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At least 253 records · Page 14

Novel Membrane and Electrodeposition-Based Separation and Recovery of Rare Earth Elements from Coal Combustion Residues (Final Report)

This project developed a hydrometallurgical-based technology to extract and concentrate rare earth elements (REEs) from a representative group of coal combustion residuals (CCRs) from major coal sources in the United States. The approach for REE recovery comprises two general components: (1) Leaching of REEs from CCRs and (2) Separation of REEs from other major ions in the CCR leachate. The leaching step entails acid leaching with nitric or hydrochloric acid, and in some cases, pretreatment of CCRs with alkaline roasting prior to acid leaching. The follow-up REE recovery steps involve a series of membrane-based methods to separate and concentrate rare earth ions from other major ions in acid leachates of CCRs. These methods include liquid emulsion membranes, supported liquid membranes and electrodeposition with carbon nanotube electrochemical filters. The advantage of these separation approaches (relative to conventional approaches such as solvent extraction) is a reduction in the usage of solvents and other costly chemicals and a reduction of hazardous waste products that are challenges in conventional REE separation methods. In the testing of our process, we selected a representative set of CCR samples from our collection and performed a suite of characterization measurements (total REE content and major mineralogy). The major results of this work demonstrated that heated acid leaching could efficiently extract REEs from PRB-based coal fly ashes while the Appalachian and Illinois Basin CCRs required alkaline roasting with NaOH prior to acid leaching at room temperature. The supported liquid membrane (SLM) configuration and electrochemical deposition (ED) system yielded the most promising methods of REE recovery from the acid leachates of fly ash. Our most concentrated product to date comprised 1 wt.% (dry basis) REEs produced from an Appalachian-based fly ash leached and purified by SLM. The SLM separation process was more selective for heavy REEs over the light REEs. When SLM was combined with ED, preliminary results demonstrated that a final product of >2 wt.% REEs was possible.

01 COAL, LIGNITE, AND PEAT↗

Rare earth ion transport and selectivity in large diameter nanotube porins

Selective separation of rare earth elements (REEs) in nanoporous media is very challenging due to the similar physicochemical properties of trivalent lanthanide ions. In this work, we systematically investigate the transport and selectivity of REE 3+ ions through two model nanofluidic channels: 1.5 nm diameter carbon nanotube porins (wCNTPs) and 2.1 nm diameter boron nitride nanotube porins (BNNTPs). Using a fluorescence-based vesicle assay, we find that while wCNTPs show almost no differential selectivity across the lanthanide series, a behavior consistent with bulk-dominant transport through their moderately-confined channels with chemically inert, hydrophobic walls. In contrast, BNNTPs exhibit nearly an order of magnitude higher permeability and significant differential selectivity, following a volcano-shaped trend with Eu 3+ ions showing the highest permeability. We attribute this enhanced performance to the high negative surface charge of BNNTPs, which facilitates a surface-dominated transport mechanism where ion migration within the electric double layer becomes the primary contributor to conductance. These results elucidate the distinct roles of surface charge in nanoscale confinement and provide critical design rules for the development of future membranes tailored for efficient REE separations.

Materials science↗

Multi-scale physics of bipolar membranes in electrochemical processes

Bipolar membranes (BPMs) enable control of ion concentrations and fluxes in electrochemical cells suitable for a wide range of applications. Here, in this work, we present the multi-scale physics of BPMs in an electrochemical engineering context and articulate design principles to drive the development of advanced BPMs. The chemistry, structure, and physics of BPMs are illustrated and related to the thermodynamics, transport phenomena, and chemical kinetics that dictate ion and species fluxes and selectivity. These interactions give rise to emergent structure–property–performance relationships that yield design criteria for BPMs that achieve high permselectivity, durability, and voltaic efficiency. The resulting performance trade-offs for BPMs are presented in the context of emerging applications in energy conversion or storage, and environmental remediation. By connecting the fundamental physical phenomena in BPMs to device-level performance and engineering, we aim to facilitate the development of next-generation BPMs for sustainable electrochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Simulation of Functionalized Covalent Organic Framework Membranes for Inorganic Salt Separation

