Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “solution assembly”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Initial Delayed Critical Configuration of SHEBA I and Subcritical Measurements by Californium Source-Driven Noise Analysis

In September 1980, the initial delayed critical configuration of the Solution High-Energy Burst Assembly (SHEBA I) was assembled, and the US Department of Energy’s Oak Ridge National Laboratory (ORNL) staff performed near critical and subcritical measurements using the californium source-driven noise analysis (CSDNA) method at the Los Alamos National Laboratory (LANL) Critical Experiments Facility. An unreflected 56 cm outside diameter stainless-steel cylindrical tank was partially filled with uranyl fluoride solution (235U enrichment was 4.95 wt %) until delayed criticality was achieved. Then, measurements were performed for various fuel solution heights from delayed critical to 60% of the height required for delayed criticality. The stainless-steel tank had an inside diameter of 54.6 cm and a height of 105 cm and was partially (20–36.5 cm) filled with an aqueous solution of uranyl fluoride (with a density of 2.162 g/cm 3 ). The density of the uranium in solution was 1.042 g/cm 3 , and the solution had a H/U atomic ratio of 20.43. The tank had a 6.35 mm wall thickness and an axial reentrant tube with an inside diameter of 6.02 cm and wall thickness of 0.165 cm. The tank was essentially unreflected on the top and sides because it was in a thin metal shed. The reactivity of the near–delayed critical configuration was −10.4 cents, which corresponds to a k eff value of 0.99922. In addition to the CSDNA measurements, the prompt neutron decay constants were determined from break frequency noise analysis (BNFA) measurements. The subcritical neutron multiplication factors from CSDNA and BFNA compared extremely well. These data can be used as the basis of International Nuclear Criticality Safety Evaluation benchmark for the near-critical configuration, and the k eff values at various subcritical configurations can be used as subcritical benchmarks. Furthermore, the measured prompt neutron decay constants can be used as reactor physics benchmarks. This report documents the experimental information for the measurements performed so that, at a later date, researchers could perform the required uncertainty and calculational analyses and documentation to use these data for an International Criticality Safety Benchmark Evaluation Program (ICSBEP) or Nuclear Energy Agency benchmarks. The measured prompt neutron decay constants can be used as the basis of a benchmark for the International Reactor Physics Evaluation Program (IRPhEP). The data from these measurements are available from the ORNL Records Management Services Department, and the logbook is available from ICSBEP at Idaho National Laboratory.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Controlling Rheology of Fluid Interfaces through Microblock Length of Sequence-Controlled Amphiphilic Copolymers

Previous studies have demonstrated that films of sequence-controlled amphiphilic copolymers display contact angles that depend on microblock size. This suggests that microblock length may provide a means of tuning surface and interfacial properties. In this work, the interfacial rheology of a series of sequence-controlled copolymers, prepared through the addition of bicyclo[4.2.0]oct-1(8)-ene-8-carboxamide (monomer A) and cyclohexene (monomer B) to generate sequences up to 24 monomeric units composed of (A m B n ) i microblocks, where m, n, and i range from 1 to 6. Interfacial rheometry is used to measure the mechanical properties of an air–water interface with these copolymers. As the microblock size increases, the interfacial storage modulus, G', increases, which may be due to an increase in the size of interfacial hydrophobic domains. Small-angle X-ray scattering shows that the copolymers have a similar conformation in solution, suggesting that any variations in the mechanics of the interface are due to assembly at the interface, and not on solution association or bulk rheological properties. This is the first study demonstrating that microblock size can be used to control interfacial rheology of amphiphilic copolymers. Here, the results provide a new strategy for controlling the dynamics of fluid interfaces through precision sequence-controlled polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis

