Search NASA⌕ Search

SEARCH · Search NASA

Results for “modified separator”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Interphase Engineering Enabled by Using a Separator with Electrochemically Active Carbazole Polymers for Lithium-Ion Batteries

Separators are generally considered inert components in lithium-ion batteries. In the past, some electroactive polymers have been successfully applied in separator modifications for overcharge protection or as acid scavengers. This study highlights the first use of two “electroactive” carbazole polymers (copolymer 9-phenyl-9H-carbazole-phenyl [PCP] and poly(9-vinylcarbazole) [PVC]), which were each applied separately as coatings on the cathode-facing side of commercial Celgard 2325 separators, respectively, to enhance the cycling performance of 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 //graphite (LMR-NM//Gr) full cells through interphase engineering. The team observed an irreversible polymer oxidation process of the carbazole-functionalized polymers—occurring only during the first charge—for the modified separator cells, and the results were confirmed by dQ/dV analysis, cyclic voltammetry measurements, and nuclear magnetic resonance characterizations. During this oxidation, carbazole polymers participate in the process of interphase formation, contributing to the improved cycling performance of LMR-NM//Gr batteries. Particularly, oxidation takes place at voltages of ~4.0 and ~3.5 V when PCP and PVC are used as separator coatings, which is highly irreversible. Further postmortem examinations suggest that the improvements using these modified separators arise from the formation of higher-quality and more inorganic SEI, as well as the beneficial CEI enriched in LixPOyFz. These interphases effectively inhibit the crosstalk effect by reducing TM dissolution.

carbazole↗
DOE OSTI2024

In-situ ionothermal synthesis of nanoporous carbon/oxide composites: A new key to functional separators for stable lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) with high energy density are promising for energy storage. However, conventional polypropylene-based separator cannot avoid polysulfides shuttling which impedes the practical application of LSBs. Herein, an in-situ ionothermal synthesis strategy that concurrently applies ionic liquid as the solvent, template and high-yield carbon source is proposed for the facile preparation of nanoporous carbon/oxide composite separator modifiers. The composites exhibit features of high polarity, self doping, oxygen vacancy, heteroatom doping, abundant defects and high electronic conductivity. Theoretical and experimental studies suggest that the composites can efficiently trap and convert polysulfides for high-performance LSBs. Indeed, in the composite-modified LSBs with next-generation roll-to-roll dry-processed high-loading sulfur cathodes, enhanced performance is achieved, revealing the effectiveness of the composites as functional materials towards separator modification. Therefore, the proposed strategy and its delivered nanoporous composites exhibit excellent versatility and practicality for high-performance LSBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Alumina – Stabilized SEI and CEI in Potassium Metal Batteries

Aluminum oxide (Al 2 O 3 ) nanopowder is spin-coated onto both sides of commercial polypropene separator to create artificial solid-electrolyte interphase (SEI) and artificial cathode electrolyte interface (CEI) in potassium metal batteries (KMBs). Here, this significantly enhances the stability, including of KMBs with Prussian Blue (PB) cathodes. For example, symmetric cells are stable after 1,000 cycles at 0.5 mA/cm 2 –0.5 mAh/cm 2 and 3.0 mA/cm 2 –0.5 mAh/cm 2 . Alumina modified separators promote electrolyte wetting and increase ionic conductivity (0.59 vs. 0.2 mS/cm) and transference number (0.81 vs. 0.23). Cryo-stage focused ion beam (cryo-FIB) analysis of cycled modified anode demonstrates dense and planar electrodeposits, versus unmodified baseline consisting of metal filaments (dendrites) interspersed with pores and SEI. Alumina-modified CEI also suppresses elemental Fe crossover and reduces cathode cracking. Mesoscale modeling of metal – SEI interactions captures crucial role of intrinsic heterogeneities, illustrating how artificial SEI affects reaction current distribution, conductivity and morphological stability.

