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Dynamics and yielding of binary self-suspended nanoparticle fluids

Yielding and flow transitions in bi-disperse suspensions of particles are studied using a model system comprised of self-suspended spherical nanoparticles. An important feature of the materials is that the nanoparticles are uniformly dispersed in the absence of a solvent. Addition of larger particles to a suspension of smaller ones is found to soften the suspensions, and in the limit of large size disparities, completely fluidizes the material. We show that these behaviors coincide with a speeding-up of de-correlation dynamics of all particles in the suspensions and are accompanied by a reduction in the energy dissipated at the yielding transition. We discuss our findings in terms of ligand-mediated jamming and un-jamming of hairy particle suspensions.

Agrawal, Akanksha↗

Two glass transitions in miscible polymer blends?

In contrast to mixtures of two small molecule fluids, miscible binary polymer blends often exhibit two structural relaxation times and two glass transition temperatures. Qualitative explanations postulate phenomenological models of local concentration enhancements due to chain connectivity in ideal, fully miscible systems. We develop a quantitative theory that explains qualitative trends in the dynamics of real miscible polymer blends which are never ideal mixtures. The theory is a synthesis of the lattice cluster theory of blend thermodynamics, the generalized entropy theory for glass-formation in polymer materials, and the Kirkwood-Buff theory for concentration fluctuations in binary mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An instability due to the nonlinear coupling of p-modes to g-modes: Implications for coalescing neutron star binaries

A weakly nonlinear fluid wave propagating within a star can be unstable to three-wave interactions. The resonant parametric instability is a well-known form of three-wave interaction in which a primary wave of frequency ω {sub a} excites a pair of secondary waves of frequency ω {sub b} + ω {sub c} ≅ ω {sub a}. Here we consider a nonresonant form of three-wave interaction in which a low-frequency primary wave excites a high-frequency p-mode and a low-frequency g-mode such that ω {sub b} + ω {sub c} >> ω {sub a}. We show that a p-mode can couple so strongly to a g-mode of similar radial wavelength that this type of nonresonant interaction is unstable even if the primary wave amplitude is small. As an application, we analyze the stability of the tide in coalescing neutron star binaries to p-g mode coupling. We find that the equilibrium tide and dynamical tide are both p-g unstable at gravitational wave frequencies f {sub gw} ≳ 20 Hz and drive short wavelength p-g mode pairs to significant energies on very short timescales (much less than the orbital decay time due to gravitational radiation). Resonant parametric coupling to the tide is, by contrast, either stable or drives modes at a much smaller rate. We do not solve for the saturation of the p-g instability and therefore we cannot say precisely how it influences the evolution of neutron star binaries. However, we show that if even a single daughter mode saturates near its wave breaking amplitude, the p-g instability of the equilibrium tide will (1) induce significant orbital phase errors (Δφ ≳ 1 radian) that accumulate primarily at low frequencies (f {sub gw} ≲ 50 Hz) and (2) heat the neutron star core to a temperature of T ∼ 10{sup 10} K. Since there are at least ∼100 unstable p-g daughter pairs, Δφ and T are potentially much larger than these values. Tides might therefore significantly influence the gravitational wave signal and electromagnetic emission from coalescing neutron star binaries at much larger orbital separations than previously thought.

79 ASTRONOMY AND ASTROPHYSICS↗

Contact angles from Young’s equation in molecular dynamics simulations

In this work, we propose a method to calculate the equilibrium contact angle of heterogeneous 3-phase solid/fluid/fluid systems using molecular dynamics simulations. The proposed method, which combines the phantom-wall method [F. Leroy and F. Müller-Plathe, J. Chem. Phys. 133, 044110 (2010)] and Bennett’s acceptance ratio approach [C. H. Bennett, J. Comput. Phys. 22, 245 (1976)], is able to calculate the solid/fluid surface tension relative to the solid surface energy. The calculated relative surface tensions can then be used in Young’s equation to estimate the equilibrium contact angle. A fluid droplet is not needed for the proposed method, in contrast to the situation for direct simulations of contact angles. In addition, while prior free-energy based methods for contact angles mainly focused on the wetting of fluids in coexistence with their vapor on solid surfaces, the proposed approach was designed to study the contact angles of fluid mixtures on solid surfaces above the fluid saturation pressures. Using the proposed approach, the contact angles of binary Lennard-Jones fluid mixtures on a non-polar solid substrate were calculated at various interaction parameters and the contact angle of water in equilibrium with CO 2 on a hydrophilic polar silica surface was obtained. For both non-polar and polar systems, the calculated contact angles from the proposed method were in agreement with those obtained from the geometry of a cylindrical droplet. The computational cost of the proposed method was found to be comparable to that of simulations that use fluid droplets, but the new method provides a way to calculate the contact angle directly from Young’s equation without ambiguity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Binary Power Plant CO2 Life Cycle Emissions Including Isobutane Fugitive Emission

