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At least 19 records

Morphological controls on flow conductivity and viscosity of bentonite–polymer composites

In this study, the authors investigate the morphological organisation of polymers in bentonite–polymer composites (BPCs) used in geosynthetic clay liners and controls on hydraulic conductivity and viscosity. A limited understanding of the relationship between the microstructure of BPCs and their macroscopic engineering behaviour motivates this study. The polymer resides in the inter-granular pores of bentonite based on synchrotron-based small-angle X-ray scattering measurements, scanning electron microscopy imaging and pore size analyses. On wetting, the polymer swells to produce a swollen hydrogel residing in the inter-granular pores. Enhanced tortuosity arising from hydrogel formation reduces the hydraulic conductivity of BPCs. The higher viscosity of the BPC slurry is attributed to the higher shear resistance emerging from swelling of the polymer fraction on wetting. These findings link the morphological features of BPCs to the observed hydraulic conductivity and viscosity of these materials.

Engineering↗

FY23 Progress Report on Viscosity and Thermal Conductivity Measurements of Molten Salts

As presented in this report, thermal conductivity and viscosity measurements were performed on key chloride pseudo-binary molten salt systems of relevance to molten salt reactor developers. Thermal conductivity measurements were conducted with a variable gap technique, in which a known heat flux is driven across a molten salt specimen and the temperature difference is measured, allowing calculation of the thermal conductivity. This is achieved by establishing a small gap between the bottom of a cylindrical inner containment, which houses electrical heating elements, and an outer containment, which houses cooling channels; the gap size can be varied by compression of a formed bellows. A new calibration scheme was developed herein, involving a correction factor to the heat flux based on He measurements at various temperatures. Furthermore, the data processing methodology was improved to minimize the impact of radiative heat transfer in the calculation of salt specimen thermal conductivity from the temperature difference measurements. Viscosity measurements were conducted with a rolling ball viscometer, in which a ball rolls some known distance in an angled tubular crucible, and the terminal velocity can be used to calculate the viscosity of the salt. The measurement can be performed in a quartz crucible, with which a standard camera can be used to track the ball, or in a metal crucible, with which x-ray radiography is required to track the ball. A new custom x-ray system was made and dedicated to the rolling ball viscometer to enable high throughput automated measurements with salts which require containment with metal. Both systems have been integrated with a ventilation stack which allows for off-gassing of radioactive material, enabling future measurements with U-bearing salts. The thermal conductivity measurements performed herein were with NaCl-KCl (44 mol% NaCl). This salt system was measured in the previous fiscal year, however the thermal conductivity values obtained were comparatively low, and so the system was remeasured with the aforementioned calibration scheme and improved post-processing techniques. The newly obtained thermal conductivity values for NaCl-KCl (44 mol% NaCl) indicate good agreement with kinetic theory and ab-initio models (within 5–10 %). The viscosity measurements performed herein were with three different compositions of NaCl-KCl: 75, 50, and 25 mol% NaCl; a new calibration scheme was applied to account for variable flow effects in the laminar regime. The results show reasonable agreement with literature (5–20 %, depending on the temperature, composition, and study); however, literature values are likely higher than true values based on pure end-member measurements performed in the comparative studies. The measurements conducted herein do show a trend such that viscosity increases with increasing NaCl concentration, which agrees well with one of two comparative studies. In general, the measurements conducted herein gives confidence in the capability to use these systems to accurately measure thermal conductivity and viscosity of actinide-bearing salts within the next fiscal year.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

FY2022 Progress Report on Viscosity and Thermal Conductivity Measurements of Molten Salts

