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DOE OSTI2021

Pentiptycene-based ladder polymers with configurational free volume for enhanced gas separation performance and physical aging resistance

Significance Gas separation membranes are an emerging energy-efficient alternative toward conventional, energy-intensive separation technologies such as cryogenic distillation. Ladder polymers with intrinsic microporosity show exceptional promise toward redefining state-of-the-art gas separation membranes due to their high permeability (throughput) and selectivity (separation efficiency). However, they are typically inhibited by major reductions in permeability over time due to collapsing membrane free volume (open space between polymer chains), forfeiting their greatest asset. This work explores a route toward enhanced aging resistance and overall separation performance by incorporating pentiptycene (an H-shaped scaffold containing five fused arene rings) into ladder-like polymers to incorporate natural, more permanent “micropores” that aren’t susceptible to densification of polymer chains that occurs over time in traditional microporous polymers.

36 MATERIALS SCIENCE↗

DOE OSTI2023

HP1-driven phase separation recapitulates the thermodynamics and kinetics of heterochromatin condensate formation

The spatial segregation of pericentromeric heterochromatin (PCH) into distinct, membrane-less nuclear compartments involves the binding of Heterochromatin Protein 1 (HP1) to H3K9me2/3-rich genomic regions. While HP1 exhibits liquid–liquid phase separation properties in vitro, its mechanistic impact on the structure and dynamics of PCH condensate formation in vivo remains largely unresolved. Here, using a minimal theoretical framework, we systematically investigate the mutual coupling between self-interacting HP1-like molecules and the chromatin polymer. We reveal that the specific affinity of HP1 for H3K9me2/3 loci facilitates coacervation in nucleo and promotes the formation of stable PCH condensates at HP1 levels far below the concentration required to observe phase separation in purified protein assays in vitro. These heterotypic HP1–chromatin interactions give rise to a strong dependence of the nucleoplasmic HP1 density on HP1-H3K9me2/3 stoichiometry, consistent with the thermodynamics of multicomponent phase separation. The dynamical cross talk between HP1 and the viscoelastic chromatin scaffold also leads to anomalously slow equilibration kinetics, which strongly depend on the genomic distribution of H3K9me2/3 domains and result in the coexistence of multiple long-lived, microphase-separated PCH compartments. The morphology of these complex coacervates is further found to be governed by the dynamic establishment of the underlying H3K9me2/3 landscape, which may drive their increasingly abnormal, aspherical shapes during cell development. These findings compare favorably to 4D microscopy measurements of HP1 condensate formation in live Drosophila embryos and suggest a general quantitative model of PCH formation based on the interplay between HP1-based phase separation and chromatin polymer mechanics.

3D genomics↗

DOE OSTI2016

Superhydrophobic and superhydrophilic surface-enhanced separation performance of porous inorganic membranes for biomass-to-biofuel conversion applications

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitate large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.

09 BIOMASS FUELS↗

DOE OSTI2014

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successful separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

An atom probe perspective on phase separation and precipitation in duplex stainless steels

Here, three-dimensional chemical imaging of Fe–Cr alloys showing Fe-rich (α)/Cr-rich (α') phase separation is reported using atom probe tomography techniques. The extent of phase separation, i.e., amplitude and wavelength, has been quantitatively assessed using the Langer-Bar-on-Miller, proximity histogram, and autocorrelation function methods for two separate Fe–Cr alloys, designated 2101 and 2205. Although the 2101 alloy possesses a larger wavelength and amplitude after annealing at 427 °C for 100–10 000 h, it exhibits a lower hardness than the 2205 alloy. In addition to this phase separation, ultra-fine Ni–Mn–Si–Cu-rich G-phase precipitates form at the α/α' interfaces in both alloys. For the 2101 alloy, Cu clusters act to form a nucleus, around which a Ni–Mn–Si shell develops during the precipitation process. For the 2205 alloy, the Ni and Cu atoms enrich simultaneously and no core–shell chemical distribution was found. This segregation phenomenon may arise from the exact Ni/Cu ratio inside the ferrite. After annealing for 10 000 h, the number density of the G-phase within the 2205 alloy was found to be roughly one order of magnitude higher than in the 2101 alloy. The G-phase precipitates have an additional deleterious effect on the thermal embrittlement, as evaluated by the Ashby–Orowan equation, which explains the discrepancy between the hardness and the rate of phase separation with respect to annealing time (Gladman T 1999 Mater. Sci. Tech. Ser. 15 30–36).