Geothermal energy production has one of the lowest life cycle CO2 emission factors (~ 15 g-CO2/kWh) for plants producing electricity (Hondo, 2005). This life cycle factor includes indirect emissions from plant construction as well as ongoing operations such as additional well drilling and equipment replacement. Not included in this calculation are direct emissions from geothermal power production. Geothermal flash plants emit CO2 at rates related to the reservoir concentration. Binary plants report “near zero” emissions of high global warming potential gases because of their closed loop system design. Binary plants use working fluids to drive the turbine generators and leakage of these working fluids have not yet been quantified. To assess the working fluid emissions from geothermal power production using an Organic Rankine Cycle, reported isobutane emissions were accessed for 3 California binary plants from the Great Basin Unified and Imperial County Air Pollution Control Districts as well as the California Air Resource Board. Each binary plant used in this study has been operating for more than 25 years. From the data, two types of isobutane emissions were accounted for over a 15 month period: ‘normal’ equipment leakage and equipment breakdown emissions. This preliminary analysis of working fluid emissions from these plants suggest that if a binary plant has equipment failures, the majority of the isobutane releases can be due to these events. The results indicate that a well maintained binary plant releases approximately 0.13 g-Isobutane/kWh where as a plant with equipment failures releases approximately 6 g-Isobutane/kWh. Assuming a greenhouse warming potential of 3 for isobutane, these emission values become 0.4 and 18 g-CO2e/kWh (where CO2e is the CO2 equivalent effect). The direct operation isobutane leakage for a well maintained binary plant does not significant increase the life cycle CO2 emission factor whereas a plant with significant equipment issues can effectively double the life cycle CO2 emissions. This limited data set suggests that when direct CO2e fugitive emission are add to the indirect CO2 emissions, the total CO2 emissions from binary power plants are equivalent or less than nuclear, as well as other renewables power production such as wind and solar.

15 GEOTHERMAL ENERGY↗

Molecular simulation of fluids with non-identical intermolecular potentials: Thermodynamic properties of 10-5 + 12-6 Mie potential binary mixtures

General methods for combining interactions between particles characterised by non-identical intermolecular potentials are investigated. The combination methods are tested by performing molecular dynamics simulations to determine the pressure, energy, isochoric and isobaric heat capacities, thermal expansion coefficient, isothermal compressibility, Joule-Thomson coefficient, and speed of sound of 10-5 + 12-6 Mie potential binary mixtures. In addition to the two non-identical Mie potentials, mixtures are also studied with non-identical intermolecular parameters. The combination methods are compared with results obtained by simply averaging the Mie exponents. When either the energy or size parameters are non-identical, very significant differences emerge in the thermodynamic properties predicted by the alternative combination methods. The isobaric heat capacity is the thermodynamic property that is most affected by the relative magnitude of the intermolecular potential parameters and the method for combining non-identical potentials. Either the arithmetic or geometric combination of potentials provides a simple and effective way of performing simulations involving mixtures of components characterised by non-identical intermolecular potentials, which is independent of their functional form.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scaling relationships for the elastic moduli and viscosity of mixed lipid membranes

The elastic and viscous properties of biological membranes play a vital role in controlling cell functions that require local reorganization of the membrane components as well as dramatic shape changes such as endocytosis, vesicular trafficking, and cell division. These properties are widely acknowledged to depend on the unique composition of lipids within the membrane, yet the effects of lipid mixing on the membrane biophysical properties remain poorly understood. Here, we present a comprehensive characterization of the structural, elastic, and viscous properties of fluid membranes composed of binary mixtures of lipids with different tail lengths. We show that the mixed lipid membrane properties are not simply additive quantities of the single-component analogs. Instead, the mixed membranes are more dynamic than either of their constituents, quantified as a decrease in their bending modulus, area compressibility modulus, and viscosity. While the enhanced dynamics are seemingly unexpected, we show that the measured moduli and viscosity for both the mixed and single-component bilayers all scale with the area per lipid and collapse onto respective master curves. This scaling links the increase in dynamics to mixing-induced changes in the lipid packing and membrane structure. More importantly, the results show that the membrane properties can be manipulated through lipid composition the same way bimodal blends of surfactants, liquid crystals, and polymers are used to engineer the mechanical properties of soft materials, with broad implications for understanding how lipid diversity relates to biomembrane function.