This report describes the development of and experimental measurements made with the thermal conductivity and viscosity measurement systems for molten salts at Oak Ridge National Laboratory. The thermal conductivity system is based on a steady-state measurement technique in which a heat flux is driven across a variable gap, and the changes in temperature difference across the gap are measured as the gap size is varied. The system comprises an inner containment, which possesses the heating element, and an outer containment, which possesses the salt specimen and cooling channels. The gap is formed between the outer bottom of the inner containment and the inner bottom of the outer containment. The viscosity system is based on the falling-ball technique in which a salt-filled tubular crucible is fixed at an angle and a ball rolls through the salt. The terminal velocity of the ball can be converted into viscosity via a calibration factor calculated for crucible-ball combinations which account for thermal expansion and flow characteristics. Modifications were made to both systems this fiscal year. Modifications to the thermal conductivity system included adding guard heaters to prevent axial heating losses, and modifications to the viscosity system included changing the crucible design to prevent air pocket formation and providing the ability to conduct measurements with a glass or steel crucible.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Electrochemical, thermodynamic, and physical properties of tetradecyltrihexylphosphonium ([P 6,6, 6,14 ] + ) and methyl-propyl piperidinium containing ionic liquids and their propylene carbonate solutions

Here, the viscosity, conductivity, electrochemical window and related thermodynamic properties such as excess volume and dynamic viscosity deviation of two phosphonium ionic liquids were measured and calculated for “as-supplied” and dried neat liquids and also v/v mixtures of 99/1, 95/5, 90/10, 75/25, and 50/50 of the ionic liquids with propylene carbonate (PC). Tetradecyltrihexylphosphonium dicyanamide ([P 6,6,6,14 ] + dicyanamide), Cyphos 105, and tetradecyltrihexylphosphonium bis(trifluororomethanesulfonyl)imide (called bistriflimide) ([P 6,6,6,14 ] + bistriflimide), Cyphos 109, ionic liquids were studied. Generally speaking, there were slight differences in the measured properties of the wet and dried IL solutions which were reflected in differences if the calculated properties. The measured and calculated properties were compared with those collected and derived from a piperidinium-based ionic liquid, methyl-propyl piperidinium bistriflimide. Arrhenius plots for both the viscosity and conductivity were linear, with the linearity of the Litovitz plots being slightly higher. The viscosity and conductivity of the phosphonium solutions yielded Walden Plots that differed from Walden plots of piperidinium solutions and other ionic liquid solutions. For the phosphonium based ionic liquids, the ionicity was found to increase with increasing dilution in propylene carbonate. The electrochemical windows of the ionic liquids were determined as a function of the concentration of the ionic liquid present in the solution. The size of the window generally initially decreased and then increased with the addition of PC for the [P 6,6,6,14 ] + dicyanamide ionic liquid increasing from 3.4 V in the 95/5 v/v (volume Cyphos 105) to volume of PC solvent) to 3.7 in the 50/50 dried IL case. The electrochemical windows of the dried liquids were slightly larger 3.5 V for the 95/5 v/v and 4.2 V for the 50/50 v/v Cyphos 105/PC solutions. The electrochemical window was larger and the conductivity was higher for the piperidinium IL solutions, but since the ionicity increases with dilution, the phosphonium based IL solutions may prove favorable for processes such as electrochemical reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Surrogate Fission Products on Thermal Conductivity and Viscosity of NaCl-UCl 3

Thermophysical properties of salt systems relevant to molten salt reactors (MSRs) are experimentally measured in support of the US Department of Energy Office of Nuclear Energy (DOE-NE) MSR campaign within the Advanced Reactor Technology (ART) Program. These property measurements also support the development of the thermophysical arm of the Molten Salt Database (MSD) within DOE-NE’s Nu clear Energy Advanced Modeling and Simulation (NEAMS) Program. Several US Department of Energy (DOE) laboratories, including Oak Ridge National Laboratory (ORNL), have been capitalizing on modern methodologies and sample characterization techniques to conduct thermophysical property measurements to support these programs and to provide MSR developers and modelers with more recent and higher-quality data.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Impact of the LiPF6 Concentration on the Interfacial Charge Transfer and Fast-charging Capabilities of Lithium-Ion Batteries

