Interparticle Interactions Research Articles

Rheological behaviors of Na-montmorillonite considering particle interactions: A molecular dynamics study

Understanding the rheology of bentonite suspensions is crucial for ensuring the safety of engineering practices. However, the rheological mechanisms of bentonite remain unclear due to the limitations of conventional experimental techniques, particularly in assessing the microscopic interactions between clay particles and their impact on rheological properties. In this paper, the rheological behaviors of Na-montmorillonite were studied with a focus on interparticle interactions. Both equilibrium molecular dynamics (MD) and non-equilibrium MD simulations were conducted to understand the physical properties of Na-montmorillonite under zero shear and various shear rates, respectively. The interaction between two parallel clay particles was determined in simulations, indicating that the classical Darjaguin-Landau-Verwey-Overbeek (DLVO) theory underestimates the interactions for a small separation distance. Na-montmorillonite exhibits a typical shear thinning behavior under shearing. However, as water content increases, it begins to behave more like liquid water. The yield stress of montmorillonite, as determined by the Bingham model, was found to be linearly related to the interaction pressures between clay particles. Besides MD simulations, the microstructure of clay suspension was further quantified using the separation distance and incline angle between non-parallel clay particles. Based on MD results and the quantified clay structure, a model was developed to estimate the yield stress of montmorillonite considering various influence factors, including electrolyte concentration, temperature, and solid fraction. Finally, from a comparison with calculated and experimental data, the results confirm the good performance of the proposed model. These findings provide significant insights for understanding the rheological soil behaviors and evaluating the yield stress of bentonite suspensions.

Nonlinear response theory of molecular machines

Chemical affinities are responsible for driving active matter systems out of equilibrium. At the nano-scale, molecular machines interact with the surrounding environment and are subjected to external forces. The mechano-chemical coupling which arises naturally in these systems reveals a complex interplay between chemical and mechanical degrees of freedom with strong impact on their active mechanism. By considering various models far from equilibrium, we show that the tuning of applied forces gives rise to a nonlinear response that causes a non-monotonic behaviour in the machines’ activity. Our findings have implications in understanding, designing, and triggering such processes by controlled application of external fields, including the collective dynamics of larger non-equilibrium systems where the total dissipation and performance might be affected by internal and inter-particle interactions.

Functional Noncentrosymmetric Nanoparticle-Nanofiber Hybrids via Selective Fragmentation.

Noncentrosymmetric nanostructures are an attractive synthetic target as they can exhibit complex interparticle interactions useful for numerous applications. However, generating uniform, colloidally stable, noncentrosymmetric nanoparticles with low aspect ratios is a significant challenge using solution self-assembly approaches. Herein, we outline the synthesis of noncentrosymmetric multiblock co-nanofibers by subsequent living crystallization-driven self-assembly of block co-polymers, spatially confined attachment of nanoparticles, and localized nanofiber fragmentation. Using this strategy, we have fabricated uniform diblock and triblock noncentrosymmetric π-conjugated nanofiber-nanoparticle hybrid structures. Additionally, in contrast to Brownian motion typical of centrosymmetric nanoparticles, we demonstrated that these noncentrosymmetric nanofibers undergo ballistic motion in the presence of H2O2 and thus could be employed as nanomotors in various applications, including drug delivery and environmental remediation.

Enhancing colloidal stability of nanodiamond via surface modification with dendritic molecules for optical sensing in physiological environments

