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NASA NTRS1974

Study of ceramic products and processing techniques in space

An analysis of the solidification kinetics of beta alumina in a zero-gravity environment was carried out, using computer-simulation techniques, in order to assess the feasibility of producing high-quality single crystals of this material in space. The two coupled transport processes included were movement of the solid-liquid interface and diffusion of sodium atoms in the melt. Results of the simulation indicate that appreciable crystal-growth rates can be attained in space. Considerations were also made of the advantages offered by high-quality single crystals of beta alumina for use as a solid electrolyte; these clearly indicate that space-grown materials are superior in many respects to analogous terrestrially-grown crystals. Likewise, economic considerations, based on the rapidly expanding technological applications for beta alumina and related fast ionic conductors, reveal that the many superior qualities of space-grown material justify the added expense and experimental detail associated with space processing.

Markworth, A. J.↗

NASA NTRS1974

Conductivity of boules of single crystal sodium beta-alumina

The ionic and electrochemical polarization characteristics of two boules of single crystal sodium beta-alumina (Na2O.8Al2O3), 2 cm in diameter, were investigated over the range of 25 to 300 C using 2- and 4-probe ac and dc techniques with reversible and ion-blocking electrodes. Textural (or internal) polarization at 27 C was present only in boule 1 which cleaved easily. Interfacial polarization, using solid sodium electrodes, was present at 27 C in the 2-probe conductivities for both boules. Cleaning with liquid sodium at 300 C reduced its magnitude, but some interfacial polarization was still present in the 2-probe conductivities for boule 2 below about 140 C. Above 140 C, with liquid sodium electrodes, the 2-probe conductivities, essentially polarization-free, were given by KT = 3300 exp(-3650/RT). The conductivity of boule 2 at 180 C remained essentially constant with increasing current density up to about 140 milliamps per square centimeter.

Fielder, W. L.↗

DOE OSTI2025

The Dynamical Role of Optical Phonons and Sublattice Screening in a Solid-State Ion Conductor

Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

High temperature conductivity of potassium-beta(double prime)-alumina

Potassium beta(double prime)-alumina (BDPA) single crystals have been reported by several groups to leave higher ionic conductivity than sodium BDPA crystals at room temperature, and similar conductivities are obtained at temperatures up to 600-700 K. Potassium BDPA ceramics have been reported to have significantly poorer conductivities than those of sodium BDPA ceramics, but conductivity measurements at temperatures above 625 K have not been reported. In this study, K(+)-BDPA ceramics were prepared from Na(+)-BDPA ceramic using a modified version of the exchange reaction with KCl vapor reported by Crosbie and Tennenhouse (1982), and the conductivity has been measured in K vapor at temperatures up to 1223 K, using the method of Cole et al. (1979). The results indicate reasonable agreement with earlier data on K(+)-BDPA ceramic measured in a liquid K cell, but show that the K(+)-BDPA ceramic's conductivity approaches that of Na(+)-BDPA ceramic at higher temperatures, being within a factor of four at 700 K and 60 percent of the conductivity of Na(+)-BDPA at T over 1000 K. Both four-probe dc conductivity and four probe ac impedance measurements were used to characterize the conductivity. A rather abrupt change in the grain boundary resistance suggesting a possible phase change in the intergranular material, potassium aluminate, is seen in the ac impedance behavior.

Williams, R. M.↗

DOE OSTI2024

Liquid-like solid-state diffusion of lithium ions in super-halide-rich argyrodite

The development of solid electrolytes with high ionic conductivity is essential for advancing safer, high-energy-density solid-state batteries, where lithium site distribution in the sublattice strongly affects ion transport. Here, we report a super-halide-rich argyrodite, Li 5.3 PS 4.3 Cl 1.7 , with remarkable room-temperature ionic conductivity (11.4 ± 0.7 mS cm -1 ) due to population of two additional interstitial lithium sites induced by vacancy redistribution. Prominent lithium density between lithium sites and elevated atomic displacement parameters indicate liquid-like diffusive behavior resembling sublattice melting. Combining electrochemical impedance spectroscopy, pulsed-field gradient NMR, and T 1 relaxation methods, we demonstrate that the augmented conductivity partly arises from a low energy barrier (0.08 eV) at the local scale, attributed to a three-site lithium distribution that drives correlated lithium dynamics. This work advances our understanding of the structure-dynamics interplay in super-halide-rich argyrodites, and highlighting their potential as solid-state battery electrolytes in cells with a coated single-crystal NMC82 cathode that achieve 170 mAh/g capacity at a 0.2 C rate .