Covalent organic frameworks (COFs) enable molecular-level design of nanochannels for selective separation in pressure-driven membrane processes. Through variation of building blocks and, subsequently, the pore structure and chemistry, membrane performance can be tailored. This study employs nonequilibrium molecular dynamics simulations to theoretically demonstrate the tunable selectivity of COF membranes through a bottom-up functionalization approach. Water and salt transport are evaluated for six β-ketoenamine-linked COFs with varying multilayer thicknesses. For the thinnest multilayer (0.64–0.72 nm), all COFs exhibit low sodium sulfate (Na 2 SO 4 ) rejection (55–66%). However, 20 stacked sheets (6.4–7.2 nm) provide 67–98% rejection, with the sulfonated COF providing the highest Na 2 SO 4 rejection. Analysis of time-resolved ion density profiles reveals that solute rejection is primarily governed by interfacial exclusion arising from pore size and functional group chemistry. Although increasing salt rejection compromises water permeance, the permeance of all COF membranes is at least two orders of magnitude greater than that of a commercially available nanofiltration membrane. Overall, this work guides the rational design of COF membranes for aqueous salt separation.

Nanofiltration↗

CryoEM structures of the human CLC-2 voltage-gated chloride channel reveal a ball-and-chain gating mechanism

CLC-2 is a voltage-gated chloride channel that contributes to electrical excitability and ion homeostasis in many different tissues. Among the nine mammalian CLC homologs, CLC-2 is uniquely activated by hyperpolarization, rather than depolarization, of the plasma membrane. The molecular basis for the divergence in polarity of voltage gating among closely related homologs has been a long-standing mystery, in part because few CLC channel structures are available. Here, we report cryoEM structures of human CLC-2 at 2.46 – 2.76 Å, in the presence and absence of the selective inhibitor AK-42. AK-42 binds within the extracellular entryway of the Cl – -permeation pathway, occupying a pocket previously proposed through computational docking studies. In the apo structure, we observed two distinct conformations involving rotation of one of the cytoplasmic C-terminal domains (CTDs). In the absence of CTD rotation, an intracellular N-terminal 15-residue hairpin peptide nestles against the TM domain to physically occlude the Cl – -permeation pathway. This peptide is highly conserved among species variants of CLC-2 but is not present in other CLC homologs. Previous studies suggested that the N-terminal domain of CLC-2 influences channel properties via a “ball-and-chain” gating mechanism, but conflicting data cast doubt on such a mechanism, and thus the structure of the N-terminal domain and its interaction with the channel has been uncertain. Through electrophysiological studies of an N-terminal deletion mutant lacking the 15-residue hairpin peptide, we support a model in which the N-terminal hairpin of CLC-2 stabilizes a closed state of the channel by blocking the cytoplasmic Cl – -permeation pathway.

59 BASIC BIOLOGICAL SCIENCES↗

Membrane peptides and their role in protobiological evolution

How simple membrane peptides performed such essential protocellular functions as transport of ions and organic matter across membranes separating the interior of the cell from the environment, capture and utilization of energy, and transduction of environmental signals, is a key question in protobiological evolution. On the basis of detailed, molecular-level computer simulations we explain how these peptides fold at water-membrane interfaces, insert into membranes, self-assemble into higher-order structures and acquire functions. We have investigated the interfacial behavior and folding of several peptides built of leucine and glutamine residues and have demonstrated that many of them tend to adopt ordered structures. Further, we have studied the insertion of an alpha-helical peptide containing leucine (L) and serine (S) of the form (LSLLLSL)3 into a model membrane. The transmembrane state is metastable, and approximately 15 kcal mol(-1) is required to insert the peptide into the membrane. Investigations of dimers formed by (LSLLLSL)3 and glycophorin A demonstrate how the favorable free energy of helix association can offset the unfavorable free energy of insertion, leading to self-assembly of peptide helices in the membrane. An example of a self-assembled structure is the tetrameric transmembrane pore of the influenza virus M2 protein, which is an efficient and selective voltage-gated proton channel. Our simulations explain the gating mechanism and provide guidelines how to re-engineer the channel to act as a simple proton pump. In general, emergence of integral membrane proteins appears to be quite feasible and may be easier to envision than the emergence of water-soluble proteins.