25 ENERGY STORAGE↗
DOE OSTI2026

Side-Chain Nanophase Separation Broadens the Double-Gyroid Stability Window in PS–PODMA Diblock Copolymers

Expanding access to bicontinuous network phases in block copolymers remains an important challenge because the double gyroid (DG) phase is usually stable only within a narrow composition window in conventional diblock copolymers. Here, we show that poly(styrene-block-octadecyl methacrylate) (PS-b-PODMA) exhibits an unusually broad DG window. Small-angle X-ray scattering measurements across a wide composition range reveal lamellar and hexagonally packed cylindrical phases at higher polystyrene fractions. In contrast, the DG phase appears over 0.22 ≤ fPS ≤ 0.35, with DG/BCC and DG/HEX coexistence near fPS = 0.18 and 0.40, respectively. This broad DG window is much wider than those reported for neat diblock copolymers and is not readily explained by conformational asymmetry alone. Wide-angle X-ray scattering detects a characteristic signature of nanophase separation within the PODMA-rich domains, indicating that side-chain ordering introduces an additional internal length scale. These results suggest that hierarchical side-chain nanophase separation modifies packing frustration and curvature selection, thereby broadening DG stability and providing a new molecular design strategy for stabilizing complex network morphologies.

Seko, Tamio↗
DOE OSTI2026

Jumpstart Opportunities to Unleash Leadership in Energy Storage (JOULES)

Current-generation Li-ion batteries with cobalt- and nickel-containing cathodes and graphite anodes are approaching performance and cost limits. In this program, 24M Technologies, Inc. (24M) is teaming with the Massachusetts Institute of Technology (MIT) and University of Michigan (UM) to develop low cost and fast charging sodium metal batteries with good low-temperature performance and high energy density, building upon previous work performed under ARPA-E programs. Key achievements include optimization of solid electrolyte and anode current collector, optimized cathode active materials, development of high-performance electrolyte formulations, and integration of these components into full cells. The cell design incorporates (1) an ultra-thick cathode (>9 mAh/cm 2 ) comprising advanced cobalt-free, sodium cathode active material, (2) advanced fast-charging electrolyte (up to 12 mS/cm) developed using machine learning and automated high-throughput screening technology by UM, and (3) ceramic modified separator that enable smooth Na transport and deposition, developed at MIT, enabling a high-energy density anode-free configuration and maximizing the energy density of sodium batteries. The team has successfully combined these approaches to sodium chemistry and paved the way to meeting the fast-charging, high-energy density, and low-cost requirements of next-generation drone, electric vertical take-off and -landing, and electric vehicle batteries. Performance for anode-free sodium cells developed under this program is more powerful than the commercial Li-ion batteries. The final deliverable cell design has achieved over 300 Wh/kg and volumetric energy density above 800 Wh/L (Table 1). Additionally, the team has achieved over (1) a lifetime of 340 cycles, (2) 80% capacity retention at -20 °C (compared 25 °C), and (3) the ability to fast charge to 80% SOC in 20 minutes.

25 ENERGY STORAGE↗
DOE OSTI2025

Size-Selective Nanoporous Atomically Thin Graphene Separators for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are extensively researched for their high energy densities but are hindered by the lithium polysulfide (LiPS) shuttling effect, which results in poor cyclability. A popular mitigation strategy is separator modification, where a LiPS trapping material is slurry-coated onto a conventional microporous polypropylene (PP) separator. This additional mass and volume unfortunately compromise the overall energy density of the LSB. This study aims to take a separator modification approach that avoids this issue. Nanoporous atomically thin membranes (NATMs) made of graphene are gaining attention for their scalable synthesis, tunable pore size, and negligible pore length. Herein, we apply a well-characterized graphene NATM for reasons similar to those of a size-selective interlayer in LSBs. The tailored pore size of ∼0.7–1.0 nm and atomic thinness facilitate the passage of Li + (solvated ionic diameters ∼0.54–1.26 nm) and blockage of larger LiPS (solvated ionic diameters ∼0.81–1.69 nm) without adding significant impedances or mass. The sulfur confinement is confirmed through scanning electron microscopy and energy-dispersive X-ray spectroscopy elemental analysis of the Li anode. An LSB with a NATM@PP separator shows virtually no capacity loss over 150 cycles, demonstrating efficacy of size-selective molecular sieving using NATMs in LSBs.