25 ENERGY STORAGE↗

DOE OSTI2025

Assembly of small silica nanoparticles using lipid-tethered DNA ‘bonds’

Single-stranded DNA molecules modified with cholesterol functional groups are physically tethered to silica nanoparticles (diameter 25 nm) that are encapsulated in a lipid bilayer. Such tethering increases the azimuthal mobility of the DNA molecules across the nanoparticle surface and enables nonspecific bonding, eliminating the need for specialized surface chemistries (such as silane or thiol ligands). To induce assembly, double-stranded DNA ‘bridge’ molecules are then added with complementary nucleotides to the DNA ‘anchor’ molecules that are physically tethered to the lipids on the surface of the particles. Assembly is observed to occur at room temperature and without the need for temperature annealing. Using automated liquid handling tools, assemblies are created in high throughput and rapidly characterized using SAXS. It is determined that the relative concentration of DNA-to-silica and the ionic strength of the solution are important parameters that affect the resulting assembly. Analysis of SAXS data is performed using coarse-grained particle dynamics simulations. The results support the spontaneous formation of semi-crystalline particle assemblies by particle condensation, where the interparticle distance is tuned by the sequence of the DNA ‘bridge’ used to link the particles. Crystallinity analysis performed on the resulting simulations, optimized to match SAXS observations, suggest that particle clusters display increased crystallinity in the center of the clusters, but their maximum size remains relatively small (sub-micron) before settling occurs, which limits the extent of crystallization.

Chiang, Huat Thart [Univ. of Washington, Seattle, ↗

DOE OSTI2024

A lyotropic liquid crystal-templated nanofiltration membrane with thermo- and pH-responsive 3D transport pathway

We produce controlled nanostructured membranes from cross-linking of self-assembled diacrylated poloxamers. At sufficiently high concentrations, poloxamers form lyotropic liquid crystals (LLCs), such as lamellar (L α ), cubic packing of spherical micelles, and hexagonal packing of rod-like micelles in water (H 1 ). We use the H 1 phase as a template to produce orderly packed nanofibrous membranes. The obtained membrane has a continuous 3D transport pathway and can alter its nanofiltration (NF) properties in response to changes in temperature and pH. The formulation includes Pluronic P84-diacrylate (P84DA), a thermoresponsive component that acts as both macromer and structure-directing amphiphile. P84DA facilitates changes in membrane pore size with temperature due to its thermoresponsiveness when it is in contact with water. Furthermore, the precursor contains acrylic acid (AAc) as the charged component, which upon copolymerization with P84DA, not only enables ion separation through Donnan exclusion but also imparts pH-responsive behavior for the separation of ionic species. The membrane performance is studied and compared with a commercial NF membrane (NF270). We show that the synthesized NF membrane has separation properties adjustable with temperature and pH with exceptional resistance to fouling by various solutes due to its highly hydrophilic surface. Furthermore, the membrane shows an outstanding sulfate over chloride ion selectivity, which is a requirement for salt fractionation applications. Deducted from separate experiments, the ideal chloride/sulfate selectivity for magnesium cation is about 2.38 at low ionic strengths. This study is done on a model system to show the capability of incorporating pH-responsiveness in LLC templated membranes, in which the pH-responsive range can be designed by changing the charged groups of comonomer in the formulation.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Self-assembled nanofiltration membranes with thermo- and pH-responsive behavior

36 MATERIALS SCIENCE↗

DOE OSTI2026

Structuring, stochastic behavior, and charge storage capacity of redox-active microemulsions formulated with mixtures of toluene and ionic liquid as oil phase

Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO 3 – , Cl – , ClO 4 – ) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl – > NO 3 – > ClO 4 – while the ferrocene diffusion coefficient increased as NO 3 – > Cl – > ClO 4 – . Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO 4 – exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.

diffusion↗

DOE OSTI2022

Investigation of the role of hydrogen bonding in ionic liquid-like salts with both N- and S-soft donors

In search of ionic liquids (ILs) with multiple types of soft donor atoms capable of preferentially complexing a range of soft metal ions over harder ions, we investigated structural clues to the role of hydrogen bonding in IL behavior through a series of salts with anions containing both N- and S-donor atoms based on azole thiolates. Reaction of equimolar amounts of triethylamine (Et 3 N) or diisobutylamine (DBA) with 1-phenyl-1H-tetrazole-5-thiol (PhTzSH), 1-methyl-1H-tetrazole-5-thiol (MeTzSH), or 5-methyl-1,3,4-dithiazole-2-thiol (MeDiTSH) yielded [Et 3 NH][MeTzS] (1), a yellow liquid, and the low melting yellow solids [DBAH][MeTzS] (2), [Et 3 NH][PhTzS] (3), [DBAH][PhTzS] (4), [Et 3 NH][MeDiTS] (5), and [DBAH][MeDiTS] (6). Thermal analysis revealed that all of them qualify as ILs with melting points below 100 °C. Single crystal X-ray structure analysis of 2–6 revealed the presence of an extensive H-bonding network that includes the rare N–H$\cdots$S hydrogen bonds in 3, 4, and 6. These weaker interactions appear to significantly influence thermal behavior, where strong bonding leads to higher melting temperatures and lower decomposition points.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2007