Pre-treatment of diamond surface in low-temperature plasma for oxygenation and in acids for carboxylation was hypothesized to promote the branching density of the hyperbranched glycidol polymer. This was expected to increase the homogeneity of the branching level and suppress interactions with proteins. As a result, composite nanodiamonds with reduced hydrodynamic diameters that are maintained in physiological environments were anticipated. Surfaces of 140-nm-sized nanodiamonds were functionalized with oxygen and carboxyl groups for grafting of hyperbranched dendritic polyglycerol via anionic ring-opening polymerization of glycidol. The modification was verified with Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Dynamic light scattering investigated colloidal stability in pH-diverse (2–12) solutions, concentrated phosphate-buffered saline, and cell culture media. Thermogravimetric analysis of nanodiamonds-protein incubations examined non-specific binding. Fluorescence emission was tested across pH conditions. Molecular dynamics simulations modeled interparticle interactions in ionic solutions. The hyperbranched polyglycerol grafting increased colloidal stability of nanodiamonds across diverse pH, high ionic media like 10 × concentrated phosphate-buffered saline, and physiological media like serum and cell culture medium. The hyperbranched polyglycerol suppressed non-specific protein adsorption while maintaining intensive fluorescence of nanodiamonds regardless of pH. Molecular modelling indicated reduced interparticle interactions in ionic solutions correlating with the improved colloidal stability.

Enhancing interfacial elasticity via supramolecular microgel assembly for improved Pickering emulsions stability

We propose a new method to improve the interfacial elasticity of microgel-stabilised Pickering emulsions (PEs) by introducing supramolecular host-guest interactions to promote clustering among microgel particles. To this aim, microgels based on poly(N-isopropylacrylamide) (pNIPAM) are modified with 1-benzyl-3-vinylimidazolium bromide (BVI) to create pNIPAM-co-BVI microgels (MG). Cucurbit[8]uril (CB[8]) are introduced to form supramolecular BVI/CB[8] host-guest complexes. The introduction of CB[8] affects microgel spatial distribution at the interface of Pickering droplets, promoting the formation of monolayers of microgel clusters. These structures alter the interfacial viscoelasticity of the microgel monolayers, enhancing the resistance of (MG+CB[8])-stabilised interfaces to lateral and dilational deformations. PEs stabilised by microgels with the presence of CB[8] host-guest interactions exhibit improved stability over time. These results show the possibility of tuning the interfacial properties of microgel-laden interfaces by introducing supramolecular ternary complexes that can solely alter the interparticle interactions among microgels without significantly changing their morphology and deformability at the interface, thus providing a new route for improved emulsion stabilisation.

Tuning the Superspin Dynamics in Inverse Spinel Ferrite Nanoparticle Ensembles via Indirect Cation Substitution

We used magnetic and synchrotron X-ray diffraction measurements to investigate the possibility of tuning the strength of magnetic interparticle interactions in nanoparticle ensembles via chemical manipulation. Our main result comes from temperature-resolved in-phase ac-susceptibility data collected on 8 nm average-diameter Ni0.25Zn0.75Fe2O4 (Ni25) and Ni0.5Zn0.5Fe2O4 (Ni50) nanoparticles at different frequencies, χ′ vs. T|f. We found that the relative peak temperature variation per frequency decade, ϕ=∆TT·∆log(f)—a known measure of interparticle interaction strength—exhibits a four-fold increase, from ϕ = 0.04 in Ni50 to ϕ = 0.16 in Ni25. This corresponds to a fundamental change in the nanoparticles’ superspin dynamics, as proven by the fit of phenomenological models to magnetic relaxation data. Indeed, the Ni25 ensemble exhibits superparamagnetic behavior, where the temperature dependence of the superspin relaxation time, τ, is described in the Dorman–Bessais–Fiorani (DBF) model: τT=τrexp⁡EB+EadkBT, with parameters τr = 4 × 10−12 s, and (EB + Ead)/kB = 1473 K. On the other hand, the nanoparticles in the Ni50 ensemble freeze collectively upon cooling in a spin-glass fashion according to a critical dynamics law: τ(T)=τ0TTg−1zν, with τ0 = 4 × 10−8 s, Tg = 145 K, and zν = 7.2. Rietveld refinements against powder X-ray diffraction data reveal the structural details that underlie the observed magnetic behavior: an indirect cation replacement mechanism by which non-magnetic Zn ions are incorporated in the tetrahedral sites of the inverse spinel.