battery separator↗
DOE OSTI2026

Alkali-Metal Interlocking of 2D V 4 O 10 Sheets Defines Discretized Interlayer Shear Relationships

Low-dimensional materials manifest structural anisotropy, quantum confinement, and tightly bound excitonic states, which make them attractive building blocks that can be assembled within three-dimensional laterally stitched heterostructures, stacked van der Waals solids, and complex moiré superlattices. Ion intercalation in the galleries between layered materials provides a means of modifying interlayer separation and coupling, but it is also known to drive the shearing of the layers. In this article, we explore the distinct ligand coordination environments afforded by vanadyl oxygens of singular [V 4 O 10 ] sheets and examine how the size, polarizability, and stoichiometry of Group I cations sandwiched between such layers determine the interlocking of the sheets in stacked structures. Based on the topochemical insertion of alkali-metal ions into the layered λ-V 2 O 5 , we identify seven types of guest ion coordination sites discretized into four distinct regimes of interlayer shear in units of half octahedral widths. The coordination preferences of intercalated cations govern how they interlock 2D [V 4 O 10 ] sheets and engender specific shear conformations. We present evidence that static and dynamic disorder in guest ion arrangement modulate the magnetic structure of the intercalated compounds based on electrostatic polarization, localization of charge and spin density, and lattice distortion. The results illustrate the use of topochemical ion insertion to modulate stacking relationships and magnetic transition characteristics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Leveraging Macrocyclic Chelators for Rare Earth Element Separations

The long-term objective of this project is to develop new, more energy-efficient and environmentally benign separations of the rare earth elements. The current approaches to separate the rare earth elements employ liquid-liquid extraction methods, using a biphasic mixture of aqueous and organic solvents containing different metal-binding agents. Although a significant amount of work has been carried out to develop new organic-phase extractants, significantly less has been executed for the design of aqueous complexants. Our approach to achieve better rare earth separations is to modify and optimize these aqueous complexants for achieving different rare earth-binding properties. Once synthesized, these new complexants were evaluated for more environmentally friendly and energy-efficient separations of the rare earth elements.

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

Surveying Phase Modifier Functional Groups for Applications to Ln(III) Separations

The application of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in solvent extraction systems for lanthanide (Ln) separations is well understood. In these systems, the formation of a third phase has motivated the use of phase modifiers to enable higher concentrations of H + and Ln common to industrial processes. Several different phase modifiers with applications to diglycolamide (DGA) systems have previously been reported, with a focus on tri-n-butyl phosphate (TBP), N,N'-dihexylactanamide (DHOA), N,N-dioctyl-2-hydroxyacetamide (DOHyA), N,N'-dimethyl-N,N'-dioctylhexylethoxy malonamide (DMDOHEMA), and octanol. While the primary utility of phase modifiers is the increased metal loading, they can have significant effects on the metal distribution ratios, which are well described by the energetics of the extraction process itself. However, the mechanisms by which phase modifiers impact distribution ratios are not generally understood. This work considers the ability of phase modifiers to affect Ln distribution ratios by using phase modifiers with two different functional groups (–Cl and –C≡N) and an octyl alkyl chain in a TODGA and n-dodecane system. Determining the effect of chlorooctane and octane nitrile is important for understanding how phase modifier functional groups and their hydrogen bonding interactions affect Ln extraction. Through combining distribution ratio measurements with organic phase spectroscopic investigations, the impact of chlorooctane and octane nitrile on Ln extraction and their inner-sphere complexes is reported. The addition of either chlorooctane or octane nitrile to TODGA in n-dodecane decreases Ln extraction while maintaining the same inner-sphere Ln complex. The lack of change in inner-sphere Ln-TODGA coordination upon incorporation of phase modifiers and the significant impact of these phase modifiers on distribution ratios suggest the importance of a supramolecular structure. Understanding the role of chlorooctane and octane nitrile on the organic phase structure at longer length scales has been identified as an avenue for future investigations.