59 BASIC BIOLOGICAL SCIENCES↗

General relativistic hydrodynamic simulations of binary strange star mergers

We perform fully general-relativistic simulations of binary strange star mergers considering two different approaches for thermal effects. The first uses a cold equation of state (EOS) derived from a modified version of the MIT bag model which is then supplemented by a Γ-law correction. The second approach employs a microphysical description of the finite-temperature effects. We describe results obtained with the two treatments, highlighting the influence of thermal effects. We find that the postmerger dynamics differs significantly in the two cases, leading to quantitative differences in the postmerger gravitational-wave spectrum and ejecta mass. The peak frequency of the postmerger gravitational-wave emission is consistent with the established quasi-universal relations for binary neutron star mergers and as a result, our simulations cannot distinguish between mergers of neutron stars and those of strange stars. Our models with realistic treatment of finite-temperature effects produce a significant amount of ejecta ≳0.02 M ⊙ ​. Here, the resulting flux of strangelets near the Earth, computed assuming that all neutron star mergers are in fact strange-stars mergers and that the binary considered here is representative, is in tension with experimental upper limits. As such, our results tentatively disfavor a scenario in which strange-quark matter is the lowest energy state of matter.

79 ASTRONOMY AND ASTROPHYSICS↗

Scalable and fast heterogeneous molecular simulation with predictive parallelization schemes

Multiscale and inhomogeneous molecular systems are challenging topics in the field of molecular simulation. In particular, modeling biological systems in the context of multiscale simulations and exploring material properties are driving a permanent development of new simulation methods and optimization algorithms. In computational terms, those methods require parallelization schemes that make a productive use of computational resources for each simulation and from its genesis. Here, we introduce the heterogeneous domain decomposition approach, which is a combination of an heterogeneity-sensitive spatial domain decomposition with an a priori rearrangement of subdomain walls. Within this approach and paper, the theoretical modeling and scaling laws for the force computation time are proposed and studied as a function of the number of particles and the spatial resolution ratio. We also show the new approach capabilities, by comparing it to both static domain decomposition algorithms and dynamic load-balancing schemes. Specifically, two representative molecular systems have been simulated and compared to the heterogeneous domain decomposition proposed in this work. Finally, these two systems comprise an adaptive resolution simulation of a biomolecule solvated in water and a phase-separated binary Lennard-Jones fluid.

36 MATERIALS SCIENCE↗

Asymptotic Limits for Transport in Binary Stochastic Mixtures

The Karhunen-Loeve stochastic spectral expansion of a random binary mixture of immiscible fluids in planar geometry is used to explore asymptotic limits of radiation transport in such mixtures. Under appropriate scalings of mixing parameters - correlation length, volume fraction, and material cross sections - and employing multiple- scale expansion of the angular flux, previously established atomic mix and diffusion limits are reproduced. When applied to highly contrasting material properties in the small cor- relation length limit, the methodology yields a nonstandard reflective medium transport equation that merits further investigation. Finally, a hybrid closure is proposed that produces both small and large correlation length limits of the closure condition for the material averaged equations.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Concentration fluctuations in miscible polymer blends: Influence of temperature and chain rigidity

In contrast to binary mixtures of small molecule fluids, homogeneous polymer blends exhibit relatively large concentration fluctuations that can strongly affect the transport properties of these complex fluids over wide ranges of temperatures and compositions. The spatial scale and intensity of these compositional fluctuations are studied by applying Kirkwood-Buff theory to model blends of linear semiflexible polymer chains with upper critical solution temperatures. The requisite quantities for determining the Kirkwood-Buff integrals are generated from the lattice cluster theory for the thermodynamics of the blend and from the generalization of the random phase approximation to compressible polymer mixtures. We explore how the scale and intensity of composition fluctuations in binary blends vary with the reduced temperature τ ≡ (T − T{sub c})/T (where T{sub c} is the critical temperature) and with the asymmetry in the rigidities of the components. Knowledge of these variations is crucial for understanding the dynamics of materials fabricated from polymer blends, and evidence supporting these expectations is briefly discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Source term method for binary neutron stars initial data