Fast-charging lithium-ion batteries (LIB) demand optimized electrolyte formulations to balance ionic conductivity, viscosity, and interfacial charge transfer kinetics. This study examines how LiPF 6 concentration shapes solvation structure, desolvation energy, charge transfer activation energy, and solid electrolyte interphase (SEI) properties, which are critical for fast-charging performance. Using Raman spectroscopy, electrochemical cycling, X-ray photoelectron spectroscopy, and atomistic modeling, we analyze how varying LiPF 6 concentrations impact interfacial and bulk transport properties. Our findings show that increasing LiPF 6 concentration alters lithium solvation structures, reduces desolvation energy, and accelerates charge transfer at the electrode interface. Higher concentrations lower the activation energy for charge transfer and suppress excessive SEI growth, improving interfacial kinetics. However, concentrations above a certain threshold increase viscosity and reduce ionic conductivity, limiting transport efficiency. These results offer insights into electrolyte solvation and interfacial charge transfer mechanisms, providing guidelines for designing next-generation fast-charging LIB electrolytes with enhanced efficiency, stability, and longevity.

Son, Seoung-Bum [Argonne National Laboratory (ANL)↗

Index tests for geosynthetic clay liners containing bentonite–polymer composites

The hydraulic conductivity of geosynthetic clay liners (GCLs) containing bentonite–polymer composites (BPCs) is controlled by a pore clogging mechanism related to the swelling of sodium bentonite (NaB) granules and formation of polymer gel in the pore space. Three index testing procedures that are influenced by bentonite swelling and rheology of the polymer gel were evaluated in this study for screening BPC GCLs for hydraulic conductivity: viscosity, liquid limit by fall-cone penetration and active water content. Experiments were conducted using polyacrylamide (PAM) polymer, dry-blended mixtures of PAM and NaB and a BPC from a commercially available GCL. These materials were contacted with inorganic solutions representing leachates from a range of waste containment scenarios. For the BPC that was evaluated, hydraulic conductivities less than 10 -10 m/s were obtained when the viscosity exceeded 220 mPa s and the active water content exceeded 300%. Hydraulic conductivities less than 10 -11 m/s were achieved for viscosity exceeding 350 mPa s, fall-cone liquid limit exceeding 190 and active water content exceeding 300%. Additional testing is needed to assess the generality of these index tests and the identified thresholds when applied to other BPC GCLs and other permeant liquids.

Engineering↗

Thermal Property Characterization of Molten Salt Reactor–Relevant Salts

The thermochemical and thermophysical properties of molten salt systems are necessary input for the design, licensing, and deployment of molten salt reactor concepts. The thermochemical and thermophysical property measurement capabilities being used and developed at Oak Ridge National Laboratory (ORNL) include liquid density, volumetric thermal expansion, viscosity, vapor pressure, phase behavior, and heat capacity and thermal conductivity measurement capabilities. Properties of eutectic LiF-NaF-KF (FLiNaK) and NaCl-KCl are being measured to validate the measurement techniques to be used to provide data to reactor developers and to better quantify the uncertainty of measurements. This report summarizes the status of thermal conductivity, viscosity, specific heat capacity, and density. A method for property estimation using Redlich Kister expansion is also described. This technique will be used to help validate measured properties and to guide future experiments by targeting mixtures or components for which data are uncertain or lacking.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Final Report for Tech-X Corporations’s contribution to Enhancing Understanding of High Energy Density Plasmas from Wire Array and Solid Liner Implosions Using Fluid Modeling with Kinetic Closures

Recent results from experiments and simulation of magnetically driven pulsed power liners have explored the role of the early-time electrothermal instability in the evolution of the magneto-Rayleigh-Taylor instability. Our focus will be on understanding the development of such instabilities and the potential stabilization mechanisms via electron thermal conduction, viscosity, and large magnetic fields which we expect could play a significant role in supporting the success of the MagLIF program. Experiments have shown that studies of high-energy density plasmas from wire-array implosions require physics modeling that goes well beyond simple models such as ideal magnetohydrodynamics. The goal of this work is to provide increased understanding of these experiments by employing simulations with a multi-fluid extended-MHD model which uses kinetic closures for thermal conduction, resistivity and viscosity. We will use codes easily available to the wider research community, including university students, with a secondary goal of providing the community with well-benchmarked tools capable of advanced modeling of high-energy-density plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Stockmayer fluid simulations for viscosity and glass transition temperature of ionic liquids

