Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “solutes”

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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Temporal flow variations interact with spatial physical heterogeneity to impact solute transport in managed river corridors

The interactions between surface water and groundwater in river corridors lead to temporal fluctuations in subsurface water fluxes which have a critical role on solute transport dynamics. Here, we develop a framework to analyze the relative impacts of different temporal frequencies of the flow field in a spatially heterogeneous aquifer on solute transport. Our analysis indicates that the advection-dispersion equation behaves as a low-pass filter by wiping out the effect of high-frequency velocity fluctuations on the first two spatial moments of the solute plume, namely its center of mass and spreading. The concepts discussed in the theoretical analysis are then applied to understand solute transport dynamics at the 300 Area of the Hanford site (USA) adjacent to the Columbia River. We examine the temporal behavior of the solute plume's spatial moments for different temporal frequencies utilizing geostatistical parameters estimated in the 300 Area. Due to the proximity to the Columbia river, groundwater fluxes at the Hanford site are highly dynamic resulting in a large range of characteristic temporal frequencies. Nonetheless, similar to the theoretical analysis, our results show that the effect of high-frequency fluctuations is filtered, with most of the solute transport dynamics being controlled by fluctuations characterized by a large characteristic period.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Parametric study and speciation analysis of rare earth precipitation using oxalic acid in a chloride solution system

Oxalic acid precipitation is a common step in the purification of rare earth elements (REE) from a concentrated pregnant leach solution (PLS). However, the presence of contaminants such as Al, Fe, and Ca in given amounts decreases the REE precipitation efficiency and product purity while also increasing the amount of oxalic acid needed to maximize recovery. As such, a statistically designed test program was performed to identify the optimal conditions necessary for a relatively low REE content PLS containing elevated concentrations of contaminant ions. The performance objective was maximization of REE precipitation efficiency while minimizing the oxalic acid dosage. A central composite design was utilized to quantify performance impacts and identify the ultimate set of parameter values for oxalic acid dosage, Fe(III) contamination concentration, solution pH, and reaction temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicate that increasing the oxalic acid concentration from 0 g/L to 80 g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. Here, to further the understanding of the REE-oxalate system, a fundamental solution chemistry study was performed using the equilibrium constants of the reactions. The study resulted in the development of oxalate speciation diagrams and provided an analysis of the REE precipitation characteristics at various oxalate anion concentrations and Fe(III) contamination levels using MINTEQ software. The dominant Fe(III) species in the solution system were found to be Fe-(C 2 O 4 ) 3 3- , Fe-(C 2 O 4 ) 2- , and Fe-(C 2 O 4 ) + , which consume the majority of the oxalate anions. The simulated model was found to be in agreement with the experimental findings and helped to explain the adverse impact of increased iron concentrations on REE precipitation efficiency.

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

Solution and Interface Structure and Dynamics in Geochemistry: Gateway to Link Elementary Processes to Mineral Nucleation and Growth

Our understanding of the process of mineral nucleation is starting to evolve from the solely thermodynamical aspects in classical nucleation theory toward a mechanistic study of reactions influenced by solvation structures of ions and their dynamics. A knowledge of how these atomic and molecular interactions respond to changing solution composition and/or the nature of an interface will form a fundamental foundation to understand rate-limiting reactions and processes for nucleation and growth. Here, we review recent advances from multidisciplinary experimental and computational approaches of the structure and dynamics of aqueous solutions and mineral–liquid interfaces that will influence rates of nucleation (and growth behavior) both homogeneously in aqueous solutions and heterogeneously at mineral–liquid interfaces. Furthermore, these processes include structure (and extent) of solute clustering, solvent degrees of freedom, and the presence of noninnocent charge-balancing ions, all of which can drive the selectivity and exert control over nucleation mechanisms. Similar controlling reactions can also occur at interfaces with the added complexities of how solute ions interact with and assemble on surface sites and use different mechanisms from bulk solutes, such as lateral solvent exchanges between distinct surface sites. To gain a predictive understanding of nucleation chemistry, we emphasize several key knowledge gaps that will need to be addressed in this field and highlight the importance of combining computations and experiments.

