Thermodynamic driving forces in contact electrification between polymeric materials.

Contact electrification, or contact charging, refers to the process of static charge accumulation after rubbing, or even simple touching, of two materials. Despite its relevance in static electricity, various natural phenomena, and numerous technologies, contact charging remains poorly understood. For insulating materials, even the species of charge carrier may be unknown, and the direction of charge-transfer lacks firm molecular-level explanation. Here, we use all-atom molecular dynamics simulations to investigate whether thermodynamics can explain contact charging between insulating polymers. Based on prior work suggesting that water-ions, such as hydronium and hydroxide ions, are potential charge carriers, we predict preferred directions of charge-transfer between polymer surfaces according to the free energy of water-ions within water droplets on such surfaces. Broad agreement between our predictions and experimental triboelectric series indicate that thermodynamically driven ion-transfer likely influences contact charging of polymers. Furthermore, simulation analyses reveal how specific interactions of water and water-ions proximate to the polymer-water interface explain observed trends. This study establishes relevance of thermodynamic driving forces in contact charging of insulators with new evidence informed by molecular-level interactions. These insights have direct implications for future mechanistic studies and applications of contact charging involving polymeric materials.

Minimizing the impacts of the ammonia economy on the nitrogen cycle and climate.

Ammonia (NH3) is an attractive low-carbon fuel and hydrogen carrier. However, losses and inefficiencies across the value chain could result in reactive nitrogen emissions (NH3, NOx, and N2O), negatively impacting air quality, the environment, human health, and climate. A relatively robust ammonia economy (30 EJ/y) could perturb the global nitrogen cycle by up to 65 Mt/y with a 5% nitrogen loss rate, equivalent to 50% of the current global perturbation caused by fertilizers. Moreover, the emission rate of nitrous oxide (N2O), a potent greenhouse gas and ozone-depleting molecule, determines whether ammonia combustion has a greenhouse footprint comparable to renewable energy sources or higher than coal (100 to 1,400 gCO2e/kWh). The success of the ammonia economy hence hinges on adopting optimal practices and technologies that minimize reactive nitrogen emissions. We discuss how this constraint should be included in the ongoing broad engineering research to reduce environmental concerns and prevent the lock-in of high-leakage practices.

Molecular Dynamics Investigation of Nanoscale Hydrophobicity of Polymer Surfaces: What Makes Water Wet?

The wettability of a polymer surface─related to its hydrophobicity or tendency to repel water─can be crucial for determining its utility, such as for a coating or a purification membrane. While wettability is commonly associated with the macroscopic measurement of a contact angle between surface, water, and air, the molecular physics that underlie these macroscopic observations are not fully known, and anticipating the relative behavior of different polymers is challenging. To address this gap in molecular-level understanding, we use molecular dynamics simulations to investigate and contrast interactions of water with six chemically distinct polymers: polytetrafluoroethylene, polyethylene, polyvinyl chloride, poly(methyl methacrylate), Nylon-66, and poly(vinyl alcohol). We show that several prospective quantitative metrics for hydrophobicity agree well with experimental contact angles. Moreover, the behavior of water in proximity to these polymer surfaces can be distinguished with analysis of interfacial water dynamics, extent of hydrogen bonding, and molecular orientation─even when macroscopic measures of hydrophobicity are similar. The predominant factor dictating wettability is found to be the extent of hydrogen bonding between polymer and water, but the precise manifestation of hydrogen bonding and its impact on surface water structure varies. In the absence of hydrogen bonding, other molecular interactions and polymer mechanics control hydrophobic ordering. These results provide new insights into how polymer chemistry specifically impacts water-polymer interactions and translates to surface hydrophobicity. Such factors may facilitate the design or processing of polymer surfaces to achieve targeted wetting behavior, and presented analyses can be useful in studying the interfacial physics of other systems.

A CFD-DEM investigation of powder transport and aerosolization in ELLIPTA® dry powder inhaler.

We have performed Computational Fluid Dynamics-Discrete Element Method (CFD-DEM) simulations of air and particles in a commercial ELLIPTA® inhaler. We simulated the fluidization, deagglomeration and transport of carrier and API particles, with two realistic inhalation profiles that are representative of moderate asthma and very severe COPD patients, and three different mouthpiece designs. In each of the ten cases simulated, we determined the fine particle fraction (FPF) in the stream leaving the mouthpiece, the temporal evolution of the spatial distribution of the particles, the mean air (slip) velocity seen by the carrier particles, and the average numbers and normal impact velocities of carrier-carrier and carrier-wall collisions inside the inhaler. In the cases examined, the air-carrier and carrier-carrier interactions affected the FPF, while the carrier-wall interactions were too infrequent to have a substantial effect. The simulations revealed the benefit of loading both blisters even when only a single medication needs to be delivered.