36 MATERIALS SCIENCE↗

DOE OSTI2017

Harnessing mass differential confinement effects in magnetized rotating plasmas to address new separation needs

The ability to separate large volumes of mixed species based on atomic mass appears desirable for a variety of emerging applications with high societal impact. One possibility to meet this objective consists in leveraging mass differential effects in rotating plasmas. Beyond conventional centrifugation, rotating plasmas offer in principle additional ways to separate elements based on mass. Single ion orbits show that ion radial mass separation in a uniform magnetized plasma column can be achieved by applying a tailored electric potential profile across the column, or by driving a rotating magnetic field within the column. Furthermore, magnetic pressure and centrifugal effects can be combined in a non-uniform geometry to separate ions based on mass along the field lines. In conclusion, practical application of these separation schemes hinges on the ability to produce the desirable electric and magnetic field configuration within the plasma column.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2013

Evaluating ion exchange resin efficiency and oxidative capacity for the separation of uranium(IV) and uranium(VI)

Background: Previously described methods to separate dissolved U(IV) from dissolved U(VI) under acidic anoxic conditions prior to laboratory analysis were ineffective with materials currently available commercially. Three strong anion exchange resins were examined for their efficiency in separating, recovering, and preserving both redox states during separation. Results: Under oxic conditions, recovery of U(VI) from three exchange resins (Bio-Rad AG® 1x8 Poly-Prep® prefilled columns, Bio-Rad AGW 1x8 powder, and Dowex® 1x8 powder) ranged from 72% to 100% depending on the dosed mass, eluent volume, and resin selected. Dowex® 1x8 resin was the only resin found to provide 100% recovery of U (VI) with fewer than 5 bed volumes of eluent. Under anoxic conditions, all three resins oxidized U(IV) in aqueous solutions with relatively low U(IV) concentrations (<3x10-6 M). Resin-induced oxidation was observed visually using a leuco dye, safranin-o. Oxidants associated with the resin were irreversibly reduced by the addition of Ti(III). After anoxic resin pre-treatment, a series of U(IV)/U(VI) mixtures at micro-molar levels were prepared and separated using the Dowex® 1x8 resin with 100% recovery of both U(IV) and U(VI) with no resin-induced changes in oxidation state. Conclusions: Currently available anion exchange resins with apparently identical physical properties were found to have significantly different recoveries for hexavalent uranium at micro-molar concentrations. A novel qualitative technique was developed to visually assess oxidative capacities of anion exchange resins under acidic anoxic conditions. A protocol was developed for pre-treatment and use of currently available anion exchange resins to achieve quantitative separation of U(IV) and U(VI) in aqueous solutions with low U(IV) concentrations. This method can be applied to future work to quantitatively assess dissolved U(IV) and U(VI) concentrations in both laboratory and field samples.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

Synthesis and analysis of separation networks for the recovery of intracellular chemicals generated from microbial-based conversions

Background. Bioseparations can contribute to more than 70% in the total production cost of a bio-based chemical, and if the desired chemical is localized intracellularly, there can be additional challenges associated with its recovery. Based on the properties of the desired chemical and other components in the stream, there can be multiple feasible options for product recovery. These options are composed of several alternative technologies, performing similar tasks. The suitability of a technology for a particular chemical depends on (1) its performance parameters, such as separation efficiency; (2) cost or amount of added separating agent; (3) properties of the bioreactor effluent (e.g., biomass titer, product content); and (4) final product specifications. Our goal is to first synthesize alternative separation options and then analyze how technology selection affects the overall process economics. To achieve this, we propose an optimization-based framework that helps in identifying the critical technologies and parameters. Results. We study the separation networks for two representative classes of chemicals based on their properties. The separation network is divided into three stages: cell and product isolation (stage I), product concentration (II), and product purification and refining (III). Each stage exploits differences in specific product properties for achieving the desired product quality. The cost contribution analysis for the two cases (intracellular insoluble and intracellular soluble) reveals that stage I is the key cost contributor (>70% of the overall cost). Further analysis suggests that changes in input conditions and technology performance parameters lead to new designs primarily in stage I. Conclusions. The proposed framework provides significant insights for technology selection and assists in making informed decisions regarding technologies that should be used in combination for a given set of stream/product properties and final output specifications. Additionally, the parametric sensitivity provides an opportunity to make crucial design and selection decisions in a comprehensive and rational manner. This will prove valuable in the selection of chemicals to be produced using bioconversions (bioproducts) as well as in creating better bioseparation flow sheets for detailed economic assessment and process implementation on the commercial scale.