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

Enhancing f -Element Separations with ADAAM-EH: The Impact of Phase Modifiers and a DGA Aqueous Complexant

Recent investigations have used a 2-ethylhexyl diamide amine (ADAAM-EH) for Am/Cm separations in combination with N,N,N ',N '-tetraethyldiglycolamide as an aqueous complexant to achieve an unprecedented separation factor of 41. The aim of this research effort is to understand the speciation of trivalent lanthanide (Ln) and actinide (An) ions in the organic phase of an ADAAM-EH extraction system, both with and without phase modifiers (PM) (1-octanol and tri-n-butyl phosphate (TBP)). Leveraging spectroscopic techniques in combination with distribution ratio measurements provides an understanding of organic phase f-element ligand complexation. In the absence of PM, Ln is extracted in a stoichiometric 1:1 [M(ADAAM-EH) 1 (NO 3 ) x (H 2 O) 1 ](NO 3 ) 3-x complex. The addition of 1-octanol at 20 vol % results in multiple species present. One of the species is the same as the no PM case, and the other species results in an increased -OH coordination to the inner sphere, potentially displacing some NO 3 . In the case of TBP, increasing concentration results in additional red-shifted bands in the UV-visible spectra, suggesting the complexation of additional ligands of either ADAAM-EH or TBP. Finally, the new system knowledge obtained by and spectroscopic experiments will provide benchmarking information for computational studies of the inner- and outer-sphere coordination environments of f-element cations and insights into ADAAM-EH adduct formation with PM, like 1-octanol and TBP.

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

Heterogeneous Morphologies and Hardness of Co-Sputtered Thin Films of Concentrated Cu-Mo-W Alloys

Heterogeneous microstructures in Cu-Mo-W alloy thin films formed by magnetron co-sputtering immiscible elements with concentrated compositions are characterized using scanning transmission electron microscopy (STEM) and nanoindentation. In this work, we modified the phase separated structure of a Cu-Mo immiscible system by adding W, which impedes surface diffusion during film growth. The heterogeneous microstructures in the Cu-Mo-W ternary system exhibited bicontinuous matrices and agglomerates composed of Mo(W)-rich phase. This is unique, as these are the slower-diffusing species, contrasting past reports of binary Cu-Mo thin films that exhibited Cu-rich agglomerates. The bicontinuous matrices comprised of Cu-rich and Mo(W)-rich phases exhibited bilayer thicknesses of less than 5 nm. The hardness of these thin films measured using nanoindentation is reported and compared to similar multilayers and nanocomposites in binary systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Debris-induced consequences on turbulence and vorticity in solar photovoltaic module-generated array wakes

Particle-laden flows in solar photovoltaic (PV) systems are inevitable, where wind-swept debris in open environments are carried by high winds and turbulence, coating panel surfaces or damaging structures. Particle deposition, or soiling, is a well-known issue for large-scale plants which rely on uninhibited solar rays for optimal production. But understanding the mechanisms leading to soiling requires a physical and fluid dynamics-centered focus, since turbulence dominates PV panel wakes and is also known to alter particle concentration and trajectories. This study presents an experimental campaign toward consequences of particle-laden flow between two model PV panels using time-resolved particle image velocimetry. The model array was subjected to varied particle volume fractions, including a tracer particle case and a water droplet case. Characterization of mean velocity, turbulence statistics, and mean kinetic energy within the single phase and, separately, particle phase flows showed modified features due to particle inertia. Images captured at a frequency of 1 kHz in the near wake of the upstream panel allow for a first experimental look at vorticity and convective velocity of vortex structures for single-phase and particle-phase flows which are crucial to debris transport and soiling in PV environments.