Effect of Porous Catalyst Support on Plasma-Assisted Catalysis for Ammonia Synthesis.

We report on the effect of catalyst support particle porosity on the conversion of NH3 synthesis from N2 and H2 in a coaxial dielectric barrier discharge (DBD) plasma reactor. The discharge was created using an AC applied voltage with the reactor at room temperature and near atmospheric pressure (550 Torr). Two different particles of almost equal diameter (∼1.5 mm)─porous silica (SiO2) ceramic beads (average pore size: 8 nm) and smooth, nonporous soda lime glass beads─were compared in the DBD reactor. As the pore size in the SiO2 particles was smaller than the Debye length, penetration of the plasma into the pores of the particles was unlikely; however, reactive species generated in the plasma outside the particles could diffuse into the pores. The N2 conversion and energy yield of NH3 increased with applied voltage for both particle types, and these values were consistently higher when using the SiO2 beads. Discharge and plasma properties were estimated from Lissajous plots and using calculations with the BOLSIG+ software. The effect of these two different catalyst supports on the physical properties of the discharge was negligible. High resolution optical emission spectra revealed that the concentrations of N2+, atomic N, and atomic H (Hα, Hß) in the plasma discharge were lower with the porous SiO2 beads than with the glass beads at every applied voltage tested. This indicates that these active species participate in heterogeneous reactions at support particle surfaces and that the larger surface area presented by the porous particles led to higher rates of depletion of these intermediates and a higher rate of ammonia synthesis.

Recent developments in the computational simulation of dry powder inhalers.

This article reviews recent developments in computational modeling of dry powder inhalers (DPIs). DPIs deliver drug formulations (sometimes blended with larger carrier particles) to a patient's lungs via inhalation. Inhaler design is complicated by the need for maximum aerosolization efficiency, which is favored by high levels of turbulence near the mouthpiece, with low extrathoracic depositional loss, which requires low turbulence levels near the mouth-throat region. In this article, we review the physical processes contributing to aerosolization and subsequent dispersion and deposition. We assess the performance characteristics of DPIs using existing simulation techniques and offer a perspective on how such simulations can be improved to capture the physical processes occurring over a wide range of length- and timescales more efficiently.

Effects of dose loading conditions and device geometry on the transport and aerosolization in dry powder inhalers: A simulation study.

The transport and aerosolization of particles are studied in several different dry powder inhaler geometries via Computational Fluid Dynamics-Discrete Element Method (CFD-DEM) simulations. These simulations combine Large Eddy Simulation of gas with Discrete Element Model simulation of all the carrier particles and a representative subset of the active pharmaceutical ingredient (API) particles. The purpose of the study is to probe the dominant mechanism leading to the release of the API particles and to demonstrate the value of the CFD-DEM simulations where one tracks the motion of all the carrier and API particles. Simulations are performed at different inhalation rates and initial dose loading conditions for the screen-haler geometry, a simple cylindrical tube inhaler, and five different geometry modifications that took the form of bumpy walls and baffles. These geometry modifications alter the residence time of the powder sample in the inhaler, pressure drop across the inhaler, the severity of gas-carrier interactions, and the number of collisions experienced by the carrier particles, all of which are quantified. The quality of aerosolization is found to correlate with the average air-carrier slip velocity, while collisions played only a secondary role. Some geometry modifications improved aerosolization quality with very little increase in the pressure drop across the device.

Particle-based coarse-grained approach for simulating dry powder inhaler.

Drug delivery via dry powder inhaler (DPI) is a complex process affected by multiple factors involving gas and particles. The performance of a carrier-based formulation depends on the release of active pharmaceutical ingredient (API) particles, typically characterized by fine particle fraction (FPF) and dispersion fraction (DF). Computational Fluid Dynamics coupled with Discrete Element Method (CFD-DEM) can capture relevant gas and particle interactions but is computationally expensive, especially when tracking all carrier and API particles. This study assessed the efficacy of two coarse-grained CFD-DEM approaches, the Discrete Parcel Method and the representative particle approach, through highly-resolved CFD-DEM simulations. The representative particle approach simulates all carrier particles and a subset of API particles, whereas the Discrete Parcel Method tracks parcels representing a specified number of carrier or API particles. Both approaches are viable for a small carrier-API size ratio which requires modest degrees of coarse-graining, but the Discrete Parcel Method showed limitations for a large carrier-API size ratio. The representative particle approach can approximate CFD-DEM results with reasonable accuracies when simulations include at least 10 representative API particles per carrier. Using the representative particle approach, we probed powder characteristics that could affect FPF and DF in a model problem and correlated these fractions with the maximum carrier-API cohesive force per unit mass of API particles.