09 BIOMASS FUELS↗

DOE OSTI2016

Ultem ® /ZIF-8 mixed matrix membranes for gas separation: Transport and physical properties

Mixed matrix membranes are promising options for improving gas separation processes. Zeolitic imidazolate frameworks (ZIFs) have a porous structure similar to conventional zeolites, being capable in principle of separating gases based on their differences in kinetic diameter while offering the advantage of having a partial organic character. This partial organic nature improves the compatibility between the sieve and the polymer, and a combination of the mentioned characteristics makes these hybrid materials interesting for the preparation of mixed matrix gas separation membranes. In this context the present work reports the preparation of Ultem ® /ZIF-8 mixed matrix membranes and their permeabilities to pure CO 2 , N 2 and CH 4 gases. A significant increase in permeability with increase in CO 2 /N 2 selectivity was observed for the mixed matrix systems as compared to the properties of the neat Ultem ® . Sorption results allowed to speculate that the ZIF-8 framework is not completely stable dimensionally, what influences the separation process by allowing gases with higher kinetic diameter than its nominal aperture to be sorbed and to diffuse through the crystal. Lastly, sorption and diffusion selectivities indicate that the higher separation performance of the mixed matrix membranes is governed by the diffusion process associated with the influence of gas molecule´s geometry.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Separation of tritiated water using graphene oxide membrane

In future nuclear fuel reprocessing plants and possibly for nuclear power plants, the cleanup of tritiated water will be needed for hundreds of thousands of gallons of water with low activities of tritium. This cleanup concept utilizes graphene oxide laminar membranes (GOx) for the separation of low-concentration (10 -3 -10 µCi/g) tritiated water to create water that can be released to the environment and a much smaller waste stream with higher tritium concentrations. Graphene oxide membranes consist of hierarchically stacked, overlapping molecular layers and represent a new class of materials. A permeation rate test was performed with a 2-µm-thick cast Asbury membrane using mixed gas permeability testing with zero air (highly purified atmosphere) and with air humidified with either H 2 O or D 2 O to a nominal 50% relative humidity. The membrane permeability for both H 2 O and D 2 O was high with N 2 and O 2 at the system measurement limit. The membrane water permeation rate was compared to a Nafion® membrane and the GOx permeation was approximately twice as high at room temperature. The H 2 O vapor permeation rate was 5.9 × 10 2 cc/m 2 /min (1.2 × 10 -6 g/min-cm 2 ), which is typical for graphene oxide membranes. To demonstrate the feasibility of such isotopic water separation through GOX laminar membranes, an experimental setup was constructed to use pressure-driven separation by heating the isotopic water mixture at one side of the membrane to create steam while cooling the other side. Several membranes were tested and were prepared using different starting materials and by different pretreatment methods. The average separation result was 0.8 for deuterium and 0.6 for tritium. Higher or lower temperatures may also improve separation efficiency but neither has been tested yet. A rough estimate of cost compared to current technology was also included as an indication of potential viability of the process. The relative process costs were based on the rough size of facility to accommodate the large surface area of the membranes and the energy needed to evaporate the water and pass through the membranes as compared to the currently used combined electrolysis and catalytic exchange process.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

A Physicochemical Method for Separating Rare Earths: Addressing an Impending Shortfall

