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All sources NASA NTRS DOE OSTI

DOE OSTI2018

A Highly Stretchy, Transparent Elastomer with the Capability to Automatically Self-Heal Underwater

Polymer materials that are able to self-heal in humid conditions or even in water are highly desirable for their industrial applications. However, the development of underwater self-healing polymer materials is very challenging since water molecules can readily disturb traditional noncovalent bonds, such as saturate the hydrogen bonds, coordinate with the metal cation, as well as solvate the ions. Here, a new type of dipole–dipole interactions is employed as the driving force, combining with highly polar and hydrophobic fluorinated polymers, to successfully demonstrate an underwater self-healing elastomer. Additionally, the polymer materials are transparent and stretchable. They can remain stable underwater for months without significant decay of mechanical properties. Upon mechanical damage, the material is able to self-heal automatically in air, underwater, and under very harsh aqueous conditions (including seawater, highly acidic media, and highly basic media, etc.).

36 MATERIALS SCIENCE↗

DOE OSTI2019

Conformational Equilibria of Multimodal Chromatography Ligands in Water and Bound to Protein Surfaces

Multimodal chromatography uses small ligands with multiple modes of interaction, e.g., charged, hydrophobic or hydrogen bonding, to separate proteins from complex mixtures. The mechanism by which multimodal ligands interact with proteins is expected to be affected by ligand conformations, among other factors. In this report, we determine conformational equilibria of two commercially used multimodal cation exchange ligands, Capto MMC and Nuvia cPrime, in a range of solvents, a Lennard-Jones (LJ) liquid, ethanol, and water, using molecular dynamics (MD) simulations. By mapping ligand conformations onto two key torsion angles, ω and φ, in these solvents and in low and high dielectric media, we quantify the relative importance of intramolecular and solvent-mediated interactions. In a high dielectric medium, Capto MMC preferentially samples three conformations, which are stabilized by a combination of an intramolecular torsion potential (on ω) and LJ interactions. In an LJ liquid, solvent molecules compete with intramolecular interactions while simultaneously providing an osmotic force, stabilizing both closer and farther distances between ligand sites. This has the overall result of “flattening out” the conformational landscape. Interestingly, in ethanol and water, hydrogen bonding among the amide hydrogen and solvent molecules stabilizes two additional conformations of Capto MMC in which ω takes on less favorable cis-like configurations. MD simulations of ligands in free solution with three therapeutic antibody fragments show that ligand conformational equilibria remain effectively unchanged upon binding to proteins. Although, there is 20–30% dehydration of the overall ligand upon binding, the hydrogen-bonding sites are dehydrated to a much smaller extent, particularly in cis-like configurations. Conformational preferences of Nuvia cPrime are similar to that of Capto MMC, except for the effect of symmetry arising from the absence of an alkyl thiol tail. Characterizing the conformational equilibria of these two ligands in free solution and bound to a protein provides a foundation for developing a mechanistic understanding of protein–multimodal ligand interactions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Correlating inter-particle forces and particle shape to shear-induced aggregation/fragmentation and rheology for dilute anisotropic particle suspensions: A complementary study via capillary rheometry and in-situ small and ultra-small angle X-ray scattering

Predicting the stability of suspensions composed of anisotropic particles is difficult due to the complexity and interplay of hydrodynamic and colloidal forces. For example, it is not well understood how non-spherical particle shapes affect suspension-rheological responses. This study presents evidence showing how the stacking of boehmite platelets dispersed in aqueous solution leads to moderate shear thinning, even at low boehmite mass fractions. Wide angle X-ray, small angle X-ray, and ultra-small angle X-ray scattering were used to simultaneously monitor changes to the size and fractal dimensions of boehmite aggregates from 6 – 10,000 Å as the sample was recirculated through an in situ capillary rheometer. The latter also provided simultaneous measurements of the viscosity of the suspensions. Computational fluid dynamics modeling of the apparatus was used to provide a more rigorous analysis of the fluid flow. In addition to shear-induced aggregation/fragmentation correlated to a complicated balance between hydrodynamic and colloidal forces, the results indicate that orientationally-dependent interactions, arising from non-spherical boehmite aggregate sub-units, may explain the relatively large experimental viscosity when the hydrodynamic force is small compared to colloidal forces. Ultimately, the results from this study can provide a foundation for future work investigating particle shape effects on colloidal and hydrodynamics forces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Chemical Phenomena of Atomic Force Microscopy Scanning