Bismuth-oxocluster nodes for metal–organic frameworks (MOFs) and coordination networks/polymers are less prolific than other families featuring zinc, zirconium, titanium, lanthanides, etc. However, Bi 3+ is non-toxic, it readily forms polyoxocations, and its oxides are exploited in photocatalysis. This family of compounds provides opportunity in medicinal and energy applications. Here, we show that Bi node nuclearity depends on solvent polarity, leading to a family of Bi x -sulfonate/carboxylate coordination networks with x = 1–38. Larger nuclearity-node networks were obtained from polar and strongly coordinating solvents, and we attribute the solvent’s ability to stabilize larger species in solution. Here, the strong role of the solvent and the lesser role of the linker in defining node topologies differ from other MOF syntheses, and this is due to the Bi 3+ intrinsic lone pair that leads to weak node–linker interactions. We describe this family by single-crystal X-ray diffraction (eleven structures), obtained in pure forms and high yields. Ditopic linkers include NDS (1,5-naphthalenedisulfonate), DDBS (2,2'-[biphenyl-4,4'-diylchethane-2,1-diyl] dibenzenesulphonate), and NH 2 -benzendicarboxylate (BDC). While the BDC and NDS linkers yield more open-framework topologies that resemble those obtained by carboxylate linkers, topologies with DDBS linkers appear to be in part driven by association between DDBS molecules. An in situ small-angle X-ray scattering study of Bi 38 -DDBS reveals stepwise formation, including Bi 38 -assembly, pre-organization in solution, followed by crystallization, confirming the less important role of the linker. We demonstrate photocatalytic hydrogen (H 2 ) generation with select members of the synthesized materials without the benefit of a co-catalyst. Band gap determination from X-ray photoelectron spectroscopy (XPS) and UV–vis data suggest the DDBS linker effectively absorbs in the visible range with ligand-to-Bi-node charge transfer. In addition, materials containing more Bi (larger Bi 38 -nodes or Bi 6 inorganic chains) exhibit strong UV absorption, also contributing to effective photocatalysis by a different mechanism. All tested materials became black with extensive UV–vis exposure, and XPS, transmission electron microscopy, and X-ray scattering of the black Bi 38 -framework suggest that Bi o is formed in situ, without phase segregation. This evolution leads to enhanced photocatalytic performance, perhaps due to increased light absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Single Atomic Iron Site Catalysts via Benign Aqueous Synthesis for Durability Improvement in Proton Exchange Membrane Fuel Cells

Atomically-dispersed iron-nitrogen-carbon (Fe–N–C) catalysts have arisen as promising candidates for replacing the costly precious metal catalysts in fuel cells but still face some grand challenges, such as insufficient site density and durability. Herein, we report a self-assembly method in an aqueous solution to develop an atomically-dispersed iron catalyst with high oxygen reduction reaction (ORR) activity and stability in acidic electrolytes. As determined by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption spectroscopy (XAS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), this benign aqueous synthesis strategy facilitates the formation of homogeneous atomic nitrogen-coordinated iron sites embedded in a popcorn-like porous graphitic carbon matrix. These catalyst properties contribute to the improved ORR kinetic current density and mass transport. By controlling synthesis chemistry, the correlation between structure and property is systematically investigated. In this work, the iron content is the most critical material property and can regulate site density and graphitic carbon structures in the catalyst, impacting catalytic activity and stability. The enhanced performance and durability were examined in both acidic aqueous electrolytes and membrane electrode assemblies.

25 ENERGY STORAGE↗
DOE OSTI2022

Deterministic modelling of the SPERT IV reactor transients using the multi-physics capability of WIMS

The ANSWERS WIMS reactor physics code is being developed for whole core multi-physics modelling. The established neutronics capability for lattice calculations has recently been extended to be suitable for whole core modelling of Small Modular Reactors (SMRs). A whole core transport, SP3 or diffusion flux solution is combined with fuel assembly resonance shielding. An integrated thermal hydraulic solver permits temperature and density variations to feedback to the neutronics calculation. This capability can be applied to both steady state and time dependent transient problems. Nuclear reactor design and safety case development requires assessment of a range of reactor transients, to inform both normal operation limitations and accident scenario analysis. This paper presents new methodology developed in WIMS to couple the core neutronics to the integrated core thermal hydraulics solver for the simulation of reactor transients in whole core models. To support the validation of the multi-physics capability of WIMS, this capability has been applied to the reactivity insertion transient experiments performed in the plate fuelled SPERT-IV reactor. This study employs WIMS using the whole core solver MERLIN, which calculates the time-dependent flux distribution and magnitude, coupled to ARTHUR, which solves for the time-dependent thermal hydraulics solution, and provides thermal feedback via the cross sections generated by GEOM, which performs resonance shielding calculations and generates cross section data for the plate geometry. This spatial kinetics model, with dynamic cross section generation, allows for variations in the temperature and neutron flux profile with time.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2021