An integrated DEM code for tracing the entire regolith mass movement on asteroids

ABSTRACT This paper presents a general strategy for tracking the scale-span movement process of asteroid regolith materials. It achieves the tracking of the mass movement on the asteroid at a realistic scale, under conditions of high-resolution asteroid surface topography (submeter level) and actual regolith particle sizes. To overcome the memory exponential expansion caused by the enlarged computational domain, we improved the conventional cell-linked list method so that it can be applied to arbitrarily large computational domains around asteroids. An efficient contact detection algorithm for particles and polyhedral shape models of asteroids is presented, which avoids traversing all surface triangles and thus allows us to model high-resolution surface topography. A parallel algorithm based on Compute Unified Device Architecture for the gravitational field of the asteroid is presented. Leveraging heterogeneous computing features, further architectural optimization overlaps computations of the long-range and short-range interactions, resulting in an approaching doubling of computational efficiency compared to the code lacking architectural optimizations. Using the above strategy, a specific high-fidelity discrete element method code that integrates key mechanical models, including the irregular gravitational field, the interparticle and particle-surface interactions, and the coupled dynamics between the particles and the asteroid, is developed to track the asteroid regolith mass movement. As tests, we simulated the landslide of a sand pile on the asteroid’s surface during spin-up. The simulation results demonstrate that the code can track the mass movement of the regolith particles on the surface of the asteroid from local landslides to mass leakage with good accuracy.

Interactions Enable Thouless Pumping in a Nonsliding Lattice

A topological “Thouless” pump represents the quantized motion of particles in response to a slow, cyclic modulation of external control parameters. The Thouless pump, like the quantum Hall effect, is of fundamental interest in physics, because it links physically measurable quantities, such as particle currents, to geometric properties of the experimental system, which can be robust against perturbations and, thus, technologically useful. So far, experiments probing the interplay between topology and interparticle interactions have remained relatively scarce. Here, we observe a Thouless-type charge pump in which the particle current and its directionality inherently rely on the presence of strong interactions. Experimentally, we utilize a two-component Fermi gas in a dynamical superlattice which does not exhibit a sliding motion and remains trivial in the single-particle regime. However, when tuning interparticle interactions from zero to positive values, the system undergoes a transition from being stationary to drifting in one direction, consistent with quantized pumping in the first cycle. Remarkably, the topology of the interacting pump trajectory cannot be adiabatically connected to a noninteracting limit, highlighted by the fact that only one atom is transferred per cycle. Our experiments suggest that Thouless charge pumps are promising platforms to gain insights into interaction-driven topological transitions and topological quantum matter. Published by the American Physical Society 2024

Application of the Fenton reaction in silicon carbide polishing and its oxidative active center

The Fenton reaction is known for generating highly reactive hydroxyl radicals that are applied to accelerate the polishing removal rate of chemically inert SiC substrates. However, previous research primarily focuses on the polishing removal rate acceleration on the C surfaces of SiC substrates, and very limited studies have been conducted to investigate whether the hydroxyl radicals produced by the Fenton reaction serve as the primary agents of oxidative activity. Furthermore, the oxidation ability of hydroxyl radicals on the C surface and its relationship with their concentration are still not well-established. Therefore, more extensive research is needed to gain comprehensive understanding on the role of hydroxyl radicals in the oxidative activity on the C surface and their concentration-dependent effects. In this study, the polishing results of alumina, cerium oxide, and silica containing polishing slurries with and without Fenton reaction were compared and analyzed. The material removal rate (MRR) of the C surfaces of SiC substrates was significantly improved after the introduction of the Fenton reaction in alumina-containing slurry at pH 4, resulting in a smoother surface. Low-field nuclear magnetism, atomic force microscopy (AFM), ultraviolet spectrophotometry, and X-ray photoelectron spectroscopy (XPS) were employed to gain insights on inter-particle interactions and oxidation mechanisms of C face of SiC in presence of Fenton reaction. The results revealed that while hydroxyl radicals demonstrated potent oxidation ability, they alone were incapable of oxidizing C face of SiC.