Atomic force microscopy is widely used for nanoscale characterization of materials by scientists worldwide. The long-held belief of ambient AFM is that the tip is generally chemically inert but can be functionalized with respect to the studied sample. This implies that basic imaging and scanning procedures do not affect surface and bulk chemistry of the studied sample. However, an in-depth study of the confined chemical processes taking place at the tip–surface junction and the associated chemical changes to the material surface have been missing as of now. Here, we used a hybrid system that combines time-of-flight secondary ion mass spectrometry with an atomic force microscopy to investigate the chemical interactions that take place at the tip–surface junction. Investigations showed that even basic contact mode AFM scanning is able to modify the surface of the studied sample. In particular, we found that the silicone oils deposited from the AFM tip into the scanned regions and spread to distances exceeding 15 μm from the tip. These oils were determined to come from standard gel boxes used for the storage of the tips. In conclusion, the explored phenomena are important for interpreting and understanding results of AFM mechanical and electrical studies relying on the state of the tip–surface junction.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Layered Atlantic Smoke Interactions with Clouds (LASIC) Field Campaign Report

Southern Africa is the world’s largest emitter of biomass burning aerosols. Their westward transport over the remote southeast Atlantic Ocean co-locates some of the largest atmospheric loadings of absorbing aerosol with the least examined of the Earth’s major subtropical stratocumulus decks. Global aerosol model results highlight that the largest positive top-of-atmosphere (TOA) forcing in the world occurs in the southeast Atlantic, but this region exhibits large differences in magnitude and sign between reputable models, in part because of high variability in the underlying model cloud distributions. Many uncertainties contribute to the highly variable model radiation fields: the aging of the shortwave-absorbing aerosol during transport, how much of the aerosol mixes into the cloudy boundary layer, and how the low clouds adjust to smoke-radiation and smoke-cloud interactions. In addition, the ability of the biomass burning aerosol to absorb shortwave radiation is known to vary seasonally as the fuel type on land changes. LASIC (Layered Atlantic Smoke Interactions with Clouds) is a strategy to improve our understanding of aged carbonaceous aerosol, its seasonal evolution, and the mechanisms by which clouds adjust to the presence of the aerosol. The observational strategy centers on deploying the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility first ARM Mobile Facility (AMF1) cloud, aerosol, and atmospheric profiling instrumentation to Ascension Island, located within the trade-wind shallow cumulus regime (14.50W, 80S) 3000 km offshore of continental Africa. The location is within the latitude zone of the maximum outflow of aerosol, with the deepening boundary layer known to entrain free-tropospheric smoke. The primary activities for LASIC are: 1) to improve current knowledge on aged biomass burning aerosol and its radiative properties as a function of the seasonal cycle; 2) to use surface-based remote sensing to sensitively interrogate the atmosphere for the relative vertical location of aerosol and clouds; 3) to improve our understanding of the cloud adjustments to the presence of shortwave-absorbing aerosol within the vertical column, both through aerosol-radiation and through aerosol-cloud interactions; 4) to aid low cloud parameterization efforts for climate models. The measurements span June 1, 2016-October 31, 2017, encompassing two July-October biomass burning seasons. The August-September, 2016, months include an intensive operational period (IOP) with 8x/daily radiosondes. In 2017, from 16 August through 7 September, the United Kingdom Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 plane was deployed from Ascension, providing complementary data on the atmosphere’s vertical structure as part of the Cloud-Aerosol-Radiation Interactions and Forcing (CLARIFY) project, with similar scientific goals. The National Aeronautics and Space Administration (NASA) Observations of Clouds above Aerosols and their Interactions (ORACLES) aircraft campaign, sharing similar objectives to LASIC, deployed from Namibia in September, 2016, and Sao Tome in August, 2017. The latter included a suitcase flight to Ascension spanning August 18-21. In 2017 a cavity-attenuated phase shift single-scattering albedo (CAPS-SSA) instrument belonging to Aerodyne was brought to Ascension, gathering data primarily for August, towards providing a second, independent measurement of aerosol absorption. Ascension Island is also an Aerosol Robotic Network (AERONET) site.