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

Numerical Study of Coupled Water and Vapor Flow, Heat Transfer, and Solute Transport in Variably-Saturated Deformable Soil During Freeze-Thaw Cycles

As climate change intensifies, soil water flow, heat transfer, and solute transport in the active, unfrozen zones within permafrost and seasonally frozen ground exhibit progressively more complex interactions that are difficult to elucidate with measurements alone. For example, frozen conditions impede water flow and solute transport in soil, while heat and mass transfer are significantly affected by high thermal inertia generated from water-ice phase change during the freeze-thaw cycle. To assist in understanding these subsurface processes, the current study presents a coupled two-dimensional model, which examines heat conduction-convection with water-ice phase change, soil water (liquid water and vapor) and groundwater flow, advective-dispersive solute transport with sorption, and soil deformation (frost heave and thaw settlement) in variably saturated soils subjected to freeze-thaw actions. This coupled multiphysics problem is numerically solved using the finite element method. The model's performance is first verified by comparison to a well-documented freezing test on unsaturated soil in a laboratory environment obtained from the literature. Then based on the proposed model, we quantify the impacts of freeze-thaw cycles on the distribution of temperature, water content, displacement history, and solute concentration in three distinct soil types, including sand, silt and clay textures. The influence of fluctuations in the air temperature, groundwater level, hydraulic conductivity, and solute transport parameters was also comparatively studied. The results show that (a) there is a significant bidirectional exchange between groundwater in the saturated zone and soil water in the vadose zone during freeze-thaw periods, and its magnitude increases with the combined influence of higher hydraulic conductivity and higher capillarity; (b) the rapid dewatering ahead of the freezing front causes local volume shrinkage within the non-frozen region when the freezing front propagates downward during the freezing stage and this volume shrinkage reduces the impact of frost heave due to ice formation. This gradually recovers when the thawed water replenishes the water loss zone during the thawing stage; and (c) the profiles of soil moisture, temperature, displacement, and solute concentration during freeze-thaw cycles are sensitive to the changes in amplitude and freeze-thaw period of the sinusoidal varying air temperature near the ground surface, hydraulic conductivity of soil texture, and the initial groundwater levels. Our modeling framework and simulation results highlight the need to account for coupled thermal-hydraulic-mechanical-chemical behaviors to better understand soil water and groundwater dynamics during freeze-thaw cycles and further help explain the observed changes in water cycles and landscape evolution in cold regions.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1994

CoSb(sub 3)-IrSb(sub 3)Solid Solutions: Preparations and Characterization

The binary antimonide compounds of the skutterudite family have a good potential for thermoelectric applications as recent results at JPL have shown. However, the room temperature thermal conductivity of these materials is about 10 Wm(sup -1)K(sup -1) with an 80 % contribution from the lattice. To achieve maximum ZT values, the lattice thermal conductivity needs to be lowered. Because the lattice thermal conductivity of solid solutions can substantially decrease due to the addition of point defect phonon scattering (all state-of-the-art thermoelectric materials are solid solutions), a study of the formation of solid solutions between the antimonide skutterudite compounds is of interest. The preparation and characterization of both p-type and n-type CoSb(sub 3)-IrSb(sub 3) solid solutions by several techniques is reviewed in this paper. Experimental results showed that solid solutions were successfully formed in a wide range of compositions. The changes in the thermoelectric properties indicated the influence of a strong point defect scattering, resulting in large decreases in Hall mobility and thermal conductivity. The potential for high ZT values in CoSb(sub 3)-IrSb(sub 3) solid solutions is discussed.

mobility↗
DOE OSTI2021

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Abstract High‐energy X‐ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long‐range order, but is underutilized for molecular complexes in solution. We demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal⋅⋅⋅metal distances separated by over 12 Å. The metal⋅⋅⋅metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub‐Ångström conformational differences by direct comparison of solution phase and solid‐state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