In Situ Tracking of Water Oxidation Generated Nanoscale Dynamics in Layered Double Hydroxides Nanosheets.

Layered double hydroxides (LDHs) are potential catalysts for water oxidation, and it is recognized that they undergo dynamic evolution during the operation. However, little is known about the interfacial behaviors at the nanoscale under working conditions nor the underlying effects on electrocatalytic performance. Herein, using electrochemical atomic force microscopy, we in situ visualize the heterogeneous evolution of LDH nanosheets during oxygen evolution reaction (OER). By further combining density functional theory calculations, we elucidate the origin of the heterogeneous dynamics and their impact on the OER efficiency. Our findings demonstrate that NiCo LDHs transform to the catalytically active NiCoOx(OH)2-x phase during OER, and the redox transition between is accompanied by compressive and tensile strain, leading to in-plane contraction and reversible expansion of the nanosheets. Nonisotropic strain and out-of-plane strain relaxation due to defects and interparticle interactions result in cracking and wrinkling in the nanostructure, which is responsible for the partial activation and long-term deterioration of LDH electrocatalysts toward the OER. With this knowledge, we suggest and validate that engineering defects can precisely tune these dynamic behaviors, improving the OER activity and stability among LDH-based electrocatalysts.

A new discrete element method for small adhesive non-spherical particles

Small adhesive particles with non-spherical shapes are common in natural and industrial processes. However, it is challenging to accurately simulate the dynamic behaviors of non-spherical particulate systems, not only due to the complex local geometry at the contact region but also to the non-linear coupling between the van der Waals adhesion and the elastic deformation. In this paper, we develop a discrete element method (DEM) framework for small non-spherical particles. Particularly, we present a simple algorithm for solving the implicit equations of the dimensionless generalized JKR model, to accurately resolve the local surface geometry at the contact region and the strong coupling between the elastic deformation and the surface adhesion. New explicit expressions are established for the pull-off force, overlap and minor-to-major ratio of the contact ellipse, to naturally capture the pull-off point upon collision. Then the actual contact parameters including the contact radius, curvatures and overlap are used to modify the interparticle interactions, including the normal elastic-adhesive-dissipative force and sliding-rolling-twisting resistances. Finally, the framework is quantitatively validated by four random packing problems, including adhesive spheres, ellipsoids, spherocylinders and dimers, and the representative non-adhesive ellipsoids. Both the microscopic and macroscopic properties of packings agree well with a large number of classic theories, experiments and simulations, showing the satisfactory accuracy and effectiveness. The newly developed adhesive DEM framework has the full capability to dynamically simulate the collision-related behaviors of complex shaped particles in the presence of van der Waals adhesion and frictional forces.

Digital design and manufacturing of microstructural granular materials

Particulate materials in granular forms are commonly used in industry such as pharmaceutical tablets, energy storage composites, and energetic materials. The microstructures affect product performance during particulate material handling, such as breakage characteristics, and flow permeability. It is essential to establish numerical models to understand complex multi-physics mechanisms in this field. Discrete Element Method (DEM) simulations were commonly used with proper definition of the inter-particle interactions. Recently novel research has been devoted to utilizing machine learning to investigate the effect of granular material microstructures. This paper highlights potential applications of hybrid physics modeling and machine learning approaches for digital design of granular materials. Additionally, potential fabrication techniques especially additive manufacturing are discussed to materialize the digital design of granular materials.

Superadiabatic dynamical density functional theory for colloidal suspensions under homogeneous steady-shear.

The superadiabatic dynamical density functional theory (superadiabatic-DDFT) is a promising new method for the study of colloidal systems out-of-equilibrium. Within this approach, the viscous forces arising from interparticle interactions are accounted for in a natural way by explicitly treating the dynamics of the two-body correlations. For bulk systems subject to spatially homogeneous shear, we use the superadiabatic-DDFT framework to calculate the steady-state pair distribution function and the corresponding viscosity for low values of the shear-rate. We then consider a variant of the central approximation underlying this superadiabatic theory and obtain an inhomogeneous generalization of a rheological bulk theory due to Russel and Gast. This paper thus establishes for the first time a connection between DDFT approaches, formulated to treat inhomogeneous systems, and existing work addressing nonequilibrium microstructure and rheology in bulk colloidal suspensions.