We develop a Stockmayer fluid model for molecular dynamics simulations of ionic liquids that captures molecular polarization, ionic conductivity, viscosity, and glass transition temperature, using ethylammonium nitrate (EAN) as an example. The ions in EAN are treated as spheres interacting via the Lennard-Jones potential with an embedded point charge and a permanent dipole moment. We show that our simulation results for EAN are consistent with experimental data and then explore the effects of the molecular parameters on the viscosity of ionic liquids. Our results indicate that viscosity monotonically increases with ionic charge and dipole moment but non-monotonically changes with ionic diameter (or molar volume). This non-monotonic trend arises from the competition among the electrostatic interactions, molecular packing, and size asymmetry between the cation and anion. In conclusion, our model also shows that long-lived ion pairs result in higher viscosities.

Coarse-grained simulations↗

Completion of Transport Property Measurements on Multiple Actinide Fluoride Mixtures

One of the missions of the US Department of Energy’s Office of Nuclear Energy (DOE-NE) Molten Salt Reactor (MSR) Campaign under the Advanced Reactor Technology program has been to experimentally measure thermophysical properties of MSR-relevent salt systems, with the intent of supporting the development of the Molten Salt Thermal Properties Database (MSTDB). This database is jointly funded by the DOE-NE Nuclear Energy Advanced Modeling and Simulation Program and the MSR Campaign. Multiple DOE national laboratories, including Oak Ridge National Laboratory (ORNL), have been conducting measurements of thermophysical properties to support MSTDB development and provide MSR developers with access to new data that has been measured using modern methodologies and more advanced sample characterization techniques. These data may either fill gaps in the database or provide updated higher quality data to replace legacy data. Researchers at ORNL have recognized significant gaps in the transport property data of actinide-bearing fluoride salt systems of MSR industry interest. Moreover, for the data present in MSTDB in this category, the uncertainty margins are generally high, leading to questionability in our current understanding of the thermophysical characterization of actinide fluoride mixtures. As such, the focus of this study has been to generate new transport property data of actinide fluoride mixtures that are of immediate interest to MSR developers. Specifically, the mixtures NaF-UF 4 (78 - 22 mol%) and NaF-KF-UF 4 (57-16.04-26.91 mol%) have been studied—NaF-UF 4 for thermal conductivity and viscosity and NaF-KF-UF 4 for viscosity. Thermal conductivity measurements have been conducted with a variable gap apparatus, whereas viscosity has been measured with a rolling ball viscometer. Methodological and calibration details are provided for both measurement processes, along with measurement system updates that have enabled easier manufacturing of components and fewer challenges associated with conducting the measurements themselves. The resultant data collected for NaF-UF 4 (78–22 mol%) and NaF-KF-UF 4 (57-16.04-26.91 mol%) have been compared with relevant mixture data within the thermophysical arm of the MSTDB (MSTDB-TP).

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

The effect of hydroxyl spacing in diols on the solvation structure, dynamics, and transport properties of choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) are a class of liquids that offer great potential in alleviating some of the challenges present in today's long-term energy storage methods because they have physical properties that are favorable for storable electrolyte solutions. In this work, a series of glycols (ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol) were studied as potential hydrogen bond donors (HBD) with a common choline chloride (ChCl) as the hydrogen bond acceptor (HBA). The solvation dynamics of the prepared systems were studied by measuring the solvent reorganization response using femtosecond transient absorption spectroscopy (fs-TA). Conductivity, viscosity, density, ET(30) polarity, and dynamics of the prepared DESs were analyzed, with a particular interest in determining the effect of HBD chain length on these parameters. Here, classical molecular dynamics simulations were employed to investigate how the local liquid structure, solvent dynamics, and bulk solvent properties vary with changes in glycol chain length.