A slip-spring framework to study relaxation dynamics of entangled wormlike micelles with kinetic Monte Carlo algorithm

Hypothesis: Wormlike micelles (WLMs) formed due to the self-assembly of amphiphiles in aqueous solution have similar viscoelastic properties as polymers. Owing to this similarity, in this work, it is postulated that kinetic Monte Carlo (kMC) sampling of slip-springs dynamics, which is able to model the rheology of polymers, can also be extended to capture the relaxation dynamics of WLMs. Theory: The proposed modeling framework considers the following relaxation mechanisms: reptation, union-scission, and constraint release. Specifically, each of these relaxation mechanisms is simulated as separate kMC events that capture the relaxation dynamics while considering the living nature of WLMs within the slip-spring framework. As a case study, the model is implemented to a system of sodium oleate and sodium chloride to predict the linear rheology and the characteristic relaxation times associated with the individual relaxation mechanisms at different pH and salt concentrations. Findings: Linear rheology predictions were found to be in good agreement with experimental data. Furthermore, the calculated relaxation times highlighted that reptation contributed to a continuous increase in viscosity while union-scission contributed to the decrease in viscosity of WLM solutions at a higher salinity and pH. Finally, this manifests the proposed model’s capability to provide insights into the key processes governing WLM’s rheology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Minimal implicit-solvent coarse-grained simulation of Pluronic block copolymers with ionic liquids

Pluronic block copolymers, composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) in a triblock structure (PEO–PPO–PEO), are well known for their amphiphilic character and ability to self‐assemble into micelles in aqueous solution. The addition of ionic liquids (ILs) can further modulate the core–shell structures of these copolymers, influencing their stability, critical micellization temperature, and size. However, fully atomistic simulations often become prohibitively expensive due to the size and complexity of these systems. In this work, coarse‐grained simulations using a minimal implicit‐solvent model were performed to examine how two classes of ILs, namely, 1‐alkyl‐3‐methylimidazolium ([C n C 1 im]) and 1‐alkyl‐3‐methylpyrrolidinium ([C n C 1 pyrr]), change the micellization of Pluronic block copolymers in aqueous solution. The effects of IL concentration and alkyl group length were investigated, and the model greatly improved the efficiency of simulating large‐scale micelle systems. Furthermore, the numerical simulations are qualitatively compared with experimental investigations. Our results show that adding ILs expands the micelle core by embedding IL tails among the PPO blocks, thereby increasing overall micelle size. Less polar ILs generally induce more pronounced micellar growth. However, the effect of IL tail length on conformation and micellar packing is non‐monotonic. Up to moderate chain lengths (around C8–C10), the IL tails can extend sufficiently to increase local separation within the micelle; at longer tail lengths, enhanced hydrophobic clustering and steric hindrance cause the tails to bend or fold, capping further expansion. In addition, although block copolymer chains tend to pack more closely in the presence of longer‐tailed ILs, the random coil size of an individual polymer chain does not necessarily shrink. Meanwhile, these insights provide a deeper understanding of how Pluronic/IL systems interact, informing applications in drug delivery, cosmetics, food, and environmental engineering. Finally, our minimal implicit‐solvent model can be applied to larger systems and longer timescales, substantially reducing computational cost while reproducing key structural trends observed experimentally.