Xie, Zhu‐Lin↗
DOE OSTI2021

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

High-energy X-ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long-range order, but is underutilized for molecular complexes in solution. Here we demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu I /Ru II /Os II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal...metal distances separated by over 12 Å. The metal…metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub-Ångström conformational differences by direct comparison of solution phase and solid-state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of solution concentration on ethylene propylene diene monomer (EPDM) nonmetallic components used in caustic liquid waste transfer lines

The hose-in-hose transfer lines (HIHTL) used to transfer waste at the United States Department of Energy’s Hanford Site Tank Farm are fabricated from an ethylene propylene diene monomer (EPDM) synthetic rubber. During waste transport, these hoses are exposed to several stressors including caustic solutions at high temperatures and high pressures, as well as β and γ radiation. The aging behavior of HIHTL and dog-bone shaped EPDM specimens were evaluated by exposure to solutions at 77 °C containing 0.00, 6.25, 12.50, and 25.00 % (v/v) sodium hydroxide (NaOH) for 12-months. After the exposure, the material properties of the specimens were measured and compared to the unaged samples. The material properties evaluated included the tensile strength of the EPDM dog-bone samples and the burst pressure of the HIHTL. Both the tensile strength of the EPDM dog-bone samples and the burst pressure of the HIHTL specimens exposed to the 6.25 % NaOH solution exhibited the most significant deterioration and those exposed to 25.00 % NaOH solution had the least deterioration. Finally, examination of the HIHTL and the EPDM dog-bone specimens with scanning electron microscopy showed that the deterioration for the specimens exposed to 6.25 % NaOH solution were the most severe and the samples exposed to 25.00 % NaOH solution had the least deterioration.

42 ENGINEERING↗
DOE OSTI2023

A comparative study of solute trapping in Fe-(33–45 at%) Cu alloys manufactured by laser directed energy deposition

The high cooling rates in laser directed energy deposition (DED-LB) of alloys lead to substantial amounts of solute trapping as solute atoms cannot diffuse away from the solid/liquid interface before it advances. In some concentrated alloys, this results in supersaturated solid phases that form nanoscale hierarchical microstructures when the solute atoms precipitate out during reheating from subsequent laser passes. We choose the Iron-Copper (Fe-Cu) binary alloy as model system as it is chemically homogeneous in the liquid phase and has negligible solid solubility at room temperature. Two alloys with nominal compositions in atomic (at.) %, Fe67Cu33 and Fe55Cu45, were manufactured using DED-LB. Scanning transmission electron microscopy (STEM), energy dispersive spectroscopy (EDS) and wavelength dispersive spectroscopy (WDS) were used to characterize the nanostructures and heterogeneous chemical compositions. A non-equilibrium solute partitioning model was used to compute the supersaturated chemistries of the constituent phases and validated with experimentally measured compositions. The measured phase compositions of the two alloys were very similar, at roughly 12 at.% Cu and 4 at.% Fe in the α(bcc)-Fe and ε(fcc)-Cu phases respectively, despite having different processing parameters and mechanical behavior. This indicates that the total thermal history, that depends on both the processing parameters and laser scan pattern, plays a stronger role on the final microstructure evolution than just the initial quantity of trapped solute. In addition, we find that current non-equilibrium solute partitioning models applied on the continuum scale fall short of predicting accurate quantitative phase compositions in concentrated alloys, although the qualitative trends are captured correctly.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A novel energy balance approach for a verifiable and accurate solution of radiation extinction in purely absorbing particle clouds

Here we consider the problem of radiation transport through purely absorbing particle clouds. The gold-standard solution of particle-resolved Monte Carlo ray-tracing method to this problem is computationally expensive and therefore solving the radiation transport equation (specifically, the Beer-Bouguer law (BB-law)) on a Eulerian mesh is often preferred. While the absorption coefficient in the real problem is infinite, the BB-law approximates it to be a finite number in the form of number density through a set of assumptions. For particle clouds that do not obey these assumptions, the BB-law predicts an incorrect exponential decay. Also, when the number density is computed using the nearest-neighbor approach, the BB-law solution diverges when the Eulerian mesh size becomes closer to or smaller than the particle size. This numerical divergence is due to the homogenization error. Although the filtering strategy for number density minimizes the homogenization error, it still converges to an incorrect exponential decay for particle clouds that break the BB-law constraints and the cost of the filtering is equivalent to that of the gold-standard solution. In this study, we develop a novel, highly accurate, verifiable and cost-effective solution to the radiation transport equation on a Eulerian domain using an energy balance approach where we derive an expression for the absorption coefficient as a function of particle and Eulerian mesh sizes. We apply our new method to Poisson and turbulent particle clouds that violate all the BB-law constraints and show that the solution is converging upon the mesh refinement, and eventually, we recover the same gold-standard solution for a much cheaper computational cost.