Conductivity↗

Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small-Angle X-Ray Scattering

The fundamental understanding of nanostructures of liquid electrolytes is expected to enable transformative gains in electrochemical energy storage capacities. However, the solvation structures and molecular dynamics in electrolytes are hard to probe, which limits further performance improvements in macroscopic properties such as ionic conductivity, viscosity, and stability. Small-angle X-ray scattering (SAXS), a non-destructive method for nanostructures characterization in liquids, offers a unique perspective on molecular clusters, anion-cation pairs, solvation sheath, percolating network, aggregates, and domain sizes of electrolytes. Notably, the SAXS method has excellent time-resolution, enabling the study of molecular dynamics by operando characterization. This review focuses on the microscopic understanding of liquid electrolytes by SAXS and operando SAXS. The unique capabilities of X-ray scattering for intra- and inter-molecular relationship and nanostructure characterization of electrolytes are highlighted.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Solvation dynamics of choline fluoride in ethylene glycol – Water mixtures

Due to their favorable physical properties, deep eutectic solvents (DESs) have been of interest in many applications in the energy and industry sectors. In this study, we investigate the new deep eutectic solvent ethalineF (a 1:2 M ratio of choline fluoride:ethylene glycol) and the effect of water addition on the solvation dynamics compared to the better known ethaline (a 1:2 M ratio of choline chloride:ethylene glycol). Femtosecond transient absorption spectroscopy and NMR diffusometry were used to study the solvation dynamics. 19 F NMR spectra were obtained for ethalineF solutions with different water additions. The 19 F NMR spectra show two fluorine signals; one can be assigned to fluoride anions solvated by EG and the other signal to fluoride anions associated with the much heavier and less mobile choline cation. Density, viscosity, conductivity, and E T (30) polarity measurements are also provided for ethalineF. The nuclear spin nature of fluorine atom permits to measure the self-diffusion coefficient of the negative ion in addition of the cation diffusion in a choline halide based deep eutectic solvent system. This allows to calculate the NMR-predicted conductivities σ NMR . The obtained ion dissociation coefficients α D at different water concentrations suggest a partial ion dissociation which was commensurate with the relatively low ion conductivity. Furthermore, the observed modest conductivity of ethalineF is explained in terms of ion association as well as the gradual increase in conductivity caused by the addition of water.

19F NMR↗

Progress Towards Extended Cycle Life Si-based Anodes: Investigation of Fluorinated Local High Concentration Electrolytes

Silicon (Si) anodes are promising candidates for Li-ion batteries due to their high specific capacity and low operating potential. Implementation has been challenged by the significant Si volume changes during (de)lithiation and associated growth/regrowth of the solid electrolyte interphase (SEI). In this report, fluorinated local high concentration electrolytes (FLHCEs) were designed such that each component of the electrolyte (solvent, salt, diluent) is fluorinated to modify the chemistry and stabilize the SEI of high (30%) silicon content anodes. FLHCEs were formulated to probe the electrolyte salt concentration and ratio of the fluorinated carbonate solvents to a hydrofluoroether diluent. Higher salt concentrations led to higher viscosities, conductivities, and contact angles on polyethylene separators. Electrochemical cycling of Si-graphite/NMC622 pouch cells using the FLHCEs delivered up to 67% capacity retention after 100 cycles at a C/3 rate. Post-cycling X-ray photoelectron spectroscopy (XPS) analyses of the Si-graphite anodes indicated the FLHCEs formed a LiF rich solid electrolyte interphase (SEI). The findings show that the fluorinated local high concentration electrolytes contribute to stabilizing the Si-graphite electrode over extended cycling.

36 MATERIALS SCIENCE↗

Elucidating the Effects of Temperature on Nonaqueous Redox Flow Cell Cycling Performance