biomass burning, aerosols, black carbon, boundary-↗

DOE OSTI2019

Laboratory Studies of Cloud Particle Formation, Mixing State, and Physiochemical and Optical Properties of Carbonaceous Aerosols

Aerosol particles affect climate through direct and indirect interactions. In direct interactions, non-absorbing particles such as sulfate aerosols, backscatter solar radiation to space, leading to atmospheric cooling. By contrast, particles containing absorbing material such as refractory black carbon (rBC) produced during incomplete fuel combustion and to some extent also brown carbon components of biomass burning organic aerosol (BBOA) and secondary organic aerosol (SOA), absorb incoming solar radiation leading to atmospheric warming. Indirect effects include the ability of aerosol particles to alter the formation and properties of liquid water clouds (acting as cloud condensation nuclei or CCN) and ice clouds (acting as ice nuclei or IN), thereby affecting cloud albedo, coverage and lifetimes. The largest uncertainty in the modeling of climate impacts due to radiative forcing is caused by inadequate representation of aerosol-cloud interactions. The total radiative forcing on climate due to aerosol particles may be as large as that of the greenhouse gases, but predominantly opposite in sign (in the direction of cooling) and much more uncertain. All the direct and indirect radiative forcing effects may be influenced by the chemical composition of the particles.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2023

Effects of Forcing Differences and Initial Conditions on Inter-Model Agreement in the VolMIP Volc-Pinatubo-Full Experiment

This paper provides initial results from a multi-model ensemble analysis based on the volc-pinatubo-full experiment performed within the Model Intercomparison Project on the climatic response to Volcanic forcing (VolMIP) as part of the sixth phase of the Coupled Model Intercomparison Project (CMIP6). The volc-pinatubo-full experiment is based on an ensemble of volcanic forcing-only climate simulations with the same volcanic aerosol dataset across the participating models (the 1991–1993 Pinatubo period from the CMIP6-GloSSAC dataset). The simulations are conducted within an idealized experimental design where initial states are sampled consistently across models from the CMIP6-piControl simulation providing unperturbed preindustrial background conditions. The multi-model ensemble includes output from an initial set of six participating Earth system models (CanESM5, GISS-E2.1-G, IPSL-CM6A-LR, MIROC-E2SL, MPI-ESM1.2-LR and UKESM1). The results show overall good agreement between the different models on the global and hemispheric scales concerning the surface climate responses, thus demonstrating the overall effectiveness of VolMIP's experimental design. However, small yet significant inter-model discrepancies are found in radiative fluxes, especially in the tropics, that preliminary analyses link with minor differences in forcing implementation; model physics, notably aerosol–radiation interactions; the simulation and sampling of El Niño–Southern Oscillation (ENSO); and, possibly, the simulation of climate feedbacks operating in the tropics. We discuss the volc-pinatubo-full protocol and highlight the advantages of volcanic forcing experiments defined within a carefully designed protocol with respect to emerging modelling approaches based on large ensemble transient simulations. We identify how the VolMIP strategy could be improved in future phases of the initiative to ensure a cleaner sampling protocol with greater focus on the evolving state of ENSO in the pre-eruption period.

metadata↗

NASA NTRS2014

Abrupt Increases in Amazonian Tree Mortality Due to Drought-Fire Interactions

Interactions between climate and land-use change may drive widespread degradation of Amazonian forests. High-intensity fires associated with extreme weather events could accelerate this degradation by abruptly increasing tree mortality, but this process remains poorly understood. Here we present, to our knowledge, the first field-based evidence of a tipping point in Amazon forests due to altered fire regimes. Based on results of a large-scale, longterm experiment with annual and triennial burn regimes (B1yr and B3yr, respectively) in the Amazon, we found abrupt increases in fire-induced tree mortality (226 and 462%) during a severe drought event, when fuel loads and air temperatures were substantially higher and relative humidity was lower than long-term averages. This threshold mortality response had a cascading effect, causing sharp declines in canopy cover (23 and 31%) and aboveground live biomass (12 and 30%) and favoring widespread invasion by flammable grasses across the forest edge area (80 and 63%), where fires were most intense (e.g., 220 and 820 kW x m(exp −1)). During the droughts of 2007 and 2010, regional forest fires burned 12 and 5% of southeastern Amazon forests, respectively, compared with less than 1% in nondrought years. These results show that a few extreme drought events, coupled with forest fragmentation and anthropogenic ignition sources, are already causing widespread fire-induced tree mortality and forest degradation across southeastern Amazon forests. Future projections of vegetation responses to climate change across drier portions of the Amazon require more than simulation of global climate forcing alone and must also include interactions of extreme weather events, fire, and land-use change.