42 ENGINEERING↗
DOE OSTI2024

Self-consistent solution of the Frank–Bilby equation for interfaces containing disconnections

The quantized Frank–Bilby equation can be used to identify interfacial line defect array configurations which relax the misorientation and/or misfit of a coherent crystalline interface. These line defect arrays may be comprised of dislocations and/or disconnections, which are interfacial steps with dislocation character. When an interface contains disconnections, solution of the quantized Frank–Bilby equation is complicated by the fact that the habit plane orientation is not known in advance because it depends on the unknown spacing of the disconnection array. We present a root-finding-based method for addressing this issue, enabling a self-consistent solution for arbitrary defect content. Our method has been implemented in an open-source code which enumerates all possible solutions given a list of candidate line defects. Two cases are presented employing the code: a misoriented FCC twin boundary and an FCC/BCC phase boundary with the Nishiyama-Wasserman orientation relationship. Both cases exhibit more than 10,000 solutions to the Frank–Bilby equation, with several hundred solutions categorized as ‘‘low energy’’ and thus plausible configurations for the actual interface. The resulting set of solutions can be utilized to predict and understand the properties of a given interface.

42 ENGINEERING↗
DOE OSTI2023

Enhanced Carbon Dioxide Capture Using a Mixed Amino Acid Salt Solution

This study investigated the carbon dioxide (CO 2 ) absorption and desorption performance of a mixed amino acid solution (containing glycine (G), alanine (A), proline (P), and lysine (L), GAPL). These four amino acids were intentionally selected to reflect the chemical and structural variations (pK a and steric hindrance of amino groups) of amino acids. The single cycle CO 2 capture experiment showed that the GAPL salt solution had 19% higher CO 2 absorption (0.91 mol CO 2 /mol amino acids) compared to the absorption calculated by adding the proportional capacities of G, A, P, and L (0.77 mol CO 2 /mol amino acids). 13 C NMR data delineated the effects of individual amino acids on carbamate and bicarbonate/carbonate formation and elucidated the distribution of captured CO 2 in the GAPL salt solution. The recirculation experiment concluded that the GAPL salt solution had much better CO 2 capture performance than the conventional monoethanolamine process. Less than 10% of the absorption and cyclic capacity of the GAPL salt solution was lost after ten cycles of CO 2 capture. Furthermore, this study demonstrated an approach that blended amino acid solutions can be tailored and designed as new, efficient reagents to massively capture CO 2 in a technically feasible, economically viable, and environmentally friendly manner.

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

Theory-Guided Inelastic Neutron Scattering of Crystalline Alkaline Aluminate Salts Bearing Principal Motifs of Solution-State Species