The impact of cell temperature is a relatively underexplored area within the burgeoning field of nonaqueous redox flow batteries (NAqRFBs). Here, we investigate the effect of elevated temperature on the performance of nonaqueous redox electrolytes and associated flow cells. Using a model compound, N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT), in a propylene-carbonate-based electrolyte, we experimentally measure the temperature dependence of relevant physicochemical properties (i.e., electrolyte conductivity, viscosity, diffusivity) and electrochemical characteristics (i.e., chemical and electrochemical reversibility) across a temperature range of 30 °C to 70 °C. We then perform flow cell studies, finding that while ohmic and mass transport resistances decrease significantly with increases in temperature for the MEEPT/MEEPT +· redox couple, accessible electrolyte capacity gradually reduces at temperatures > 50 °C. Ex-situ, post-test characterization using microelectrode voltammetry suggests that this capacity fade is due to instability of the MEEPT radical cation. Finally, using MEEPT as a posolyte and a model viologen negolyte (bis(2-(2-methoxyethoxy)ethyl)viologen), we assemble a full cell and perform polarization analyses, observing a 2× increase in the peak power density when the operating temperature is increased from 30 °C to 70 °C. Broadly, this work highlights opportunities for systematic engineering of nonaqueous electrolytes and flow cells for higher power operation at elevated temperatures.

Electrochemistry↗

Atomistic Simulations for Thermophysical Properties of Uranium-Containing Halide Molten Salts

Characterizing the thermophysical properties in both fuel and coolant salts are critical in modeling, developing, process optimizing and utilizing molten salt reactors (MSRs), as these properties directly relate to operation metrics and can inform on the selection of candidate salts. The demand for consistent, accurate and publicly available thermophysical property data has become more apparent in recent years as interests have increased from molten salt reactor developers. There are a number of challenges in experimentally measuring properties such as thermal conductivity, viscosity, density and heat capacity , which have led to sparse and often times conflicting data points or molten salts in general. Additionally, there are a number of hazards to consider when synthesizing, storing, using, treating and disposing of molten salts. With the advances in computational capabilities over the last 10 years, the use of atomistic simulations can be implemented to support these efforts. The primary objective of this work is characterize the thermophysical transport properties in a number of molten chloride salts, and in particular NaCl-UCl 3 using ab-initio molecular dynamic (AIMD) simulations. In this binary salt the UCl 3 acts as the primary fissile material and NaCl acts as a carrier salt due with its’ high solubility for actinides A number of studies on the thermophysical properties of NaCl-UCl 3 have been published but there is not a vast amount of viscosity data for this system. In 1975, Desyatnik, et al published a study reporting dynamic viscosities that were calculated from kinematic viscosity measurements, and using the coefficients provided the viscosity in a 70:30 NaCl:UCl 3 mixture is 2.29 cP and 2.88 for a 60:40 mixture. Termini et al. recently reported viscosities in the range of 2.75 – 3 cP for the 63:37 NaCl-UCl 3 mixture in the same temperature range using rolling ball viscosity measurements. Computational viscosity of a similar mixture (64:36) can be obtained from the work Andersson et al. using the reported diffusion coefficients, and the hydrodynamic radius from the pair-radial distribution functions (RDFs). Using Eq (1) (vida infra), the viscosity would be 2.50 cP at 1100K. This is not to say that these values are incorrect due to the varying reported values, but aims to highlight the necessity of this work. The data reported in this ongoing work are computations on a 64:36 mixture of NaCl-UCl 3 at 987K. This work is likely to be expanded into varying concentrations of this mixture along with the inclusion of other salt candidate mixtures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Enhanced HLW glass property-composition models - phase 3

During the present phase (Phase 3) of work to enhance and expand the HLW glass property-composition models, test data for 137 glasses were collected and incorporated into the combined WTP/ORP database. The new data include those collected on glasses from two statistically designed matrices to augment the moderate alumina region (the HLW16-MA matrix covering the region of 9 wt% < Al2O3 < 12 wt% with 16 glasses) and the ultra-high alumina region (the HLW16-UHA matrix covering the region of 26 wt% < Al2O3 < 29 wt% with 29 glasses). The addition of ORP glasses over the different phases of testing has significantly expanded the combined WTP/ORP database. The compiled data include glass compositions, PCT (B, Li and Na) releases, spinel T1%, electrical conductivity, viscosity, TCLP-Cd releases, and nepheline formation upon CCC. With the exception of the CCC spinel formation data – the CCC data will be used to support the further development of nepheline models for Hanford HLW glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