Energy & Fuels↗
DOE OSTI2025

High precision measurements of the proton elastic electromagnetic form factors and their ratio at 𝑄 2 = 0.50, 2.64, 3.20, and 4.10 GeV 2

The advent of high-intensity, high-polarization electron beams led to significantly improved measurements of the ratio of the proton’s charge to electric form factors, 𝐺 𝐸⁢ 𝑝 ⁡/𝐺 𝑀⁢ 𝑝 . However, high-𝑄 2 measurements of this ratio yielded significant disagreement with extractions based on unpolarized scattering measurements, raising questions about the reliability of the measurements and consistency of the techniques. Jefferson Lab experiment E01-001 was designed to provide a high precision extraction of 𝐺 𝐸⁢ 𝑝 ⁡/𝐺 𝑀⁢ 𝑝 from unpolarized cross-section measurements using a modified version of the Rosenbluth separation technique to allow for a more precise comparison with polarization data. Rosenbluth separations involve precise measurements of the angular dependence of the elastic 𝑒−𝑝 cross section at fixed momentum transfer, 𝑄 2 . Conventional Rosenbluth separations detect the scattered electron, requiring the comparisons of measurements with very different detected electron energy and rate for electrons at different angles. Our ‘‘super-Rosenbluth’’ measurement detected the struck proton, rather than the scattered electron to extract the elastic 𝑒−𝑝 cross section. This yielded a fixed momentum for the detected particle and dramatically reduced variation of the cross section with angle, significantly reducing rate- and momentum-dependent corrections and uncertainties. We measure the cross section vs angle with high relative precision, allowing for extremely high precision extractions of 𝐺 𝐸⁢ 𝑝 ⁡/𝐺 𝑀⁢ 𝑝 at 𝑄 2 = 2.64, 3.20, and 4.10 GeV 2 . Our results are consistent with traditional Rosenbluth extractions, but with much smaller corrections and systematic uncertainties, comparable to the uncertainties from polarization measurements. Our data confirm the discrepancy between Rosenbluth and polarization extractions of the proton form factor ratio using an improved Rosenbluth extraction that yields smaller and less-correlated uncertainties than those typical of previous Rosenbluth extractions. Here, we compare our results to calculations of two-photon exchange effects and find that the observed discrepancy can be relatively well explained by such effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Compatibilization Strategy and Mechanism for Co-stabilizing Commingled Plastics and Pyrolyzed Rubber in Asphalt

Hot mix asphalt mixture is considered the ideal approach to reuse waste plastics in high-value applications because of its very high amount of usage in highway construction. However, the differences in polarity and density between polymers and asphalt lead to polymer coalescence and therefore the poor storage stability of modified asphalt. These challenges are exalted when recycling commingled plastics. This study introduced an innovative compatibilization strategy and mechanism for co-stabilizing commingled plastics and pyrolyzed rubber in asphalt. Commingled plastics were first grafted with maleic anhydride for surface activation, followed by reactive kneading with pyrolyzed rubber and crosslinking agent to form an integrated thermoplastic elastomer (ITPE) for asphalt modification. The mechanical, thermal, and interfacial behaviors of the ITPE were evaluated through tensile testing, thermogravimetric analysis, and scanning electron microscopy. The storage stability and rheological properties of the modified binder blends were evaluated through the cigar tube test and dynamic shear rheometer testing. Results demonstrated a successful formation of imide bonds in the ITPE, which can improve the strength, ductility, and thermal stability of rubber–plastic composites. Appropriate utilization of crosslinking agents can improve both rutting and fatigue resistance of ITPE-modified asphalt with good storage stability because of the co-existence of rigid plastic and soft rubbery regimes and the formation of a crosslink network. Furthermore, excessive content of crosslinker led to severe phase separation and reduced storage stability of modified binder blends. Extra crosslinker tended to float in asphalt because of its low density and caused an excessive formation of the crosslink network in the top section of the asphalt.

asphalt binder modifiers↗
DOE OSTI2026

Hierarchical Epoxy Structures via Tunable Polymerization-Induced Phase Separation Combined with Additive Manufacturing