The initial condition problem for a binary neutron star system requires a Poisson equation solver for the velocity potential with a Neumann-like boundary condition on the surface of the star. Difficulties that arise in this boundary value problem are: (a) the boundary is not known a priori, but constitutes part of the solution of the problem; (b) various terms become singular at the boundary. In this work, we present a new method to solve the fluid Poisson equation for irrotational/spinning binary neutron stars. The advantage of the new method is that it does not require complex fluid surface fitted coordinates and it can be implemented in a Cartesian grid, which is a standard choice in numerical relativity calculations. This is accomplished by employing the source term method proposed by Towers, where the boundary condition is treated as a jump condition and is incorporated as additional source terms in the Poisson equation, which is then solved iteratively. The issue of singular terms caused by vanishing density on the surface is resolved with an additional separation that shifts the computation boundary to the interior of the star. We present two-dimensional tests to show the convergence of the source term method, and we further apply this solver to a realistic three-dimensional binary neutron star problem. By comparing our solution with the one coming from the initial data solver cocal, we demonstrate agreement to approximately 1%. We report our method can be used in other problems with non-smooth solutions like in magnetized neutron stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Bridging confined phase behavior of CH 4 -CO 2 binary systems across scales

Phase behavior of confined fluids may deviate significantly from that of the bulk fluid due to the fluid-wall interactions being a significant portion of all intermolecular interactions under confinement. Despite recent advancements in understanding confined phase behavior of pure fluids, confined phase behavior of mixtures remains an understudied topic. In this work, we examine the confined phase behavior of a CH 4 -CO 2 binary system by combining Monte Carlo (MC) simulations, a cubic equation of state (EoS), and the lattice Boltzmann method (LBM). First, the effects of confinement on density and phase distribution in nano-size pores are established using Gibbs Ensemble MC calculations, which produce precise results of liquid and vapor confined pressures and account for the modification of the phase change location. By comparing the phase envelopes of bulk and confined mixtures at a fixed temperature, here it is observed that the phase envelopes shrink with reductions in pore size. Based on this observation, we extend a modified Peng-Robinson EoS, which was originally developed for pure fluids under confinement, to mixtures via van-der-Waals-type mixing rules and by accounting for shifts in the critical properties of confined CH 4 -CO 2 . The resulting phase envelopes are in good agreement with the MC data. In addition, a local density model is used in combination with the confined EoS to calculate adsorption isotherms of CH 4 -CO 2 mixtures and to characterize the behavior of confined matter in nanopores. Finally, we incorporate this EoS in a multicomponent multiphase LBM that uses a pseudopotential model to represent intermolecular forces. This workflow utilizes multiscale simulation techniques to bridge the behavior of multicomponent systems across scales and to shed light on the confined phase behavior of CH 4 -CO 2 binary systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Binary Complexes (DBC) as Super-Adjustable Viscosity Modifiers for Hydraulic Fracturing Fluids

In the preceding project year two, we refined three DBC formulations from a selection of over 50 different chemistries. The optimization study primarily encompassed testing for (i) reversibility extent, (ii) performance in the presence of chemical additives, (iii) adhesion and friction behavior during displacement in wellbores and pipelines, (iv) corrosion protection performance, and (v) injection performance with model fracture systems at the laboratory scale. Highly promising results obtained from all these tests signify the significant potential of DBCs in enhancing hydrocarbon recovery from unconventional reservoirs. The primary activities in the third project year included publishing experimental findings across multiple articles and conducting outreach initiatives. Throughout the year, we undertook tasks such as replicating experimental results, further optimizing various formulations and their associated experimental sets, and conducting additional tests to address missing components based on reviewer feedback and suggestions. We also explored the surfactant and friction-reduction aspects of selected formulations through drag reduction tests. In addition, we constructed an improved fracturing performance setup and performed flow injection tests. The specific DBC formulations focused on during this project period were A8/B1, A12/B5, and A10/B12. We also obtained results for additional DBC formulations and a select few commercial fracturing fluids for the purpose of comparison. Within the project's scope, we aim to enhance the experimental findings with the development of various models. The first two years focused on two key aspects: (i) the creation of a high-fidelity hydraulic fracturing model for non-Newtonian fluids to gain insights into the implementation of DBC fluids in fracking environments, and (ii) the development of a multiphase flow simulator for estimating total production, fluid saturation in the reservoir, and the creation of a fracture propagation model and kinetic Monte Carlo (kMC) models for diverse applications. In the third year, we delved into the fundamental nanostructural properties of DBCs, exploring aspects such as material chemistry, pH tunability, and control of DBC formation and stability. Subsequently, in the extension year, we conducted a systematic investigation of various building blocks containing primary, secondary, and tertiary amine functional groups to understand their impact on rheological and viscoelastic properties. Furthermore, we explored a Dissipative Particle Dynamics (DPD) model to simulate self-assembly processes with precision, creating a high-fidelity representation of relevant nanostructures. The tasks performed this year with the significant results obtained have been discussed in Section 2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced quantum spin fluctuations in a binary Bose-Einstein condensate