Atomistic simulations↗
DOE OSTI2020

Evaluation of Technologies for Enhancing Grout for Immobilizing Hanford Supplemental Low-Activity Waste (SLAW)

An expert panel consisting of the document authors was assembled by Washington River Protection Solutions, LLC (WRPS) and tasked with (1) identifying technical and regulatory limitations to treating and disposing of grouted low-activity waste (LAW), and (2) with identifying and evaluating a wide range of technical solutions to these limitations. The analysis included technologies to allow inventory management and/or improve retention of iodine, technetium, and nitrate either in the waste packages, or within the Integrated Disposal Facility (IDF), and, technologies to ensure regulated organics are below Resource Conservation and Recovery Act of 1976 (RCRA) Land Disposal Restriction (LDR) levels.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Layer-by-Layer Nanoarchitectonics of Electrochemically Active Thin Films Comprised of Radical-Containing Polymers

Electroactive coatings based on non-conjugated redox-active polymers have increased in popularity with the development of thin film organic batteries. Here, control over coating deposition, redox-activity, and ion transport are key to improving their energy storage performance. In this work, the synthesis, solution state electrochemical characterization, and layer-by-layer (LbL) assembly of a nitroxide-based polycation and polyanion are presented. Solution state electrochemical characterization indicates that the rate of electron transfer for the nitroxide polyanion is much higher as compared to the nitroxide polycation. LbL thin films of the nitroxide polyanion and nitroxide polycation are assembled, demonstrating linear growth and tunable thickness (28 nm/layer pair). This work confirms that the ion transport mechanism of the LbL films during the redox reaction is influenced depending on the charge of the terminating layer, where the nitroxide polyanion can participate in self-doping, which leads to a contribution from cation transport. The nitroxide polyanion-terminated film also exhibits a higher capacity and a slightly reduced charge transfer resistance. However, it was also observed that a more pronounced capacity fade occurred for the polyanion-terminated film than the polycation-terminated film. Taken together, this highlights how oppositely charged radical-containing polyelectrolytes can form electroactive coatings for possible applications in energy storage or sensing.

25 ENERGY STORAGE↗
DOE OSTI2024

Microscopic origin of tunable assembly forces in chiral active environments

Across a variety of spatial scales, from nanoscale biological systems to micron-scale colloidal systems, equilibrium self-assembly is entirely dictated by—and therefore limited by—the thermodynamic properties of the constituent materials. In contrast, nonequilibrium materials, such as self-propelled active matter, expand the possibilities for driving the assemblies that are inaccessible in equilibrium conditions. Recently, a number of works have suggested that active matter drives or accelerates self-organization, but the emergent interactions that arise between solutes immersed in actively driven environments are complex and poorly understood. Here, we analyze and resolve two crucial questions concerning actively driven self-assembly: (i) how, mechanistically, do active environments drive self-assembly of passive solutes? (ii) Under which conditions is this assembly robust? We employ the framework of odd hydrodynamics to theoretically explain numerical and experimental observations that chiral active matter, i.e., particles driven with a directional torque, produces robust and long-ranged assembly forces. Overall, these developments constitute an important step towards a comprehensive theoretical framework for controlling self-assembly in nonequilibrium environments.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Ionic assemblies, or clusters, determine the structure and dynamics of ionizable polymers and enable their many applications. Fundamental to attaining well-defined materials is controlling the balance between van der Waals interactions that govern the backbone behavior and the forces that drive the formation of ionic clusters. Here, using small angle neutron scattering and fully atomistic molecular dynamics simulations, the structure of a model ionomer, sulfonated polystyrene in toluene solutions, was investigated as the cluster cohesion was tweaked by the addition of ethanol. The static structure factor was measured by both techniques and correlated with the size of the ionic clusters as the polymer concentration was varied. The conjunction of SANS results and molecular insight from MD simulations enabled the determination of the structure in these inhomogeneous networks on multiple length scales. Additionally, we find that across the entire concentration range studied, a network driven by the formation of ionic clusters was formed, where the size of the clusters drives the inhomogeneity of these systems. Tweaking the ionic clusters through the addition of ethanol impacts the packing of the sulfonated groups, their shape, and their size distribution, which in turn, affects the structure of these networks.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evaluation of flame propagation of retrofit energy efficient wall assemblies

Leveraging safety science experience and industry relationships, UL Solutions and the International Association of Fire Fighters (IAFF) initiated a joint project in 2022 under an agreement with the US Department of Energy to evaluate the flame propagation of retrofit energy efficient wall assemblies. A draft of the protocol from the ASTM work was used to test and comparatively study various retrofit energy efficient designs to gain a better understanding of their fire behavior. The goals of this study were as follows: Develop an understanding of fire propagation across new, cost effective, and energy efficient exterior retrofit wall assemblies. Refine the flame propagation draft test method for exterior wall assemblies based on ASTM E2707. Identify conditions that create fire propagation hazards in exterior wall assemblies and educate the fire service on the findings.