There are currently zero operating suppliers of critical rare earth elements La–Lu, Sc, Y (REs), in the western hemisphere. REs are critical materials due to their importance in clean energy and defense applications, including permanent magnets in wind turbines and phosphors in energy efficient lighting. It is not economically viable to produce pure REs in the U.S. given current separations technology. REs production is dominated by suppliers in the People’s Republic of China (PRC) because of their capacity in liquidliquid solvent extraction (SX) used to purify mixtures. Weak environmental regulations in the PRC also contribute to a competitive advantage. SX is a cost, time, solvent and waste intensive process but is highly optimized and scalable. The low efficiency of SX derives from the small thermodynamic differences in solvation enthalpy between the RE3+ cations. To foster stable domestic RE production there is a critical need for fundamentally new REs chemistry that contributes to disruptive technologies in RE separations. The overall goal of this project was to develop new thermodynamic bases, and apply them, for the solution separation of rare earth metals. We have developed the chemistry of rare earth metals: La–Lu, Sc and Y, with redox active ligands. Our hypothesis for the project was that electronhole coupling in complexes of certain lanthanide metals with redox active ligands can be used to manifest chemical distinctiveness and affect separations. We also developed separations based on unique solution equilibria from tailored ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Fundamental Structure/Property Studies of Gas Separation Membrane Polymers

Solution-processable polybenzimidazoles (PBIs) present opportunities for new gas separation membranes. We plan to develop systematic structure/property relations for this relatively new class of membrane materials. The fundamental questions we will address are: (1) How do chemical structure modifications of PBIs influence their gas solubility, diffusivity and permeability properties for a systematic series of gases? (2) Is the separation performance of PBIs affected by plasticization under operating conditions that are relevant to, for example, natural gas purification or olefin/paraffin separation and, if so, can this family of materials be tuned structurally to minimize deleterious effects of plasticization on separation properties? (3) What is the effect of water vapor on PBI separation performance? (4) What is the influence of physical aging on permeation properties of thin (i.e., <1 µm) PBI polymer films, and how does the rate of physical aging relate to polymer chemical structure? The primary focus of this research program is to develop a fundamental, molecular-based mechanistic understanding of the influence of chemical structure on the gas transport properties of PBIs and to establish structure/property relationships for this unique platform of materials.

08 HYDROGEN↗

DOE OSTI2026

Liquid centrifugation-based isotope separation of 7 Li, 37 Cl and D

Liquid centrifugation is an emerging method to separate isotopes. By spinning a liquid containing target isotopes (e.g., pure chemical or solution), the heavier isotope will be enriched at the outer part of a centrifuge, and the lighter ones will be enriched at the inner part of a centrifuge. The separation capability is positively correlated with rotation speed, outer radius and mass difference between isotopes to separate. This award targets to understand whether liquid centrifugation is effective in separating isotopes important for nuclear fission technologies. The results include the following three sections: 1) Effects of solute concentration on isotope separation; 2) Preliminary progress of building a low-speed countercurrent centrifuge, and 3) Analysis on possible candidates for 7 Li and 37 Cl. The award trained one research scientist, one Ph.D. student, one master student, and one undergraduate on liquid centrifugation and isotope measurements.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2015

Size-separation of silver nanoparticles using sucrose gradient centrifugation

Size and shape distributions of nanoparticles can drastically contribute to the overall properties of nanoparticles, thereby influencing their interaction with different chemotherapeutic molecules, biological organisms and or materials and cell types. Therefore, to exploit the proper use of nanoparticles for various biomedical and biosensor applications, it is important to obtain well-separated monodispersed nanoparticles. However, gaining precise control over the morphological characteristics of nanoparticles during their synthesis is often a challenging task. Consequently, post-synthesis separation of nanoparticles is necessary. In the present study, we demonstrate the successful one-pot post-synthesis separation of anisotropic silver nanoparticles to near modispersities using sucrose density gradient sedimentation. The separation of the nanoparticles was evidenced based on optical confirmation, and spectrophotometric and transmission electron microscopy measurements. Our results clearly demonstrate the facile separation of anisotropic silver nanoparticles using sucrose density gradient sedimentation and can enable the use of nanoparticles for various biomedical applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2022

Techno-Economic Analysis and Life-Cycle Assessment of Emerging Technologies for Bioprocessing Separations