Models, Chemical↗

Electrochemical cells with ionic sequestration provided by porous separators

Provided are electrochemical cells including separators permeable to some materials and impermeable to other materials in electrolytes. Also provide are methods of forming such separators. The selective permeability of a separator is achieved by its specific pore diameter and a narrow distribution of this diameter. Specifically, a species responsible for ion transport in an electrochemical cell are allowed to pass through the separator, while another species is blocked thereby preventing degradation of the cell. For example, a species containing lithium ions is allowed to pass in rechargeable cells, while one or more species containing transition metals are blocked. In some embodiments, a separator may include a membrane layer with at least 90% of pores of this having a diameter of between about 0.1 nanometers and 1.0 nanometer. The membrane layer may be a standalone layer or supported by a membrane support.

25 ENERGY STORAGE↗

Ultra-Fast Vertical Ordering of Lamellar Block Copolymer Films on Unmodified Substrates

To utilize the full potential of block copolymer (BCP) thin films for use in technological devices ranging from ion conduction membranes, transistors to nanowire array antennas, rapid self- assembly of lamellar block copolymers (l-BCPs) with vertically oriented lamellar domains on a variety of unmodified substrates is needed. l-BCPs have an inherently larger interfacial area for transport compared to their cylindrical counterpart. Our observations demonstrate that the as-cast weakly ordered vertically oriented state of l-BCP films of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) from directional evaporation of select solvents, act as “seed templates” for their ultra-fast evolution (~30 s) into well-ordered vertically oriented nanostructures, using a thermal gradient-based Cold Zone Annealing (CZA) technique. Furthermore, vertical lamellae are obtained on unmodified substrates, Quartz and Kapton, and the kinetics of l-BCP ordering is much faster by CZA as compared to the isotropic oven annealing. The rapid ordering kinetics of vertical l-BCPs is tested and found applicable to different molecular weights and film thicknesses ranging from 20 nm to 480 nm, which ultimately flip over to their equilibrium parallel morphology at upper limits of annealing times. This rapid ordering strategy for vertical orientation of l-BCPs using roll-to-roll compatible CZA would be highly relevant for fundamental studies of interfacial transport as well as for industrial applications from membranes to nanowires.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Continuous, Oriented Covalent Organic Framework Membranes for Precise Molecular Separations

The goal of achieving energy-efficient, precise molecular separations has motivated interest in developing and employing porous crystalline frameworks as membrane materials. Covalent organic frameworks (COFs) are ordered crystalline matrices composed of covalently bonded organic monomers and are synthesized via reversible reticular chemistry. COFs possess high porosity, structural tunability, and chemical and thermal stability, making them ideally suited for emerging, high-value membrane separation processes, such as ion separations, organic solvent nanofiltration, and gas separations. Although a range of COF membranes have been fabricated and tested in the past decade, these membranes are primarily polycrystalline, weakly crystalline, and/or discontinuous, resulting in suboptimal performance. In this review, we identify the properties that make COFs well-suited as membrane materials, while critically outlining the shortcomings of existing disordered COF membranes. We then highlight the recent emergence of highly crystalline, continuous, oriented two-dimensional COF membranes as a promising path forward for highly selective molecular separations. These continuous, oriented COF membranes exhibit tunable one-dimensional nanochannels, allowing for ultrafast molecular transport and precise species selectivity, thereby expanding the set of separations that can be practically achieved with membrane systems. We discuss synthesis and modification techniques that result in continuous, oriented COF membranes and evaluate the performance of such membranes for a variety of molecular separations. We conclude by identifying ongoing challenges in the development of COF membranes and outlining the future of their applications in molecular separations, which will necessarily rely on advancements in the synthesis of continuous, oriented membranes.

