and to simultaneously visualize the mechanisms underlying the damage evolution and complexities in the stress-stretch response, namely fiber-matrix debonding. The micromechanical model is based on modifications to the classic shear lag model, which include incorporation of fiber length distribution as a function of volume fraction and use of Weibull distributions to account for the probability of fiber-matrix debonding. The continuum model is based on hyperelastic strain energy with damage parameters for both matrix and fibers. The combination of the two models is able to capture the stress-stretch behavior and damage evolution well, and also the Mullins-like, history-dependent cyclic loading behavior we observe in experiments.

Acoustic flows in a slightly rarefied gas

The Boltzmann equation provides a rigorous description of gas flows at all degrees of gas rarefaction. Asymptotic analyses of this equation yield valuable insight into the physical mechanisms underlying gas flows. In this article, we report an asymptotic analysis of the Boltzmann-BGK equation for a slightly rarefied gas when the acoustic wavelength is comparable to the macroscopic characteristic length scale of the flow. This is performed using a three-way matched asymptotic expansion, which accounts for the Knudsen layer, the viscous layer, and the outer Hilbert region - these are separated by asymptotically disparate length scales. Transport equations and boundary conditions for these regions are derived. The utility of this theory is demonstrated by application to three problems: (1) flow generated by uniformly heating two plates, (2) oscillatory thermal creep induced between two plates, and (3) the flow generated by an oscillating sphere. Comparisons to numerical simulations of the Boltzmann-BGK equation and previous asymptotic theories (for long wavelength) are performed. The present theory is distinct from previous asymptotic analyses that implicitly assume long or short acoustic wavelength. This theory is expected to find application in the design and characterization of nanoelectromechanical devices, which often generate acoustic oscillatory flows of a rarefied nature.

Computational molecular field theory for nematic liquid crystals.

Nematic liquid crystals exhibit configurations in which the underlying ordering changes markedly on macroscopic length scales. Such structures include topological defects in the nematic phase and tactoids within nematic-isotropic coexistence. We discuss a computational study of inhomogeneous configurations that is based on a field theory extension of the Maier-Saupe molecular model of a uniaxial, nematic liquid crystal. A tensor order parameter is defined as the second moment of an orientational probability distribution, leading to a free energy that is not convex within the isotropic-nematic coexistence region, and that goes to infinity if the eigenvalues of the order parameter become nonphysical. Computations of the spatial profile of the order parameter are presented for an isotropic-nematic interface in one dimension, a tactoid in two dimensions, and a nematic disclination in two dimensions. We compare our results to those given by the Landau-de Gennes free energy for the same configurations and discuss the advantages of such a model over the latter.

Multiscale approach for magnetization dynamics: unraveling exotic magnetic states of matter

Crystallographic lattice defects strongly influence dynamical properties of magnetic materials at both microscopic and macroscopic length scales. A multi-scale approach to magnetisation dynamics, which is presented in this paper, accurately captures such effects. The method is illustrated using examples of systems with localized, non-trivial topological properties, e.g. in the form of skyrmions and chiral domain walls that interact with lattice dislocations. Technical aspects of the methodology involve multi-scale magnetisation dynamics that connects atomistic and continuum descriptions. The technique is capable of solving the Landau-Lifshitz-Gilbert equations efficiently in two regions of a magnetic material --- the mesoscopic and the atomistic regions, which are coupled in a seamless way. It is demonstrated that this methodology allows simulating realistically-sized magnetic skyrmions interacting with material defects and novel physical effects, uncovered using this theoretical methodology, are described.

Systematically Improving Espresso: Insights from Mathematical Modeling and Experiment

Summary Espresso is a beverage brewed using hot, high-pressure water forced through a bed of roasted coffee. Despite being one of the most widely consumed coffee formats, it is also the most susceptible to variation. We report a novel model, complimented by experiment, that is able to isolate the contributions of several brewing variables, thereby disentangling some of the sources of variation in espresso extraction. Under the key assumption of homogeneous flow through the coffee bed, a monotonic decrease in extraction yield with increasingly coarse grind settings is predicted. However, experimental measurements show a peak in the extraction yield versus grind setting relationship, with lower extraction yields at both very coarse and fine settings. This result strongly suggests that inhomogeneous flow is operative at fine grind settings, resulting in poor reproducibility and wasted raw material. With instruction from our model, we outline a procedure to eliminate these shortcomings.