MODIS↗

DOE OSTI2020

Implementing Chiral Three-Body Forces in Terms of Medium-Dependent Two-Body Forces

Three-nucleon (3N) forces are an indispensable ingredient for accurate few-body and many- body nuclear structure and reaction theory calculations. While the direct implementation of chiral 3N forces can be technically very challenging, a simpler approach is given by employing instead a medium-dependent NN interaction V med that reflects the physics of three-body forces at the two-body normal-ordered approximation. We review the derivation and construction of Vmed from the chiral 3N interaction at next-to-next-to-leading order (N2LO), consisting of a long-range 2π-exchange term, a mid-range 1π-exchange component and a short-range contact-term. Several applications of V med to the equation of state of cold nuclear and neutron matter, the nucleon single-particle potential in nuclear matter, and the nuclear quasiparticle interaction are discussed. We also explore differences in using local vs. nonlocal regulating functions on 3N forces and make direct comparisons to exact results at low order in perturbation theory expansions for the equation of state and single-particle potential. We end with a discussion and numerical calculation of the in-medium NN potential V med from the next-to-next-to-next-to-leading order (N3LO) chiral 3N force, which consists of a series of long-range and short-range terms.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Finite-temperature vibrational full configuration interaction

Thermodynamic functions of an ideal molecular gas due to its anharmonic vibrations are evaluated in a wide range of temperature (T) by the vibrational full-configuration-interaction (FCI) method using a quartic force field and a finite number (N) of harmonic-oscillator basis functions along each normal mode. The thermodynamic functions considered are the grand potential (Ω), internal energy (U), and entropy (S). They are compared with those obtained from the Bose–Einstein theory with or without truncation of the harmonic-oscillator basis functions after quantum number N–1. The comparison reveals that the finite-basis-set errors in Ω and U are, respectively, k B Tln(k B T/Nℏω) and k B T per mode in the high-T limit, obscuring anharmonic effects when k B T > ℏω, where ω is the lowest mode frequency. Here, the benchmark data for several low-order perturbation corrections to Ω, U, and S are also obtained as the numerical derivatives of their FCI values with respect to dimensionless perturbation strength, and the domain of T and N in which these data are reliable (for the N → ∞ limits) is discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2022

Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water

We study NaCl ion-pair dissociation in a dilute aqueous solution using computer simulations both for the full system with long-range Coulomb interactions and for a well-chosen reference system with short-range intermolecular interactions. Analyzing results using concepts from Local Molecular Field (LMF) theory and the recently proposed AI-based analysis tool “State predictive information bottleneck” (SPIB), we show that the system with short-range interactions can accurately reproduce the transition rate for the dissociation process, the dynamics for moving between the underlying metastable states, and the transition state ensemble. Contributions from long-range interactions can be largely neglected for these processes because long-range forces from the direct interionic Coulomb interactions are almost completely canceled (>90%) by those from solvent interactions over the length scale where the transition takes place. Thus, for this important monovalent ion-pair system, short-range forces alone are able to capture detailed consequences of the collective solvent motion, allowing the use of physically suggestive and computationally efficient short-range models for the dissociation event. Here, we believe that the framework here should be applicable to disentangling mechanisms for more complex processes such as multivalent ion disassociation, where previous work has suggested that long-range contributions may be more important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Transport methods and interactions for space radiations

A review of the program in space radiation protection at the Langley Research Center is given. The relevant Boltzmann equations are given with a discussion of approximation procedures for space applications. The interaction coefficients are related to solution of the many-body Schroedinger equation with nuclear and electromagnetic forces. Various solution techniques are discussed to obtain relevant interaction cross sections with extensive comparison with experiments. Solution techniques for the Boltzmann equations are discussed in detail. Transport computer code validation is discussed through analytical benchmarking, comparison with other codes, comparison with laboratory experiments and measurements in space. Applications to lunar and Mars missions are discussed.