Aluminate salts precipitated from caustic alkaline solutions exhibit a correlation between the anionic speciation and the identity of the alkali cation in the precipitate, with the aluminate ions occurring either in monomeric (Al(OH) 4 – ) or dimeric (Al 2 O(OH) 6 2– ) forms. The origin of this correlation is poorly understood as are the roles that oligomeric aluminate species play in determining the solution structure, prenucleation clusters, and precipitation pathways. Characterization of aluminate solution speciation with vibrational spectroscopy results in spectra that are difficult to interpret because the ions access a diverse and dynamic configurational space. To investigate the Al(OH) 4 – and Al 2 O(OH) 6 2– anions within a well-defined crystal lattice, inelastic neutron scattering (INS) and Raman spectroscopic data were collected and simulated by density functional theory for K 2 [Al 2 O(OH) 6 ], Rb 2 [Al 2 O(OH) 6 ], and Cs[Al(OH) 4 ]·2H 2 O. These structures capture archetypal solution aluminate species: the first two salts contain dimeric Al 2 O(OH) 6 2– anions, while the third contains the monomeric Al(OH) 4 – anion. Here, comparisons were made to the INS and Raman spectra of sodium aluminate solutions frozen in a glassy state. In contrast to solution systems, the crystal lattice of the salts results in well-defined vibrations and associated resolved bands in the INS spectra. The use of a theory-guided analysis of the INS of this solid alkaline aluminate series revealed that differences were related to the nature of the hydrogen-bonding network and showed that INS is a sensitive probe of the degree of completeness and strength of the bond network in hydrogen-bonded materials. Results suggest that the ionic size may explain cation-specific differences in crystallization pathways in alkaline aluminate salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigation of the Solution Chemistry of Hybrid Organic–Inorganic Indium Halides for New Material Discovery

Recently, metal halide perovskites (MHPs) have emerged as a new class of materials for optical and electronic applications such as solar cells and ionizing radiation detectors. Although the solution-processability of MHPs is among their greatest advantages, the solution chemistries of most metal halide systems and their relationship with the observed structural and chemical diversity are poorly understood. In this work, we study the solution chemistry of a model indium halide system, methylammonium (MA)–In–Br, using a combination of the UV–vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS) measurements, small-angle X-ray scattering (SAXS), and density functional theory (DFT) calculations. Our results show that indium could form either octahedral [InBr 6 3– ] or tetrahedral [InBr 4 – ] anions in solution or a combination of both, depending on the loading ratios of MABr and InBr 3 reactants. Understanding the solution chemistry of this system and recognizing the optical fingerprints of these polyanions allow for targeted crystallization of two novel compounds: MAInBr 4 featuring tetrahedral [InBr 4 – ] anions and MA 2 InBr 5 containing both octahedral [InBr 6 3– ] and tetrahedral [InBr 4 – ] anions. Further increase of the MABr content leads to the formation of previously reported MA 4 InBr 7 , containing only octahedral [InBr 6 3– ] anions separated by Br – anions. Furthermore, our results suggest that understanding the solution chemistry of multinary metal halide systems could be a valuable tool for discovering functional materials for practical applications.

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

Solution Structure and Hydration Forces between Mica and Hydrophilic Versus Hydrophobic Surfaces

Solid-liquid interfaces are central to a range of interesting phenomena including catalysis, heterogeneous nucleation, water desalination, and biomolecular assembly. While three-dimensional Fast Force Mapping (3D FFM) has emerged as a technique for resolving interfacial solution structure at the molecular scale, key challenges for data interpretation persist, most notably regarding the influence of the probe on the measured structure. Using the mica-water system as a case study, we investigate the effect of hydrophilic and hydrophobic probes on interfacial solution structure measured by 3D FFM. Data from hydrophilic silicon-based probes are in good agreement with molecular dynamics simulations, wherein the innermost water molecules adsorb preferentially at the surface ditrigonal cavity sites followed by two subsequent hydration layers. In contrast, the hydrophobic carbon-based probes detect vertical oscillatory features, but do not show lateral patterning that matches the underlying mica lattice. At high ionic strength, up to six of these oscillatory features are observed extending 2 nm into the solution phase with an average spacing of 0.29 ± (0.04) nm. Further, we also determine that the repulsive hydration force between mica and the hydrophilic probe depends on the nature and concentration of ions in solution. Specifically, solutions with stronger ion-water and ion-ion interactions increase the interfacial viscosity, which results in a stronger repulsive hydration force as the probe approaches the surface. Based on these observations, we present a scheme for controlling the outcomes of particle attachment and aggregation by varying the solution conditions to tune the hydration force.