42 ENGINEERING↗
DOE OSTI2022

Solvation Thermodynamics of Solutes in Water and Ionic Liquids Using the Multiscale Solvation-Layer Interface Condition Continuum Model

We report molecular assembly processes are generally driven by thermodynamic properties in solutions. Atomistic modeling can be very helpful in designing and understanding complex systems, except that bulk solvent is very inefficient to treat explicitly as discrete molecules. The SLIC/CDC multiscale model combines continuum solvent electrostatics based on the solvent layer interface condition (SLIC) with statistical thermodynamic models for hydrogen bonding and nonpolar modes: cavity formation, dispersion interactions, combinatorial mixing (CDC). The SLIC/CDC model predicts Gibbs energies of solvation for a database of 500 solutes in water with average accuracy better than 1 kcal/mol both for experimental measurements and for explicit-solvent molecular dynamics simulations. The separate SLIC/CDC energy mode values agree quantitatively with those computed from explicit-solvent molecular dynamics. The SLIC/SASA multiscale model combines the SLIC continuum electrostatic model with the solvent accessible surface area (SASA) nonpolar energy mode. The SLIC/SASA model predicts Gibbs energies of solvation with better than 1.4 kcal/mol average accuracy in aqueous systems and better than 1.6 kcal/mol average accuracy in ionic liquids. Both models predict solvation entropies, and are the first implicit-solvation models capable of predicting solvation heat capacities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Role of the Solvent–Surfactant Duality of Ionic Liquids in Directing Two-Dimensional Particle Assembly

Nanoparticle self-assembly plays a key role in formation of superlattices, which exhibit remarkable physical and chemical properties. However, controlling assembly remains a challenge partly due to a lack of understanding of the assembly dynamics and the difficulty in linking interfacial solution properties to interparticle forces. In this study, using liquid-cell transmission electron microscopy, self-assembly of gold nanoparticles (NPs) into superlattices in mixtures of water and ionic liquid (IL) was visualized, revealing a dual role of the IL in the assembly process. At intermediate concentrations, the IL acts as a surfactant stabilizing the particles at a well-defined equilibrium separation corresponding to the length of hydrogen bonded IL cations adsorbed onto neighboring NPs. Analysis of the interparticle forces reveals attractive long-range interactions of a van der Waals nature. At separations of 1-3 nm, interactions are dominated by attractive ion correlation and repulsive hydration forces giving rise to an energy minimum at 1.5 nm separation. The superlattice is further stabilized by hydrogen bonding, which shifts the equilibrium interparticle distance to 1.1 nm. In contrast, at higher concentrations, IL accumulates and forms a structured network in the gap between nanoparticles, where it acts as a solvent that eliminates the repulsive barrier and thus promotes particle coalescence. This solvent-surfactant duality of IL opens new opportunities for their use in directing particle assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Cation-Driven Assembly of Bilayered Vanadium Oxide and Graphene Oxide Nanoflakes to Form Two-Dimensional Heterostructure Electrodes for Li-Ion Batteries