Field driven recovery of the collective spin dynamics of the chiral soliton lattice

We investigate the magnetic field dependence of the spin excitation spectra of the chiral soliton lattice (CSL) in the helimagnet CrNb3S6, by means of microwave resonance spectroscopy. The CSL is a prototype of a noncollinear spin system that forms periodically over a macroscopic length scale. Following the field initialization of the CSL, we found three collective resonance modes over an exceptionally wide frequency range. Upon further reducing the magnetic field toward 0 T, the spectral weight of these collective modes was disrupted by the emergence of additional resonances whose Kittel-like field dependence was linked to coexisting field polarized magnetic domains. The collective behavior at a macroscopic level was only recovered upon reaching the helical magnetic state at 0 T. The magnetic history of this noncollinear spin system can be utilized to control microwave absorption, with potential use in magnon-driven devices.

Temperature Increases and Thermoplastic Microstructural Evolution in Adiabatic Shear-Bands in a High-Strength and High-Toughness 10 wt.% Ni Steel

A 10 wt.% nickel-steel has been developed for high pressures and low-temperature applications, due to its high strength, excellent toughness, and low ductile-to-brittle transition temperature (DBTT). Under dynamic loading conditions this steel is, however, prone to shear localization that manifests as adiabatic shear bands (ASBs). The temperature increases and thermoplastic microstructural evolution in the ASB are studied in detail, from the macroscopic length scale to the atomic-scale employing correlative electron-backscatter diffraction (EBSD), transmission electron microscopy (TEM), and atom-probe tomography (APT). From a calculation of the temperature increase under adiabatic conditions, based on the conversion of plastic-work to heat generation, the microstructural transitions in the ASB are discussed specifically for: (i) a b.c.c.-f.c.c. phase-transformation and their elemental partitioning; (ii) the thermodynamic model for the compositional change of the V(Nb)-rich carbonitride precipitates during a temperature increase; and (iii) grain-refinement and rotation by dynamic/mechanical recrystallization processes. Solute segregation at subgrain boundaries, measured using the Gibbsian interfacial excess methodology, reveals how solute segregation contributes to the instability of localized shear-deformation by promoting the depinning of solute elements and the migration of a grain boundary. Finally, a kinetic model for grain refinement/rotation within an ASB is described by the dynamic recrystallization behavior with: (i) subgrain formation; (ii) rotation/refinement by deformation; and (iii) grain growth by subgrain coalescence with further rotation and a temperature increase. The temperature increase under dynamic deformation in an ASB promotes grain boundary migration and subgrain coalescence to create a large degree of equiaxed grains with a low density of imperfections.

A general theoretical and experimental framework for nanoscale electromagnetism.

The macroscopic electromagnetic boundary conditions, which have been established for over a century1, are essential for the understanding of photonics at macroscopic length scales. Even state-of-the-art nanoplasmonic studies2-4, exemplars of extremely interface-localized fields, rely on their validity. This classical description, however, neglects the intrinsic electronic length scales (of the order of ångström) associated with interfaces, leading to considerable discrepancies between classical predictions and experimental observations in systems with deeply nanoscale feature sizes, which are typically evident below about 10 to 20 nanometres5-10. The onset of these discrepancies has a mesoscopic character: it lies between the granular microscopic (electronic-scale) and continuous macroscopic (wavelength-scale) domains. Existing top-down phenomenological approaches deal only with individual aspects of these omissions, such as nonlocality11-13 and local-response spill-out14,15. Alternatively, bottom-up first-principles approaches-for example, time-dependent density functional theory16,17-are severely constrained by computational demands and thus become impractical for multiscale problems. Consequently, a general and unified framework for nanoscale electromagnetism remains absent. Here we introduce and experimentally demonstrate such a framework-amenable to both analytics and numerics, and applicable to multiscale problems-that reintroduces the electronic length scale via surface-response functions known as Feibelman d parameters18,19. We establish an experimental procedure to measure these complex dispersive surface-response functions, using quasi-normal-mode perturbation theory and observations of pronounced nonclassical effects. We observe nonclassical spectral shifts in excess of 30 per cent and the breakdown of Kreibig-like broadening in a quintessential multiscale architecture: film-coupled nanoresonators, with feature sizes comparable to both the wavelength and the electronic length scale. Our results provide a general framework for modelling and understanding nanoscale (that is, all relevant length scales above about 1 nanometre) electromagnetic phenomena.