Wilson, John W.↗

NASA NTRS1996

Non-linear resonance of fluids in a crystal growth cavity

In the microgravity environment, the effect of gravity on fluid motion is much reduced. Hence, secondary effects such as vibrations, jitters, surface tension, capillary effects, and electromagnetic forces become the dominant mechanism of fluid convection. Numerous studies have been conducted to investigate fluid behavior in microgravity with the ultimate goal of developing processes with minimal influence from convection. Industrial applications such as crystal growth from solidification of melt and protein growth for pharmatheutical application are just a few examples of the vast potential benefit that can be reaped from material processing in space. However, a space laboratory is not immune from all undesirable disturbances and it is imperative that such disturbances be well understood, quantifiable, and controlled. Non-uniform and transient accelerations such as vibrations, jitters, and impulsive accelerations exist as a result of crew activities, space vehicle maneuvering, and the operations of on-board equipment. Measurements conducted on-board a U.S. Spacelab showed the existence of vibrations in the frequency range of 1 to 100 Hz with a dominant mode of 17 Hz and harmonics of 54 Hz. The observed vibration is not limited to any coordinate plane but exists in all directions. Similar situation exists on-board the Russian MIR space station. Due to the large structure of its design, the future International Space Station will have its own characteristic vibration spectrum. It is well known that vibration can exert substantial influence on heat and mass transfer processes, thus hindering any attempts to achieve a diffusion-limited process. Experiments on vibration convection for a liquid-filled enclosure under one-g environment showed the existence of different flow regimes as vibration frequency and intensity changes. Results showed the existence of a resonant frequency, near which the enhancement is the strongest, and the existence of a high frequency asymptote. Numerical simulations of vibration convection have been conducted by Yurkov, Fu and Shieh, and by Wang. These analyses considered a two-dimensional air-filled cell under weightlessness condition and showed results similar to those of the experiments. It is not yet known whether resonance convection can be triggered by jitter alone or whether it requires the interaction of jitter with other convective forces in low gravity. An order of magnitude analysis, however, can be used to show the dependence of the resonance frequency on the fluid Prandtl number. Even though the onset of resonance convection may depend on other factors, results indicates that fluids with low Prandtl numbers are more susceptible to resonance than those with high Prandtl numbers. The current study is aimed at gaining additional insights to this problem using germanium as working fluid. Germanium was chosen for this analysis because of its common usage in solidification process and its relatively low Prandtl number (Pr = 0.02).

Wang, Francis C.↗

DOE OSTI2020

Structure and dynamics of hydrodynamically interacting finite-size Brownian particles in a spherical cavity: Spheres and cylinders

The structure and dynamics of confined suspensions of particles of arbitrary shape are of interest in multiple disciplines from biology to engineering. Theoretical studies are often limited by the complexity of long-range particle-particle and particle-wall forces, including many-body fluctuating hydrodynamic interactions. Here, we report a computational study on the diffusion of spherical and cylindrical particles confined in a spherical cavity. We rely on an immersed-boundary general geometry Ewald-like method to capture lubrication and long-range hydrodynamics and include appropriate non-slip conditions at the confining walls. A Chebyshev polynomial approximation is used to satisfy the fluctuation-dissipation theorem for the Brownian suspension. We explore how lubrication, long-range hydrodynamics, particle volume fraction, and shape affect the equilibrium structure and the diffusion of the particles. It is found that once the particle volume fraction is greater than 10%, the particles start to form layered aggregates that greatly influence particle dynamics. Hydrodynamic interactions strongly influence the particle diffusion by inducing spatially dependent short-time diffusion coefficients, stronger wall effects on the particle diffusion toward the walls, and a sub-diffusive regime-caused by crowding-in the long-time particle mobility. The level of asymmetry of the cylindrical particles considered here is enough to induce an orientational order in the layered structure, decreasing the diffusion rate and facilitating a transition to the crowded mobility regime at low particle concentrations. Our results offer fundamental insights into the diffusion and distribution of globular and fibrillar proteins inside cells.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Fluorophilic Sigma(σ)‐Lock Self‐Healable Copolymers