For quantum fluids, the role of quantum fluctuations may be significant in several regimes such as when the dimensionality is low, the density is high, the interactions are strong, or for low particle numbers. In this paper, we propose a fundamentally different regime for enhanced quantum fluctuations without being restricted by any of the above conditions. Instead, our scheme relies on the engineering of an effective attractive interaction in a dilute, two-component Bose-Einstein condensate (BEC) consisting of thousands of atoms. In such a regime, the quantum spin fluctuations are significantly enhanced (atom bunching with respect to the noninteracting limit) since they act to reduce the interaction energy, a remarkable property given that spin fluctuations are normally suppressed (antibunching) at zero temperature. In contrast to the case of true attractive interactions, our approach is not vulnerable to BEC collapse. Here, we numerically demonstrate that these quantum fluctuations are experimentally accessible by either spin or single-component Bragg spectroscopy, offering a useful platform on which to test beyond-mean-field theories. We also develop a variational model and use it to analytically predict the shift of the immiscibility critical point, finding good agreement with our numerics.

74 ATOMIC AND MOLECULAR PHYSICS↗

Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Absorption/Desorption based high efficiency Supercritical Carbon Dioxide Power Cycles - Final Scientific/Technical Report

The team of Southwest Research Institute® (SwRI®) and Thar Energy LLC (Thar) are advancing the state of the art in fossil-fired closed Brayton supercritical carbon dioxide (sCO 2 ) power cycles. This current effort is focused on evaluating the integration of a fossil-based thermal system with closed Brayton sCO 2 power blocks to understand the impact of thermal integration on plant performance and identification of current technology gaps. This effort is extending the current understanding of how fossil-based thermal systems may best be integrated with recuperated closed Brayton cycles based on the overall impact on the integrated plant efficiency, cost, and operating characteristics. System Engineering Design and Thermodynamic Analysis is being utilized to (1) identify technical challenges impacting the integration of fossil-based thermal sources with highly recuperated closed Brayton sCO 2 power cycles, (2) evaluate the impact of boiler design and sCO 2 cycle configuration on integrated plant performance, cost, and operability, and (3) evaluate technology readiness of the integrated system and identify specific technologies requiring development of advanced fossil-based sCO 2 cycles. Engineering evaluation is being applied to coal- and natural gas-fired thermal systems for sCO 2 power cycles to evaluate current boiler technologies and challenges associated with adapting those to a sCO 2 based configuration. This includes technical evaluation of the sCO 2 heat exchanger design and anticipated performance impacts on the thermal system. In addition to the general evaluation of indirect fossil fires closed Brayton sCO 2 cycles, this effort is also evaluating a novel indirect sCO 2 power cycle that utilizes an absorption/desorption circuit to minimize compression work by 40% to 65%. This translates to a thermodynamic cycle efficiency improvement of 3.2 points for a simple recuperated cycle using a binary CO 2 + Acetone working fluid.

20 FOSSIL-FUELED POWER PLANTS↗

Closures and Simulation for Thermal Radiation Transport in Stochastic Media with Nonlinear Temperature Dependence

Because of the practical challenge of rendering very complex realistic spatial structures for numerical work, it is common practice to resort to characterizing such media as stochastic mixtures of materials, ideally parametrized with low order statistics such as the mean, variance, and correlation functions of the now random material properties. This enables realizations of the medium to be repeatedly generated and radiation transport computations to, in principle, be performed for a large ensemble of these realizations to obtain a statistically well-characterized radiation field. Statistical post-processing yields desired quantities such as conditional and unconditional mean radiation flux and probability distributions of transmitted radiation. However, such computations prove expensive for all but the simplest stochastic geometries and are most suited for benchmarking approximate models. The most common approximations lead to homogenized media so that transport computations are required only on a single medium realization but by construct provide only limited statistical information on the radiation field. Almost all approximate approaches to this problem attempt to develop equations for low order moments of the radiation intensity (mean, second moment, correlation function) but inevitably encounter a closure problem: the equation for any statistical moment will contain terms depending on unknown higher-order moments. Thus, the challenge shifts to one of developing closure relations that relate the unknown moments to the lower order moments. Under very special conditions, an exact closure can be derived but in general closures are heuristically stated constitutive relations. Also, closure approaches depend on whether the mixing statistics are spatially and/or temporally continuous as in fluctuating turbulent fields, or discontinuous as in randomly mixed solid chunks of material. Thus, unconditional averaging is generally applied in the former case but conditional averaging is more appropriate when the mixing is discontinuous. In this work, the emphasis is on binary statistical mixtures of immiscible fluids as as such the quantities of interest are averages (flux, temperature) conditioned on the material type.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