Polymerization-induced phase separation (PIPS) allows for the control of thermoset morphologies and properties, enabling the tuning of domain sizes and thermomechanical response. However, its use in generating substructural features in additively manufactured materials has been limited. In this work, we combine epoxy PIPS with UV curable acrylate and rheological modifiers to print nano- to macro-phase separating materials via a two-step, dual-cure approach. This method enables direct ink write printing of hierarchical structures with both controlled morphologies through phase separation and macroscale architecture through print design. We find that formulations for phase-separating materials require judicious incorporation of additives to enable printability and to provide sufficient green strength. Atomic force microscopy-nano infrared mapping reveals tunable, reticulated nano- to micron-scale domains of the resultant multiphase materials and their morphology changes due to additives, resulting in alterations to thermomechanical and tensile properties. Shape memory behavior is also demonstrated through multimaterial additive manufacturing of epoxies with functionally graded internal morphology using active mixing techniques, highlighting this method’s ability to fabricate complex architectures with controlled morphologies and thermomechanical response.

Van Meter, Kylie E [Organic Materials Science, San↗
DOE OSTI2025

Transient plasma-detachment events induced by multiple gas puffs in ADITYA-U tokamak

Application of periodic short bursts of gas leads to periodic separation of the plasma column edge from the limiter in the Ohmically heated discharges of ADITYA-U tokamak. After every gas-puff, injecting around 10 17 –10 18 m −3 molecules of fuel gas in the edge of the plasma column, a significant reduction in plasma density, temperature, H α emission intensity and an increase in the H β /H α ratio is observed in the vicinity of the limiter radius for a certain time duration before these parameters regain their pre-gas puff values. A decline in the ion-flux to the limiter is also observed simultaneously. The global confinement of plasma also increases after each gas-puff. These observations, which repeat after each gas-injection, imply that the plasma–neutral interaction occurs further away from the limiters after the gas-injection and indicate a periodic plasma separation from the limiter surface. Further investigation revealed that the gas-injection modifies the radial and toroidal electric field, which may be playing a role in the separation of the plasma column from the limiter surface. It was further demonstrated by an electrode bias experiment in the absence of gas-injection that an application of an external radial electric field can result in obtaining a separated plasma state.

Physics - Plasma physics↗
DOE OSTI2026

Testing Scale-Dependent Modified Gravity with DESI DR1

The Dark Energy Spectroscopic Instrument (DESI) provides an unprecedented opportunity to test deviations from general relativity (GR) that introduce a new physical scale within its redshift range. Using the connection between a Yukawa-like potential and the Hu-Sawicki $f(R)$ model, we place strong constraints on the range of a hypothetical fifth force mediated by a massive scalar field. We analyze the power spectrum measurements from DESI Data Release 1 using a baseline EFT model that employs the fkpt approach for the loop integrals. We find no evidence for deviations from GR and obtain the constraint $\log_{10} |f_{R_0}| < -4.59$ (95% C.L.). This corresponds to an upper bound at redshift zero on the scale at which corrections to GR become important, $λ< 17.81$ Mpc, or equivalently, a lower bound on the mass of the additional gravitational mediator of $m_ϕ> 3.60 \times 10^{-31}$ eV. We find that the modified gravity parameter $f_{R_0}$ is largely orthogonal to the cosmological parameters in the model, such that no additional projection effects relative to the GR case are introduced in this Full-Shape analysis. Furthermore, a second modified gravity parameter, the power index $n$, which modulates the time-variation of the associated mass, is found to be consistent with previous analyses that fixed it to unity. Adding DESI BAO data or other cosmological probes does not significantly change these results. The conclusions remain similar if the background evolution is described by evolving dark energy instead of a cosmological constant. Additionally, we test the robustness of the baseline model by varying the maximum wavenumber used in the Full-Shape analysis and analyzing the DESI targets separately. Finally, we analyze the degeneracies between the modified-gravity parameters and the sum of neutrino masses.

Gonzalez, D. [Guanajuato U.; UNAM, CCF] (ORCID:000↗
DOE OSTI2025

Impacts of molecular architecture on the radiation-induced degradation and reaction kinetics of hydrophobic diglycolamides with the solvated electron and the dodecane radical cation

Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (e solv − ) and the corresponding dodecane radical cation (RH˙ + ) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10 −3 , (4.19 ± 0.09) × 10 −3 , and (4.65 ± 0.09) × 10 −3 kGy −1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.

Arrhenius parameters↗