COF modification↗

Membrane-based solvent extraction for the recovery of rare earths from phosphate mining process streams

This study reports on the capture of rare earth elements (REEs) from phosphate industry process streams, including phosphoric acid (PA) sludge and phosphogypsum (PG), using a membrane solvent extraction (MSX) process. While MSX has been proven effective for a relatively concentrated feed, its effectiveness for dilute REEs solutions remains unexplored. Investigated PA-sludge and PG particles contain total REEs concentrations of ∼1100 and ∼320 ppm, respectively. Acid leaching, implemented to dissolve the REEs, significantly dilutes the REEs concentration to ∼210 ppm for PA-sludge leachate and ∼60 ppm for PG leachate. These low concentrations, compounded by the higher levels of non-REE ions and radioactive species, uranium (U) and thorium (Th), poses challenges to the MSX process. Here, we demonstrated that N,N,N′,N′-tetraoctyl-diglycolamide (TODGA) selectively binds REEs from a >3 M nitric-acid leachate while effectively rejecting U and Th. Concentrations of light REEs in strip solution were doubled compared to the feed, while heavy REEs were preferentially extracted. Furthermore, >99% purity gypsum, free of U and Th, was precipitated during the acid leaching process, aiding separation by removing significant amounts of non-REEs species (e.g., calcium) prior to the MSX process. Molecular simulations support the experimental data, suggesting preferential separation of heavy over light REEs. Based on these results, a cost-effective integrated process including pretreatment, acid leaching, MSX, and wastewater treatment is proposed for the co-recovery of REEs, phosphoric acid, gypsum, and U. This study shows MSX as a technically and economically feasible process for the recovery of REEs from low-concentration process streams, offering advantages over conventional solvent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High‐Energy‐Density Chelated Chromium Flow Battery Electrolyte at Neutral pH

Abstract High‐concentration operation of redox flow batteries (RFBs) is essential for increasing their energy‐storage capacity, but non‐acidic electrolytes struggle to achieve the high concentrations of metal ions dissolved in acid, limiting the development of energy‐dense neutral pH electrolytes. We report neutral pH RFB operation of chromium 1,3‐propylenediaminetetraacetate (CrPDTA) at concentrations of 1.2 M at room temperature and 1.6 M at 40 °C, demonstrating 60% higher negolyte capacity, up to 42.9 Ah L −1 , than previously reported for non‐additive‐utilizing solutions of this promising material. With extended full cell cycling, we demonstrate the importance of buffer selection and pH when using the Fumasep E‐620(K) membrane. Finally, we expand the pH operation range of CrPDTA to pH 7, which when cycled at 100 mA cm −2 against a ferrocyanide posolyte demonstrated excellent coulombic efficiencies >99.7% and energy efficiencies >87%, while operating at almost 700 mV more negative than the thermodynamic hydrogen evolution window.

Chemistry↗

Electron/hole selectivity in organic semiconductor contacts for solar energy conversion (Final Report)

Four major and accomplishments for the project "Electron/hole selectivity in organic semiconductor contacts for solar energy conversion.'' are reported. The first is a development of a model describing the contact-determined behavior of a solar cell. The most basic solar cell consists of an intrinsic (pure) semiconductor that acts as an absorber to which contacts are made that provide the asymmetry needed to create a driving force (voltage) for the directional flow of electrons (current), in other words, to convert sunlight into electrical energy. The asymmetry at the contacts comes from the different rate at which electrons and holes, the charge carriers generated by illumination, are collected. We developed a model that describes the ideal current-voltage, and hence energy converting properties, of an ideal photovoltaic that is entirely determined by the kinetics for these charge collection processes. Second, we measured how organic semiconductor interfacial layers impact contact electron and hole transfer rates at semiconductor interfaces and described how these concepts do or do not determine the open-circuit voltage of a solar cell. The work clearly controverts common general misconceptions about the action of contact interfacial layers, such as the idea that improved selectivity for one carrier over the other results from decreased recombination, and quantitatively demonstrates how specific interfacial layer materials act to improve the efficiency of a solar cell. Third, we measured the sub-band gap external quantum efficiency (EQE) of a series of organometal halide perovskite (“perovskite”) solar cells. These measurements quantified band-tailing and revealed defect states, which can cause recombination, that correlate with composition, performance, and hysteresis. Finally, we developed a semiconductor bipolar membrane that uses light to pump ions. This structure is unique among systems that drive ion gradients using light in that it is designed to pump salt rather than one sign of ion; it is a photochemical salt pump.