Mid-Infrared Scattering in γ-Al2O3 Catalytic Powders.

The energy efficiency of heterogeneous catalytic processes may be improved by using mid-infrared light to excite gas-phase reactants during the reaction, since vibrational excitation of molecules has been shown to increase their reactivity at the gas-catalyst interface. A primary challenge for such light-enabled catalysis is the need to ensure close coupling between light-excited molecules and the catalyst throughout the reactor. Thus, it is imperative to understand how to couple infrared light efficiently to molecules near and inside catalytic material. Heterogenous catalysts are often nanoscale metal particles supported on high surface area, porous oxide materials and exhibit feature sizes across multiple scattering regimes with respect to the mid-infrared wavelength. These complex powders make a direct measurement of the scattering properties challenging. Here, we demonstrate that a combination of directional hemispherical measurements along with the in-line transmission measurement allow for a direct measurement of the scattered light signal. We implement this technique to study the scattering behavior of the catalytic support material γ-Al2O3 (with and without metal loading) between 1040 and 1220 cm-1. We first study how both the mean grain size affects the scattering behavior by comparing three different mean grain sizes spanning three orders of magnitude (2, 40, and 900 µm). Furthermore, we study how the addition of metal catalyst nanoparticles, Ru, or Cu, to the support material impacts the light scattering behavior of the powder. We find that the 40 µm grain size scatters the most (up to 97% at 1220 cm-1) and that the addition of metal nanoparticles narrows the scattering angle but does not decrease the scattering efficiency. The strong scattering of the 40 µm grains makes them the most ideal support material of those studied for the given spectrum because of their ability to distribute light within the reactor. Finally, we estimate that less than 100 mW of laser power is needed to cause significant excitation for testing mid-infrared catalysis in a Harrick Praying Mantis diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reactor, a magnitude easily available using commercial mid-infrared lasers. Our work also provides a mid-infrared foundation for a wide range of studies of light-enabled catalysis and can be extended to other wavelengths of light or to study the scattering behavior of other complex powders in other fields, including ceramics, biomaterials, and geology.

Effects of Polarization on Particle-Laden Flows.

Simulations of particle-laden flow with dielectric particles are carried out with varying levels of electrical charging and particle polarization. Simulation results reveal three distinct flow regions. For low particle charge and polarizability, flow is nearly symmetric and nonmeandering. For strong charging and polarization, particles form a continuous and tightly clustered sheet close to one of the walls. Between these extremes, particles form localized particle-rich regions, around which the gas executes a meandering flow. These results indicate that polarization can lead to qualitative changes in the characteristics of particle-laden flows subject to tribocharging.

Toward Constitutive Models for Momentum, Species, and Energy Transport in Gas-Particle Flows.

As multiscale structures are inherent in multiphase flows, constitutive models employed in conjunction with transport equations for momentum, species, and energy are scale dependent. We suggest that this scale dependency can be better quantified through deep learning techniques and formulation of transport equations for additional quantities such as drift velocity and analogies for species, energy, and momentum transfer. How one should incorporate interparticle forces, which arise through van der Waals interaction, dynamic liquid bridges between wet particles, and tribocharging, in multiscale models warrants further study. Development of multiscale models that account for all the known interactions would improve confidence in the use of simulations to explore design options, decrease the number of pilot-scale experiments, and accelerate commercialization of new technologies.

Dynamics of Tissue-Induced Alignment of Fibrous Extracellular Matrix.

Aligned fibers of extracellular matrix (ECM) affect the direction, efficiency, and persistence of migrating cells. To uncover the mechanisms by which multicellular tissues align their surrounding ECM before migration, we used an engineered three-dimensional culture model to investigate the dynamics of ECM alignment around tissues of defined geometry. Analysis of ECM alignment over time revealed that tissues rapidly reorganize their surrounding matrix, with a characteristic time that depends on the type of cell and the initial tissue geometry. We found that matrix metalloproteinase activity is not required for matrix alignment before cell migration. Instead, alignment is driven by Rho-mediated cytoskeletal contractility and accelerated by propagation of tension through intercellular adhesions. Our data suggest that multicellular tissues align their surrounding matrix by pulling collectively to exert strain, which is primarily a physical process. Consistently, the pattern of matrix alignment depends on tissue geometry and the resulting distribution of mechanical strain, with asymmetric tissues generating a higher degree of matrix alignment along their longest axes. The rapid ability of multicellular tissues to physically remodel their matrix enables their constituent cells to migrate efficiently along aligned fibers and to quickly change their direction according to other microenvironmental cues, which is important for both normal and disease processes.