Limited availability, rising costs, and environmental concerns about fossil fuels have generated considerable interest in finding alternative, renewable sources including biomass, which can be converted into a number of biofuels and bioproducts. In comparison to petroleum-based products, high processing costs, mainly associated with bioprocessing separations, limit widespread implementation of biofuels and bioproducts. Bioprocess-related separations are also complicated, regardless of the conversion pathway, due to the dilute nature of products and the chemically complex mixtures that result from biomass deconstruction. In many cases, bioprocessing separation approaches lack a technology baseline, or definition of the state of technology (SOT). This work focuses on evaluating the technology readiness of novel separations technologies for the conversion of biomass into biofuels and bioproducts and will address three key topics: 1) SOT description, 2) economic viability analysis of both SOT and innovative separations, and 3) environmental impact assessment of both SOT and novel processes. The current SOT for lignin valorization, dilute carbon recovery, and impurity removal is used to identify potential opportunities for improvement and provide a baseline for comparison with the emerging technologies. Detailed techno-economic analysis (TEA) and life cycle assessment (LCA) are applied to understand the key drivers and challenges related to the economic feasibility and environmental impacts, respectively.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

DOE OSTI2019

Low‐Cost Self‐Assembled Oxide Separator for Rechargeable Batteries

Abstract Rechargeable battery cells having a liquid electrolyte require a separator permeable to the electrolyte between the two electrodes. Because the electrodes change their volume during charge and discharge, the porous separators are flexible polymers with an electronic energy gap E g large enough for the Fermi levels of the two electrodes to be within it. In this work, a porous film of self‐assembled SiO 2 nanoparticles is developed as the separator for a Li‐ion battery with a liquid electrolyte. This coating does not require the plasticity of a polymer membrane and has the required large E g . If adsorbed water is removed from the SiO 2 surface, the nanoparticles bond to one another and to an oxide cathode to form a plastic self‐assembling porous layer into which the liquid electrolyte can penetrate. The Li‐ion batteries with a LiCoO 2 cathode coated with SiO 2 as a separator show similar performance to cells with a traditional polypropylene separator and improved cyclability with a reduced volume of liquid electrolyte owing to the electrolyte wetting properties of the SiO 2 nanoparticles. The SiO 2 nanoparticles are easy to prepare, cheap, and environmentally friendly.

Grundish, Nicholas S.↗

DOE OSTI2021

Mathematical modeling and parameter estimation of MFI membranes for para/ortho‐xylene separation

Abstract A mathematical model of a membrane with a thin, oriented, and selective MFI layer, which also includes contributions from defects, pore blockages, support layer, and external mass transfer, was formulated based on the Maxwell‐Stefan equations. It was validated using reported (Kim et al., Angew Chemie Int Ed, 2018, 57:480–485; Jeon et al., Nature, 2017, 543:690–694) para/ortho‐xylene separation data from five MFI membranes. The diffusivities of the xylenes were considered to be the same for all membranes, while the thickness and the density of defects and pore blockage were treated as unique properties of each membrane, and their contributions were estimated by fitting the model to the corresponding separation data. The effects of these properties and the role of permeate pressure on the separation performance were subsequently analyzed. The proposed modeling, parameter estimation, and analysis framework allow one to quantitatively interpret the variation of separation performance, to understand separation bottlenecks, and to provide guidance for designing membranes with desired performance.

Liu, Jingjun↗

DOE OSTI2017

Electro‐kinetic Separation of Rare Earth Elements Using a Redox‐Active Ligand

Abstract Purification of rare earth elements is challenging due to their chemical similarities. All of the deployed separation methods rely on thermodynamic properties, such as distribution equilibria in solvent extraction. Rare‐earth‐metal separations based on kinetic differences have not been examined. Herein, we demonstrate a new approach for rare‐earth‐element separations by exploiting differences in the oxidation rates within a series of rare earth compounds containing the redox‐active ligand [{2‐( t BuN(O))C 6 H 4 CH 2 } 3 N] 3− . Using this method, a single‐step separation factor up to 261 was obtained for the separation of a 50:50 yttrium–lutetium mixture.

Fang, Huayi↗