Crystal Field Effects and Siderophile Element Partitioning: Implications for Mars HSE Geochemistry

Analyses of martian (SNC) meteorites indicate that Pt abundances do not vary much compared to other highly siderophile elements (HSE). Therefore, Jones et al. [1] inferred that D(Pt) during basalt petrogenesis was of order unity. This inference was at odds with previously published experiments that gave a D(sub ol/liq) for Pt of approx. 0.01 [2]. Because olivine is likely to be an important constituent of any reasonable martian mantle, the implication of these findings is that minor minerals must have D(Pt) much greater than 1, which seemed improbable. However, not only did the SNC evidence point to a D(sub ol/liq) approx. equal to 1, but so did plots of D(sub ol/liq) vs. ionic radius (Onuma diagram). The ionic radius of Pt(2+) suggested that D(sub ol/liq) for Pt was of order unity, in agreement with the inferences from SNC meteorites. New experiments have failed to detect measurable Pt in olivine, even at high oxygen fugacities [3]. Therefore, some other parameter, other than ionic charge and radius, must hold sway during olivine liquid partitioning of Pt.

Jones, John H.↗

NASA NTRS2005

Novel Applications of Magnetic Fields for Fluid Flow Control and for Simulating Variable Gravity Conditions

Static and dynamic magnetic fields have been used to control convection in many materials processing applications. In most of the applications, convection control (damping or enhancement) is achieved through the Lorentz force that can be tailored to counteract/assist dominant system flows. This technique has been successfully applied to liquids that are electrically conducting, such as high temperature melts of semiconductors, metals and alloys, etc. In liquids with low electrical conductivity such as ionic solutions of salts in water, the Lorentz force is weak and hence not very effective and alternate ways of flow control are necessary. If the salt in solution is paramagnetic then the variation of magnetic susceptibility with temperature and/or concentration can be used for flow control. For thermal buoyancy driven flows this can be accomplished in a temperature range below the Curie point of the salt. The magnetic force is proportional to the magnetic susceptibility and the product of the magnetic field and its gradient. By suitably positioning the experiment cell in the magnet, system flows can be assisted or countered, as desired. A similar approach can be extended to diamagnetic substances and fluids but the required magnetic force is considerably larger than that required for paramagnetic substances. The presentation will provide an overview of work to date on a NASA fluid physics sponsored project that aims to test the hypothesis of convective flow control using strong magnetic fields in protein crystal growth. The objective is to understand the nature of the various forces that come into play, delineate causative factors for fluid flow and to quantify them through experiments, analysis, and numerical modeling. The seminar will report specifically on the experimental results using paramagnetic salts and solutions in magnetic fields and compare them to analytical predictions. Applications of the concept to protein crystallization studies will be discussed. The use of strong magnetic fields for terrestrially simulating variable gravity environments and applications supporting the NASA Exploration Initiative will also be briefly discussed.

Ramachandran, N.↗

DOE OSTI2025

Efficient machine learning interatomic potentials robust for liquid and multiple solid polymorphs of NaF and KF

Achieving atomic-level understanding of crystallization of molten salts is of importance to a wide range of technological applications. Recent work [Fan et al., Proc. Natl. Acad. Sci. USA 122, e2425702122 (2025)] revealed that crystal nucleation in molten LiF salt is a multistage process according to the molecular-dynamics (MD) simulations based on an atomic cluster expansion (ACE) machine-learning interatomic potential (MLIP). In order to understand the influence of increasing cation size on nucleation pathways and nucleation rates of molten fluoride salts, here we develop two new ACE MLIPs for NaF and KF. The two ACE MLIPs feature DFT-SCAN-level accuracy for liquid and multiple solid polymorphs over a wide temperature (0–2000 K) and pressure (0–100 GPa) range, and also reproduce well a number of experimental data for solid and liquid equilibrium properties. The efficiency of the two ACE MLIPs enable million-atom-scale or microsecond-scale MD simulations. The two general-purpose ACE MLIPs are expected to be useful for atomistic simulations for different purposes, in addition to studying crystallization of molten NaF and KF salts.