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

Onsager Transport Coefficients and Transference Numbers in Polyelectrolyte Solutions and Polymerized Ionic Liquids

Electrolytes featuring negatively charged polymers, such as nonaqueous polyelectrolyte solutions and polymerized ionic liquids, are currently under investigation as potential high cation transference number (t+) electrolytes for lithium-ion batteries. Herein, we use coarse-grained molecular dynamics simulations to characterize the Onsager transport coefficients of polyelectrolyte solutions as a function of chain length and concentration. For all the systems studied, we find that the rigorously computed transference number is substantially lower than that approximated by the ideal solution (Nernst-Einstein) equations typically used to characterize these systems due to the presence of strong anion-anion and cation-anion correlations. None of the polyelectrolyte solutions achieve t+ greater than that of the conventional binary salt electrolyte, with some solutions having negative t+. Overall, this work demonstrates that the Nernst-Einstein assumption does not provide a physically meaningful estimate of the transference number in these solutions and calls into question the expectation of polyelectrolytes to exhibit a high cation transference number.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Pivotal Roles of Triple Screening-Topological, Electrostatic, and Hydrodynamic-On Dynamics in Semidilute Polyelectrolyte Solutions

For semidilute polyelectrolyte solutions, it is generally assumed that topological, electrostatic, and hydrodynamic interactions are screened (called triple screening). Despite a large body of research focused on polyelectrolyte solutions, the concept of triple screening has never been rigorously verified. In this work, we test the concept by probing concentration fluctuations in aqueous solutions containing a well-studied polyelectrolyte, sodium poly(styrenesulfonate) (NaPSS) with neutron scattering, theory, and molecular dynamics simulations. Neutron spin–echo (NSE) and small-angle neutron scattering (SANS) data from semidilute solutions of NaPSS are presented at different polymer and salt (NaCl) concentrations. A combined theory for structure (J. Chem. Phys. 105, 5183 (1996)) and dynamics (J. Chem. Phys. 107, 2619 (1997)), which captures effects of hydrodynamic, topological, and electrostatic screening, is used to interpret the experimental results. Here, the theory quantitatively predicts the decay rate obtained from the NSE measurements while capturing the shape and concentration dependencies of the polyelectrolyte peak observed in the SANS spectra. Detailed comparisons of the theory and the experiments reveal that the wavevector-dependent decay rate of concentration fluctuations in semidilute solutions of polyelectrolytes is dictated by the screening of hydrodynamic, topological, and electrostatic interactions. This conclusion is corroborated by coarse-grained molecular dynamics simulations, executed without any hydrodynamic interactions, which fail to capture the correct wavevector dependence of the decay rate. These results highlight that the theories based on the concept of triple screening provide a quantitative framework for predicting a relation between the structure and dynamics of polyelectrolyte solutions.

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

Controlling the Morphology of PEDOT:PSS Blend Films with Pre-Deposition Solution Composition and Deposition Technique

Understanding the relationships between morphology, fabrication processes, and thermoelectric performance in conducting polymers is essential to the development of high- efficiency organic thermoelectrics as an alternative to commonly used rare metals. Altering the film fabrication process of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with the addition of high boiling solvents to the precast solution improves the electrical conductivity and significantly increases its Seebeck value. Neutron scattering monitors the changes in the atomic, nanoscale, and mesoscale morphologies of PEDOT:PSS thin films with the addition of dimethyl sulfoxide (DMSO) to the aqueous solution prior to film formation and with varying fabrication procedures. The neutron scattering results show a decrease in the deuterated PSS domain size along with systematic variations in PEDOT fibril assemblies in the final blend film with the addition of DMSO to the pre-deposition solution. These structural modifications indicate that the increase in conductivity of PEDOT:PSS blends with addition of DMSO reported in the literature can be ascribed to the disruption of solvated PEDOT assemblies by the DMSO, forming smaller PSS domains in the pre-deposition solution and allowing smoother film formation. These improvements are observed significantly with the addition of just 1% DMSO but continue to modestly improve with the addition of up to 5% DMSO to the PEDOT:PSS blend pre-deposition solution. The fact that the variations in the measured morphology are independent of whether the films were deposited by spin or ultrasonic spray casting methods emphasizes the crucial importance of the structure of the blend in the pre-deposition solution in determining the final thin film blend morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