14 SOLAR ENERGY↗

Advanced CO2 Removal Technology Development

The Advanced CO2 Removal Technical Task Agreement covers three active areas of research and development. These include a study of the economic viability of a hybrid membrane/adsorption CO2 removal system, sorbent materials development, and construction of a database of adsorption properties of important fixed gases on several adsorbent material that may be used in CO2 removal systems. The membrane/adsorption CO2 removal system was proposed as a possible way to reduce the energy consumption of the four-bed molecular sieve system now in use. Much of the energy used by the 4BMS is used to desorb water removed in the device s desiccant beds. These beds might be replaced by a desiccating membrane that moves the water from [he incoming stream directly into the outlet stream. The approach may allow the CO2 removal beds to operate at a lower temperature. A comparison between models of the 4BMS and hybrid systems is underway at Vanderbilt University. NASA Ames Research Center has been investigating a Ag-exchanged zeolites as a possible improvement over currently used Ca and Na zeolites for CO2 removal. Silver ions will complex with n:-bonds in hydrocarbons such as ethylene, giving remarkably improved selectivity for adsorption of those materials. Bonds with n: character are also present in carbon oxides. NASA Ames is also continuing to build a database for adsorption isotherms of CO2, N2, O2, CH4, and Ar on a variety of sorbents. This information is useful for analysis of existing hardware and design of new processes.

Finn, John E.↗

Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes

The plasticization of a polymer electrolyte usually promotes its ionic conductivity but decreases its storage modulus due to the increased polymer chain flexibility. Herein, we show that such a tradeoff between the ionic conductivity and the mechanical robustness of the polymer electrolyte can be alleviated by selective plasticization of the ion-conductive block, such as poly(ethylene oxide) (PEO) in a polystyrene (PS)– PEO–PS block copolymer (SEO) electrolyte using an ether type plasticizer, tetraethylene glycol dimethyl ether (TEGDME). In this work, at maximum plasticizer loading, the room temperature ionic conductivity increases by up to 3 orders, whereas the storage modulus, G' reduces to half, is still on the order of 10 2 MPa. At above the melting temperature of the PEO block, the dynamic storage modulus, G' of the plasticized membrane surpasses its dry PS-PEO-PS counterpart. Such a phenomenon results from that, a) TEGDME co-crystallizes with PEO to promote its crystallinity and hence the storage modulus, b) TEGDME swells the amorphous PEO phase to enhance the polymer chain segmental mobility and hence ionic conductivity, and c) the PS phase remains intact from TEGDME to keep the SEO elastic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contemplating the plasmalemmal control center model

An abundant epidermal mechanosensory calcium-selective ion channel appears able not only to detect mechanical stimuli such as those that initiate gravitropism but also to detect thermal, electrical, and various chemical stimuli. Because it responds to multimodal input with a second messenger output, this channel system seems likely to be an integrator that can engage in feedbacks with many other systems of the cell--and feedback is the hallmark of regulation. In general, the mechanical tension required for channel activation is likely transmitted from the relatively rigid cell wall to the plasma membrane system via linkage or adhesion sites that display antigenicities recognized by antibodies to animal beta-1 integrin, vitronectin, and fibronectin and which have mechanical connections to the cytoskeleton. Thus, functionally, leverage exerted against any given adhesion site will tend to control channels within a surrounding domain. Reactions initiated by passage of calcium ions through the channels could presumably be more effectively regulated if channels within the domains were somewhat clustered and if appropriate receptors, kinases, porters, pumps, and some key cytoskeletal anchoring sites were in turn clustered about them. Accumulating evidence suggests not only that activity of clusters of channels may contribute to control of cytoskeletal architecture and of regulatory protein function within their domain, but also that both a variety of regulatory proteins and components of the cortical cytoskeleton may contribute to control of channel activity. The emerging capabilities of electronic optical microscopy are well suited for resolving the spatial distributions of many of these cytoskeletal and regulatory molecules in living cells, and for following some of their behaviors as channels are stimulated to open and cytosolic calcium builds in their vicinity. Such microscopy, coupled with biochemical and physiological probing, should help to establish the nature of the feedback loops putatively controlled by the linkage sites and their channel domains.