Use of a Thermally Degradable Chemical Vapor Deposited Polymer Film for Low Damage Plasma Processing of Highly Porous Dielectrics

Nanoporous materials show a large surface area and co-continuous topology, leading to a high sensitivity to chemically active components over macroscopic length scales. The processing of nanoporous systems can be complex, causing modifications of the original material, or appearance of unwanted contaminants. The present work report on a protection method based on temporary filling by a sacrificial template polymer, forming in-situ a reversible urea linkage. Microporous organo-silicate low-k dielectric thin films are used as demonstrators, exposed to aggressive plasma discharges. Depending on the studied material, the fraction of filled pore volume varies between 29 and 66 %, with a homogeneous spatial distribution. The filling component is formed by a blend of urea-linked polymer and isocyanate-terminated monomers, is stable during plasma processing and can be fully removed by annealing above 300°C. This sacrificial filler protect the internal structure of the porous dielectric from the plasma, leading to...

Dichroic Plasmon Superstructures of Au Nanorods over Macroscopic Areas via Directed Self‐Assemblies of Diblock Copolymers

AbstractThe ability to organize metal nanoparticles over the macroscopic length scale has fundamental implications for advanced plasmonic applications. In particular, linear assemblies of anisotropic nanorods (NRs) may represent a dichroic superstructure, in which plasmonic extinction is inherently dependent on the direction of light polarization. As plasmonic properties are interconnected with optics, electronics, catalysis, and sensing, dichroism in plasmonic systems can stimulate interesting opportunities in many fields of chemistry. However, the preparation of dichroic structures with a single orientation at the centimeter scale remains a significant challenge. Herein, directed self‐assemblies of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) diblock copolymers on lithographical patterns are applied to produce a linear pattern of Au NRs. Periodic nanogrooves from plasma‐etched PS‐b‐PMMA nanodomains facilitate the dense packing of Au NRs into end‐to‐end alignment, which entail strong plasmonic coupling among longitudinal plasmonic modes. Because the resulting NR assemblies have uniform orientation, their dichroic functions can be examined by conventional UV–vis spectroscopy without the aid of single‐particle measurements. Interestingly, both transverse and longitudinal localized surface plasmonic resonance peaks can be turned on and off under two polarized lights in orthogonal directions. Moreover, the resulting superstructures can be transferred onto various substrates, allowing the implantation of dichroic functions for numerous plasmonic applications.

Low-cycle fatigue life prediction of a polycrystalline nickel-base superalloy using crystal plasticity modelling approach

A crystal plasticity model is developed to predict the cyclic plasticity during the low-cycle fatigue of GH4169 superalloy. Accumulated plastic slip and energy dissipation as fatigue indicator parameters (FIPs) are used to predict fatigue crack initiation and the fatigue life until failure. Results show that fatigue damage is most likely to initiate at triple points and grain boundaries where severe plastic slip and energy dissipation are present. The predicted fatigue life until failure is within the scatter band of factor 2 when compared with experimental data for the total strain amplitudes ranging from 0.8% to 2.4%. Microscopically, the adjacent grain arrangements and their interactions account for the stress concentration. In addition, different sets of grain orientations with the same total grain numbers of 150 were generated using the present model. Results show that different sets have significant influence on the distribution of stresses between each individual grain at the meso-scale, although little effect is found on the macroscopic length-scale.