Rheology of cohesive granular materials across multiple dense-flow regimes.

We investigate the dense-flow rheology of cohesive granular materials through discrete element simulations of homogeneous, simple shear flows of frictional, cohesive, spherical particles. Dense shear flows of noncohesive granular materials exhibit three regimes: quasistatic, inertial, and intermediate, which persist for cohesive materials as well. It is found that cohesion results in bifurcation of the inertial regime into two regimes: (a) a new rate-independent regime and (b) an inertial regime. Transition from rate-independent cohesive regime to inertial regime occurs when the kinetic energy supplied by shearing is sufficient to overcome the cohesive energy. Simulations reveal that inhomogeneous shear band forms in the vicinity of this transition, which is more pronounced at lower particle volume fractions. We propose a rheological model for cohesive systems that captures the simulation results across all four regimes.

Carbon Capture Simulation Initiative: a case study in multiscale modeling and new challenges.

Advanced multiscale modeling and simulation have the potential to dramatically reduce the time and cost to develop new carbon capture technologies. The Carbon Capture Simulation Initiative is a partnership among national laboratories, industry, and universities that is developing, demonstrating, and deploying a suite of such tools, including basic data submodels, steady-state and dynamic process models, process optimization and uncertainty quantification tools, an advanced dynamic process control framework, high-resolution filtered computational-fluid-dynamics (CFD) submodels, validated high-fidelity device-scale CFD models with quantified uncertainty, and a risk-analysis framework. These tools and models enable basic data submodels, including thermodynamics and kinetics, to be used within detailed process models to synthesize and optimize a process. The resulting process informs the development of process control systems and more detailed simulations of potential equipment to improve the design and reduce scale-up risk. Quantification and propagation of uncertainty across scales is an essential part of these tools and models.

Lattice-Boltzmann-based two-phase thermal model for simulating phase change.

A lattice Boltzmann (LB) method is presented for solving the energy conservation equation in two phases when the phase change effects are included in the model. This approach employs multiple distribution functions, one for a pseudotemperature scalar variable and the rest for the various species. A nonideal equation of state (EOS) is introduced by using a pseudopotential LB model. The evolution equation for the pseudotemperature variable is constructed in such a manner that in the continuum limit one recovers the well known macroscopic energy conservation equation for the mixtures. Heats of reaction, the enthalpy change associated with the phase change, and the diffusive transport of enthalpy are all taken into account; but the dependence of enthalpy on pressure, which is usually a small effect in most nonisothermal flows encountered in chemical reaction systems, is ignored. The energy equation is coupled to the LB equations for species transport and pseudopotential interaction forces through the EOS by using the filtered local pseudotemperature field. The proposed scheme is validated against simple test problems for which analytical solutions can readily be obtained.

Dynamics of single rising bubbles in neutrally buoyant liquid-solid suspensions.

We experimentally investigate the effect of particles on the dynamics of a gas bubble rising in a liquid-solid suspension while the particles are equally sized and neutrally buoyant. Using the Stokes number as a universal scale, we show that when a bubble rises through a suspension characterized by a low Stokes number (in our case, small particles), it will hardly collide with the particles and will experience the suspension as a pseudoclear liquid. On the other hand, when the Stokes number is high (large particles), the high particle inertia leads to direct collisions with the bubble. In that case, Newton's collision rule applies, and direct exchange of momentum and energy between the bubble and the particles occurs. We present a simple theory that describes the underlying mechanism determining the terminal bubble velocity.

Bridging the rheology of granular flows in three regimes.

We investigate the rheology of granular materials via molecular dynamics simulations of homogeneous, simple shear flows of soft, frictional, noncohesive spheres. In agreement with previous results for frictionless particles, we observe three flow regimes existing in different domains of particle volume fraction and shear rate, with all stress data collapsing upon scaling by powers of the distance to the jamming point. Though this jamming point is a function of the interparticle friction coefficient, the relation between pressure and strain rate at this point is found to be independent of friction. We also propose a rheological model that blends the asymptotic relations in each regime to obtain a general description for these flows. Finally, we show that departure from inertial number scalings is a direct result of particle softness, with a dimensionless shear rate characterizing the transition.