Review↗

Sensitivity of Hollow Fiber Spacesuit Water Membrane Evaporator Systems to Potable Water Constituents, Contaminants and Air Bubbles

The Spacesuit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The first SWME prototype, designed, built, and tested at Johnson Space Center in 1999 used a Teflon hydrophobic porous membrane sheet shaped into an annulus to provide cooling to the coolant loop through water evaporation to the vacuum of space. This present study describes the test methodology and planning and compares the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME, in particular, a porous hydrophobic polypropylene, and two variants that employ ion exchange through non-porous hydrophilic modified Nafion. Contamination tests will be performed to probe for sensitivities of the candidate SWME elements to ordinary constituents that are expected to be found in the potable water provided by the vehicle, the target feedwater source. Some of the impurities in potable water are volatile, such as the organics, while others, such as the metals and inorganic ions are nonvolatile. The non-volatile constituents will concentrate in the SWME as evaporated water from the loop is replaced by the feedwater. At some point in the SWME mission lifecycle as the concentrations of the non-volatiles increase, the solubility limits of one or more of the constituents may be reached. The resulting presence of precipitate in the coolant water may begin to plug pores and tube channels and affect the SWME performance. Sensitivity to macroparticles, lunar dust simulant, and air bubbles will also be investigated.

Bue, Grant C.↗

Technology for the Recovery of Lithium from Geothermal Brines

Lithium is the principal component of high-energy-density batteries and is a critical material necessary for the economy and security of the United States. Brines from geothermal power production have been identified as a potential domestic source of lithium; however, lithium-rich geothermal brines are characterized by complex chemistry, high salinity, and high temperatures, which pose unique challenges for economic lithium extraction. The purpose of this paper is to examine and analyze direct lithium extraction technology in the context of developing sustainable lithium production from geothermal brines. In this paper, we are focused on the challenges of applying direct lithium extraction technology to geothermal brines; however, applications to other brines (such as coproduced brines from oil wells) are considered. The most technologically advanced approach for direct lithium extraction from geothermal brines is adsorption of lithium using inorganic sorbents. Other separation processes include extraction using solvents, sorption on organic resin and polymer materials, chemical precipitation, and membrane-dependent processes. The Salton Sea geothermal field in California has been identified as the most significant lithium brine resource in the US and past and present efforts to extract lithium and other minerals from Salton Sea brines were evaluated. Extraction of lithium with inorganic molecular sieve ion-exchange sorbents appears to offer the most immediate pathway for the development of economic lithium extraction and recovery from Salton Sea brines. Other promising technologies are still in early development, but may one day offer a second generation of methods for direct, selective lithium extraction. Initial studies have demonstrated that lithium extraction and recovery from geothermal brines are technically feasible, but challenges still remain in developing an economically and environmentally sustainable process at scale.

58 GEOSCIENCES↗

Microshutter Arrays for James Webb Space Telescope

Two-dimensional MEMS microshutter arrays are being developed at NASA Goddard Space Flight Center for use in the near-infrared region on the James Webb Space Telescope (JWST). The microshutter arrays are designed for the selective transmission of light with high efficiency and high contrast. The JWST environment requires cryogenic operation at 35K. Microshutter arrays are fabricated out of silicon-oxide-insulated (SOI) silicon wafers. Arrays are close-packed silicon nitride membranes with a pixel size of 100x200 p. Individual shutters are patterned with a torsion flexure permitting shutters to open 90 degrees with a minimized mechanical stress concentration. The mechanical shutter arrays are fabricated using MEMS technologies. The processing includes a multi- layer metal deposition and patterning of shutter electrodes and magnetic pads, reactive ion etching (NE) of the front side to form shutters out of the nitride membrane, an anisotropic back-etch for wafer thinning, followed by a deep RIE (DRIE) back-etch down to the nitride shutter membrane to form W e s and relieve shutters from the silicon substrate. An additional metal deposition and patterning is used to form back electrodes. Shutters are actuated using a magnetic force and latched using an electrostatic force. . . . KEYWORDS: microshutter, MEMS, RIE, DRIE, micro-optics, near inbred, space telescope

Li, Mary J.↗