Numerical study on collapsing cavitation bubble dynamics in cryogenic fluids

The paper addresses the implementation of a dual distribution function multiphase lattice Boltzmann method (DDF-MLBM) for studying the collapse of cavitation bubbles in cryogenic liquids. The present scheme incorporates the energy equation and imposes interparticle interactions and fluid–solid adhesive forces through the exact difference method (EDM). To accurately model phase changes and the molecular complexities of cryogenic fluids like liquid hydrogen (LH2) and liquid nitrogen (LN2), the Peng-Robinson (PR) equation of state is employed along with an acentric factor. The accuracy of the present numerical technique is evaluated using the Laplace law and the Maxwell equal area construction theorem for a two-phase liquid–vapor system in equilibrium. For transient solutions, the study compares results of heterogeneous cavitation with the analytical solution derived from the thermal Rayleigh-Plesset equation. The research investigates the impact of the distance between a cavitation bubble with an adjacent solid wall on velocity, pressure, temperature, and collapse time. Furthermore, it is assessed how surface wettability influences cavitation bubble collapse intensity. Additionally, the paper examines the collapse of a cavitation bubble cluster and evaluates the effects of different physical parameters on the collapse properties of the bubble cluster. The results underscore the significant influence of the distance between cavitation bubbles in the cluster, the distance between bubbles and the adjacent solid surface on the micro-jet velocity. Moreover, it is found that increasing the contact angle of the solid surface enhances the collapse intensity and micro-jet velocity of the collapsing bubble cluster.

Effect of time-dependent inter-particle interaction on the dynamics of a dissipative double-well Bose-Einstein condensate

Effect of time-dependent inter-particle interaction on the dynamics of a dissipative double-well Bose-Einstein condensate

Unified Understanding of the Structure, Thermodynamics, and Diffusion of Single-Chain Nanoparticle Fluids.

Single-chain nanoparticles (SCNPs) are a fascinating class of soft nano-objects with promising properties and relevance to protein condensates, polymer nanocomposites, nanomedicine, bioimaging, catalysis, and drug delivery. We combine molecular dynamics simulations and equilibrium and time-dependent statistical mechanical theory to construct a unified understanding of how the internal conformational structure of SCNPs, of both a simple fractal globule-like form and more complex objects with multiple internal intermediate length scales, determines nm-scale intermolecular packing correlations, thermodynamic properties, and center-of-mass diffusion over a wide range of concentrations up to dense melts. The intermolecular pair correlations generically exhibit a distinctive deep correlation hole form due to SCNP internal connectivity structure and repulsive interparticle interactions associated with a globular-like conformation on the macromolecular scale, with concentration-dependent deviations at small separations. Unanticipated exponential-like dependences of the equation-of-state, osmotic compressibility, and center-of-mass diffusion constant on SCNP macromolecular packing fraction are theoretically predicted and confirmed via simulations. System-specific behaviors are found associated with SCNP internal structure, but overarching regularities are identified and understood based on a generalized effective globule conformation on macromolecular scales. Diffusivity slows down by 2-3 decades with increasing concentration and is understood as a consequence of a nonactivated excluded volume-driven weak-caging process associated with space-time correlated intermolecular forces experienced by the SCNP. Good agreement between the theory and simulations is established, testable predictions are made, and a quantitative comparison with viscosity measurements on a specific SCNP fluid is carried out. The basic theoretical approach can potentially be extended to treat the chemical and physical consequences of varying the structure of other classes of soft nanoparticles with distinctive internal nanoscale organization relevant in nanotechnology and nanomedicine, and the possible emergence of macromolecular kinetically arrested glasses.