Abstract Although F‐Containing molecules and macromolecules are often used in molecular biology to increase the binding with Lewis acidic groups by introducing favorable C−F dipoles, there is virtually no experimental evidence and limited understanding of the nature of these interactions, especially their role in synthetic polymeric materials. These studies elucidate the molecular origin of inter‐ and intra‐Chain interactions responsible for self‐healing of F‐Containing copolymers composed of pentafluorostyrene and n‐butyl acrylate units (p(PFS/nBA). Guided by dynamic surface oscillating force (SOF) and spectroscopic measurements supported by molecular dynamics (MD) simulations, these studies show that the reformation of σ‐σ orbitals in −C−F of PFS and CH 3 CH 2 − of nBA units enables the recovery of entropic energy via fluorophilic‐σ‐lock van der Waals forces when PFS/nBA molar ratios are ~50/50. The strength of these interactions determined experimentally for self‐healable PFS/nBA compositions is in the order ~0.3 kcal/mol which primarily comes from fluorophilic‐σ‐lock (~70 %) contributions. These interactions are significantly diminished for non‐self‐healable counterparts. Strongly polarized −C−F σ orbitals create lateral dipolar forces enhancing the affinity towards −C−H orbitals, facilitating energetically favorable interactions. Entropic recovery driven by non‐Covalent bonding offers a valuable tool in designing materials with unique functionalities, particularly self‐healable batteries and energy storage devices.

Gaikwad, Samruddhi↗

DOE OSTI2021

Hidden Spin-Isospin Exchange Symmetry

The strong interactions among nucleons have an approximate spin-isospin exchange symmetry that arises from the properties of quantum chromodynamics in the limit of many colors, N c . However this large- N c symmetry is well hidden and reveals itself only when averaging over intrinsic spin orientations. Furthermore, the symmetry is obscured unless the momentum resolution scale is close to an optimal scale that we call Λ large-N c . We show that the large-N c derivation requires a momentum resolution scale of Λ large-N c ~ 500 MeV. We derive a set of spin-isospin exchange sum rules and discuss implications for the spectrum of 30 P and applications to nuclear forces, nuclear structure calculations, and three-nucleon interactions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1980

Plasma double-layers produced by ponderomotive force

Non-linear rectification of the RF electric fields excited in a convectively amplifying electron beam-plasma interaction results in a dc electric field, and a corresponding ponderomotive force acting on the charged particles to produce a space-charge separation, i.e. a type of plasma double-layer. This paper analyses the effect, taking into account plasma electron temperature and electron-neutral collisions. To measure such double-layers, an electron beam probe constitutes a convenient non-perturbing diagnostic technique, but great care is required in its calibration. An analysis is presented taking into account significant non-linear effects which had been neglected in previous work. The paper concludes with some preliminary experimental results illustrating the use of the technique in a beam-plasma interaction for which a weak double-layer electric field is predicted.

Levine, J. S.↗

DOE OSTI2022

Crystallization pathways and interfacial drivers for the formation of hierarchical architectures

The development of structural hierarchy on various length scales during crystallization process is ubiquitous in biological systems and is also observed in synthetic nanomaterials. The driving forces for the formations of complex architectures range from local interfacial interactions, that modify interfacial speciation, local supersaturation, and nucleation barriers, to macroscopic interparticle forces. Although it is enticing to interpret the formation of hierarchical architectures as the assembly of independently nucleated building blocks, often crystallization pathways follow monomer-by-monomer addition with structural complexity arising from interfacial chemical coupling and strongly correlated fluctuation dynamics in the electric double layers. Here, the mechanism of the development of structural hierarchy through heterogeneous nucleation, coupled interfacial nucleation and assembly, and oriented attachment of independently nucleated particles is discussed. In this article, the emphasis is made on the discussion of the underlying interfacial forces and chemical coupling that drives crystallization pathways towards the formation of structural hierarchy.

36 MATERIALS SCIENCE↗