Crystal melting↗

DOE OSTI2025

Mk-IV Salt Crystallization Hot Finger Apparatus for Partitioning Used Electrorefiner Salt

Electrorefining is a controlled redox process used to regulate the behavior of ionic species. Through this process, metals can be deposited onto a cathode from an electrolyte solution in a controlled manner. The Mk-IV electrorefiner (Mk-IV ER) at Idaho National Laboratory is an engineering-scale, molten salt-based electrorefining cell that has been used for decades to recover metallic uranium from spent fuel. As a result, highly stable fission product chlorides have accumulated in the electrolyte. This accumulation results in changes to the salt’s properties, such as melting temperature, thermal conductivity, and density, as well as elevated product impurity and fissile materials criticality margin. These factors prompt the need for a salt regeneration process, such as melt-crystallization and species drawdown. This work focuses on providing a conceptual design to regenerate ER salt from used Mk-IV-ER salt in-situ, while minimizing salt waste volumes by concentrating the fission products in a final processed salt heal. We propose using a hot-finger crystallization apparatus design to fractionally crystallize salt in the Mk-IV-ER head space (or baffle space), allowing the collection of solid and liquid fractions. By using a cup-drain design, the used salt will be allowed to slowly solidify on the walls of a stainless-steel cup. The apparatus drain plug will then open to allow the liquid salt phase to drain to a lower cup, effectively separating the liquid phase from the solid phase. Under the hypothesis that the liquid phase salt concentrates the fission products, which is under examination in the accompanying work package, this separation allows the recovered solid salt to be reused while minimizing the high-level salt waste volume of used ER salt.

36 - MATERIALS SCIENCE↗

DOE OSTI2025

Undercooling minimization in ultrasound coupled DTA measurements of molten salts

Molten salts are ionic liquids that are used for the electrolytic pyroprocessing of metals and as heat transfer fluids in very high temperature processes. Recently, halide-based molten salt reactors (MSR) have gained momentum for high density and environmentally responsible electricity generation. The function of these reactors and their fuel cycle depend on a knowledge of the halide salt’s thermodynamic properties [1]. Therefore, high accuracy phase equilibria of MSR relevant base halide and actinide containing salts are needed. Modern thermal analysis of the phase transitions of halide salts is usually done during heating at relatively high scan rates with commercial devices. Normally such measurements are adequate for pure or pseudo-binary salts. However, as the number of components in the mixture increases, accurately resolving the liquidus becomes increasingly difficult. Reversing the scanning mode greatly increases the sensitivity of phase transition measurements but can decrease accuracy due to undercooling [2] — a common occurrence in molten halide systems [3]. This work presents the development of a differential thermal analysis (DTA) cell intended for use in radiological gloveboxes. Non-contact ultrasonic agitation of the halide salt is implemented to limit kinetic limitations on crystallization during cooling to minimize undercooling [4]. Measurements on halide salts are also presented to elucidate the effect of non-contact mixing on undercooling. Reference [1] S. Boyd and C. Taylor, “3 - Chemical fundamentals and applications of molten salts,” in Molten Salt Reactors and Thorium Energy, T. J. Dolan, Ed., Woodhead Publishing, 2017, pp. 29–91. doi: 10.1016/B978-0-08-101126-3.00003-8. [2] K. Nitsch, A. Cihlár, and M. Rodová, “Molten state and supercooling of lead halides,” J. Cryst. Growth, vol. 264, no. 1, pp. 492–498, Mar. 2004, doi: 10.1016/j.jcrysgro.2004.01.011. [3] L. Rycerz, “Practical remarks concerning phase diagrams determination on the basis of differential scanning calorimetry measurements,” J. Therm. Anal. Calorim., vol. 113, no. 1, pp. 231–238, Jul. 2013, doi: 10.1007/s10973-013-3097-0. [4] Md. H. Zahir, S. A. Mohamed, R. Saidur, and F. A. Al-Sulaiman, “Supercooling of phase-change materials and the techniques used to mitigate the phenomenon,” Appl. Energy, vol. 240, pp. 793–817, Apr. 2019, doi: 10.1016/j.apenergy.2019.02.045.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf 2 N]). Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide–actinide distances of ~5 Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO 2 ) 2 (bet) 6 (H 2 O) 2 ][Tf 2 N] 4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2002

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗

DOE OSTI2025

The Effects of Morphology and Hydration on Anion Transport in Self-Assembled Nanoporous Membranes

Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (H I ) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. Here, the water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