Lithium preintercalated bilayered vanadium oxide (LVO or δ-Li x V 2 O 5 ·nH 2 O) and graphene oxide (GO) nanoflakes were assembled using a concentrated lithium chloride solution and annealed under vacuum at 200 °C to form two-dimensional (2D) δ-Li x V 2 O 5 ·nH 2 O and reduced GO (rGO) heterostructures. Here we found that the Li + ions from LiCl enhanced the oxide/carbon heterointerface formation and served as stabilizing ions to improve structural and electrochemical stability. The graphitic content of the heterostructure could be easily controlled by changing the initial GO concentration prior to assembly. We found that increasing the GO content in our heterostructure composition helped inhibit the electrochemical degradation of LVO during cycling and improved the rate capability of the heterostructure. A combination of scanning electron microscopy and X-ray diffraction was used to help confirm that a 2D heterointerface formed between LVO and GO, and the final phase composition was determined using energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Scanning transmission electron microscopy and electron energy-loss spectroscopy were additionally used to examine the heterostructures at high resolution, mapping the orientations of rGO and LVO layers and locally imaging their interlayer spacings. Further, electrochemical cycling of the cation-assembled LVO/rGO heterostructures in Li-ion cells with a non-aqueous electrolyte revealed that increasing the rGO content led to improved cycling stability and rate performance, despite slightly decreased charge storage capacity. The heterostructures with 0, 10, 20, and 35 wt % rGO exhibited capacities of 237, 216, 174, and 150 mAh g –1 , respectively. Moreover, the LVO/rGO-35 wt % and LVO/rGO-20 wt % heterostructures retained 75% (110 mAh g–1) and 67% (120 mAh g –1 ) of their initial capacities after increasing the specific current from 20 to 200 mA g –1 , while the LVO/rGO-10 wt % sample retained only 48% (107 mAh g –1 ) of its initial capacity under the same cycling conditions. In addition, the cation-assembled LVO/rGO electrodes exhibited enhanced electrochemical stability compared to electrodes prepared through physical mixing of LVO and GO nanoflakes in the same ratios as the heterostructure electrodes, further revealing the stabilizing effect of a 2D heterointerface. The cation-driven assembly approach, explored in this work using Li + cations, was found to induce and stabilize the formation of stacked 2D layers of rGO and exfoliated LVO. The reported assembly methodology can be applied for a variety of systems utilizing 2D materials with complementary properties for applications as electrodes in energy storage devices.

25 ENERGY STORAGE↗
DOE OSTI2023

Molecular entrapment via homopolymer self-assembly

The present invention provides novel nanostructures comprising solution of PPSU 20 . Methods of preparing the novel PPSU nanostructures, and applications of such nanostructures are also provided.

Scott, Evan A.↗
DOE OSTI2026

Structure of Complex Liquid–Liquid Extraction Organic Phases for Rare Earth Separations

Complex, multicomponent liquids with hierarchical structure and phase transitions are encountered in many natural and industrial processes, including in chemical separations. One notable example is aggregation and organic phase splitting in liquid–liquid extraction (LLE) of metal ions. While these two phenomena that have long been closely associated, a mechanistic link between mesoscale structure and the capacity-limiting organic phase splitting remains elusive due to complexity of these systems. Here, in this study, we combine small-angle X-ray scattering (SAXS), X-ray photon correlation spectroscopy (XPCS), and molecular dynamics simulation to reveal a comprehensive picture of structure at the nano- and mesoscale in these complex solutions. For the representative case of rare earth extraction from an acidic aqueous phase by a malonamide extractant in dodecane, we investigate a wide range of process-relevant extractant and acid concentrations to provide a complete picture of how aggregation depends on composition. We decompose organic phase structure from SAXS into two contributions, which together can capture the scattering at all compositions: composition fluctuations described by the Ornstein–Zernike equation at low wavenumber Q, and nanostructure modeled by a “pre-peak” at intermediate Q. The former contains information about the thermodynamics of demixing, while the latter reflects nanoscopic self-assembly of the extractant and extracted solutes. While fluctuations have typically not been considered in the literature, we find they in fact dominate the total structure for nearly all practical conditions. As only the fluctuations have a strong temperature response, we confirm this attribution with temperature-dependent SAXS measurements, including for extracted europium nitrate complexes. SAXS and XPCS measurements near the critical point find static and dynamic scaling consistent with theory. Overall, this new paradigm for understanding LLE organic phases connects composition, nanoscale, and mesoscale structuring to phase behavior, providing both a comprehensive picture of solution structure and a quantitative link between aggregation and third phase formation.

Peroutka, Allison A. [Argonne National Laboratory ↗