A novel interpretation of pH-dependent microstructure and rheology evolution in silica suspension based on interparticle interactions

A novel interpretation of pH-dependent microstructure and rheology evolution in silica suspension based on interparticle interactions

Emergent dynamics: Collective motions of polar active particles on surfaces

In this study, we focus on the collective dynamics of polar active particles navigating across three distinct surfaces, each characterized by its own unique blend of topological and geometrical properties. The behavior of these active particles is influenced by a multitude of factors, including self-propulsion, inter-particle interactions, surface constraints, and under-damped stochastic forces simulated via Ornstein–Uhlenbeck processes. Our exploration unveils the prevailing collective patterns observed within these systems across three surface types: a sphere, a torus, and a landscape featuring hills and valleys, each distinguished by its specific topological and geometrical attributes. We underscore the profound impact of surface curvature and symmetry on the sustainable spatial-temporal dynamics witnessed. Our findings illuminate how the interplay between substantial surface curvature and particular symmetrical characteristics gives rise to a diverse spectrum of spatial-temporal patterns. Notably, we discern that high curvature tends to drive collective motion toward cyclic rotation on spheres and tori, or spatial-temporal periodic traveling ring patterns on landscapes with hills and valleys. Additionally, we observe that rough surfaces and the incorporation of excluded volume effects can disrupt the complexity of these collective spatial-temporal patterns. Through this investigation, we provide invaluable insight into the intricate interplay of curvature and symmetry, profoundly shaping collective behaviors among active particles across varied surfaces.

A finite-time quantum Otto engine with tunnel coupled one-dimensional Bose gases

We undertake a theoretical study of a finite-time quantum Otto engine cycle driven by inter-particle interactions in a weakly interacting one-dimensional (1D) Bose gas in the quasicondensate regime. Utilizing a c-field approach, we simulate the entire Otto cycle, i.e. the two work strokes and the two equilibration strokes. More specifically, the interaction-induced work strokes are modelled by treating the working fluid as an isolated quantum many-body system undergoing unitary evolution. The equilibration strokes, on the other hand, are modelled by treating the working fluid as an open quantum system tunnel-coupled to another quasicondensate which acts as either the hot or cold reservoir, albeit of finite size. We find that, unlike a uniform 1D Bose gas, a harmonically trapped quasicondensate cannot operate purely as a heat engine; instead, the engine operation is enabled by additional chemical work performed on the working fluid, facilitated by the inflow of particles from the hot reservoir. The microscopic treatment of dynamics during equilibration strokes enables us to evaluate the characteristic operational time scales of this Otto thermochemical engine, crucial for characterizing its power output, without any ad hoc assumptions about typical thermalization timescales. We analyse the performance and quantify the figures of merit of the proposed Otto thermochemical engine, finding that it offers a favourable trade-off between efficiency and power output, particularly when the interaction-induced work strokes are implemented via a sudden quench. We further demonstrate that in the sudden quench regime, the engine operates with an efficiency close to the near-adiabatic (near maximum efficiency) limit, while concurrently achieving maximum power output.

Superfluid excitations in rotating two-dimensional ring traps

We studied a rotating Bose–Einstein condensate confined in ring trap configurations that can be produced starting with a bubble trap confinement, approximated by a Mexican hat and shift harmonic oscillator potentials. Using a variational technique and perturbation theory, we determined the vortex configurations in this system by varying the interparticle interaction and the angular velocity of the atomic cloud. We found that the phase diagram of the system has macrovortex structures for small positive values of the interaction parameter, and the charge of the central vortex increases with rotation. Strengthening the atomic interaction makes the macrovortex unstable, and it decays into multiple singly charged vortices that arrange themselves in a lattice configuration. We also look for experimentally realizable methods to determine the vortex configuration without relying upon absorption imaging since the structures are not always visible in the latter. More specifically, we study how the vortex distribution affects the collective modes of the condensate by solving the Gross–Pitaevskii equation numerically and by analytical predictions using the sum-rule approach for the frequencies of the modes. These results reveal important signatures to characterize the macrovortices and vortex lattice transitions in the experiments.