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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.

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411 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Nanoporous Dielectric Resistive Memories Using Sequential Infiltration Synthesis

Resistance switching in metal–insulator–metal structures has been extensively studied in recent years for use as synaptic elements for neuromorphic computing and as nonvolatile memory elements. However, high switching power requirements, device variabilities, and considerable trade-offs between low operating voltages, high on/off ratios, and low leakage have limited their utility. Here, we have addressed these issues by demonstrating the use of ultraporous dielectrics as a pathway for high-performance resistive memory devices. Using a modified atomic layer deposition based technique known as sequential infiltration synthesis, which was developed originally for improving polymer properties such as enhanced etch resistance of electron-beam resists and for the creation of films for filtration and oleophilic applications, we are able to create ~15 nm thick ultraporous (pore size ~5 nm) oxide dielectrics with up to 73% porosity as the medium for filament formation. We show, using the Ag/Al 2 O 3 system, that the ultraporous films result in ultrahigh on/off ratio (>10 9 ) at ultralow switching voltages (~±600 mV) that are 10× smaller than those for the bulk case. In addition, the devices demonstrate fast switching, pulsed endurance up to 1 million cycles. and high temperature (125 °C) retention up to 10 4 s, making this approach highly promising for large-scale neuromorphic and memory applications. Additionally, this synthesis methodology provides a compatible, inexpensive route that is scalable and compatible with existing semiconductor nanofabrication methods and materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Unconventional Thermoelectric Materials for Energy Harvesting and Sensing Applications

Heat is an abundant but often wasted source of energy. Thus, harvesting just a portion of this tremendous amount of energy holds significant promise for a more sustainable society. While traditional solid-state inorganic semiconductors have dominated the research stage on thermal-to-electrical energy conversion, carbon-based semiconductors have recently attracted a great deal of attention as potential thermoelectric materials for low-temperature energy harvesting, primarily driven by the high abundance of their atomic elements, ease of processing/manufacturing, and intrinsically low thermal conductivity. This quest for new materials has resulted in the discovery of several new kinds of thermoelectric materials and concepts capable of converting a heat flux into an electrical current by means of various types of particles transporting the electric charge: (i) electrons, (ii) ions, and (iii) redox molecules. This has contributed to expanding the applications envisaged for thermoelectric materials far beyond simple conversion of heat into electricity. This is the motivation behind this review. This work is divided in three sections. In the first section, we present the basic principle of the thermoelectric effects when the particles transporting the electric charge are electrons, ions, and redox molecules and describe the conceptual differences between the three thermodiffusion phenomena. In the second section, we review the efforts made on developing devices exploiting these three effects and give a thorough understanding of what limits their performance. In the third section, we review the state-of-the-art thermoelectric materials investigated so far and provide a comprehensive understanding of what limits charge and energy transport in each of these classes of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Investigation of the Effect of Atmospheric Plasma Treatment in Nanofiber and Nanocomposite Membranes for Piezoelectric Applications

In this work, we report the effect of steady-state atmospheric plasma (Corona discharge) in nanofibers and nanocomposite membranes for piezoelectric applications. The investigation was performed in PVDF (Poly vinylidene fluoride) nanofibers, CNT (Carbon Nanotubes)-reinforced PVDF nanocomposites, and PAN (Poly acrylonitrile) nanofiber membranes. Steady-state plasma was generated with a high voltage power source with 1 mA discharge current output and 6 kV discharge voltage, and the gap between tip and the material was maintained to be 1 cm. For the fabrication of nanofibers and nanocomposite membranes, an electrospinning method was used. The electrospinning parameters, such as flow rate and voltage, were optimally tuned for obtaining uniform nanofibers and nanomembranes. Along with the plasma treatment, heat treatment above the glass transition temperature was also conducted on the nanofiber membranes. Using a Scanning Electron Microscope (SEM), the morphology of the nanofibers was observed. X-ray Diffraction (XRD) demonstrated the polycrystallinity of the nanofibers. Fourier Transform Infrared Spectroscopy (FTIR) analysis of the PVDF nanofibers shows a peak at 796 cm−1 representing α-phase (C-H rocking) in the control sample which is absent in the treated samples. Raman spectroscopy of PVDF nanofibers identifies a Raman shift from 873 cm−1 to 877 cm−1 (denoting β-phase) for plasma-treated samples only. Electron Paramagnetic Resonance (EPR) concludes that the intensity of the free radicals increases from 1.37 to 1.46 (a.u.) after plasma treatment. Then, sensors were fabricated from the PVDF nanofibers, MWCNT-reinforced PVDF nanofibers, and PAN nanofibers to characterize their piezoelectric properties. The impact test results showed that the atmospheric plasma and heat-treated samples had 86%, 277%, and 92% increases of the d33 value (piezoelectric coefficient) in the case of PVDF nanofibers, MWCNT-reinforced nanofibers, and PAN nanofibers, respectively. It was also observed that the capacitance of the nanofiber membranes has increased due to the plasma treatment.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Coherence in Polycrystalline Thin Films of Twisted Molecular Crystals

Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Chemistry↗
NASA NTRS2006

Thermal Conductivity of Ultem(TradeMark)/Carbon Nanofiller Blends

In an effort to improve polymer thermal conductivity (TC), Ultem(TradeMark) 1000 was compounded with nano-fillers of carbon allotropes. Ultem(TradeMark) 1000 was selected since it is both solution and melt processable. As-received and modified multiwalled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNF) and expanded graphite (EG) were investigated. MWCNTs were modified by functionalizing the surface through oxidization with concentrated acids, mixing with an alkyl bromide, and addition of alkyl and phosphorus compounds after initial treatment with n-butyl lithium. Functionalization was performed to improve the TC compatibility between the resin and MWCNTs. It was postulated that this may provide an improved interface between the MWCNT and the polymer which would result in enhanced TC. The nano-fillers were mixed with Ultem(TradeMark) 1000 in the melt and in solution at concentrations ranging from 5 to 40 wt%. Ribbons were extruded from the blends to form samples where the nano-fillers were aligned to some degree in the extrusion direction. Samples were also fabricated by compression molding resulting in random orientation of the nano-fillers. Thermal properties of the samples were evaluated by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analyzer (TGA). Tensile properties of aligned samples were determined at room temperature. The specimens were cut from the ribbons in the extrusion direction; hence the nano-fillers are somewhat aligned in the direction of stress. Typically it was observed that melt mixed samples exhibited superior mechanical properties compared to solution mixed samples. As expected, increased filler loading led to increased modulus and decreased elongation with respect to the neat polymer. The degree of dispersion and alignment of the nano-fillers was determined by high-resolution scanning electron microscopy (HRSEM). HRSEM of the ribbons revealed that the MWCNTs and CNFs were predominantly aligned in the flow direction. The TC of the samples was measured using a Nanoflash(TradeMark) instrument. Since the MWCNTs and CNF are anisotropic, the TC was expected to be different in the longitudinal (parallel to the nanotube and fiber axis) and transverse (perpendicular to the nanotube and fiber axis) directions. The extruded ribbons provided samples for transverse TC measurements. However, to determine the TC in the longitudinal direction, the ribbons needed to be stacked and molded under 1.7 MPa and 270 C. Samples were then obtained by cutting the molded block with a diamond saw. The largest TC improvement was achieved for aligned samples when the measurement was performed in the direction of MWCNT and CNF alignment (i.e. longitudinal axis). Unaligned samples also showed a significant improvement in TC and may be potentially useful in applications when it is not possible to align the nano-filler. The results of this study will be presented.

Ghose, S.↗
DOE OSTI2022

Quinonoid versus Aromatic π-Conjugated Oligomers and Polymers and Their Diradical Characters

Quinonoid elements in π-conjugated oligomers and polymers have promising characteristics by providing unique structures and electronic properties, including varying degrees of ground state open shell diradical character and small band gaps. So far, quinonoid ground state polymers were rarely identified, and one of the goals of this work was to expand the portfolio of such systems in which over 17 different repeat units were considered, about half preferred a quinonoid and half preferred aromatic structures plus several with the alternating A-Q composition were also included. The dependency of the diradical character as a function of size and composition opens a rich space to discover trends affecting the aromaticity and diradical character. Herein, we show that the diradical character is a useful parameter to classify a wide variety of polymers based on their ground states in a systematic study of a large number of homo- and heterosystems. Homo-polymers with quinonoid ground states show a high diradical character, while those with the aromatic ground state behave as closed-shell systems with no or a very small diradical character. The diradical character of quinonoid systems depends strongly on the size, which increases with the size of the oligomer. Here, we found a correlation between the diradical character and the interring C–C distance as well as the singlet–triplet energy gaps. In alternating copolymers mixing quinonoid and aromatic subunits, we found open-shell hetero-polymers with moderate to high diradical characters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Further Investigations of the Passive Optical Sample Assembly (POSA) - I Flight Experiment

The Passive Optical Sample Assembly-I (POSA-I), part of the Mir Environmental Effects Payload (MEEP), was designed to study the combined effects of contamination, atomic oxygen, ultraviolet radiation, vacuum, then-nal cycling, and other constituents of the space environment on spacecraft materials. The MEEP program is a Phase I International Space Station Risk Mitigation Experiment. Candidate materials for the International Space Station (ISS) were exposed in a specially designed "suitcase" carrier, with identical specimens facing either Mir or space. The payload was attached by EVA to the exterior of the Mir docking module during the STS-76 mission (f'ig. 1). It was removed during the STS-86 mission after an 18-month exposure. During the mission, it received approximately 7 x 1019 atoMS/CM2 atomic oxygen, as calculated by polymer mass loss, and 413 ESH of solar ultraviolet radiation on the Mir-facing side. The side facing away from Mir received significant contaminant deposition, so atomic oxygen fluence has not been reliably determined. The side facing away from Mir received 571 ESH of solar UV. Contamination was observed on both the Mir-facing and space-facing sides of the POSA-I experiment , with a greater amount of deposition on the space facing side than the Mir side. The contamination has been determined to be outgassed silicone photofixed by ultraviolet radiation and converted to silicate by atomic oxygen interaction. Electron spectroscopy for chemical analysis (ESCA) with depth profiling indicated the presence of 26 - 31 nm silicate on the Mir-facing side and 500 - 1000 nm silicate on the space-facing side. The depth profiling also showed that the contaminant layer was uniform, with a small amount of carbon present on the surface and trace amounts of nitrogen, phosphorus, sulfur, and tin. The surface carbon layer is likely due to post-flight exposure in the laboratory and is similar to carbonaceous deposits on control samples. EDAX and FTIR analysis concurred with ESCA for the presence of silicon, oxygen, and carbon. Nearly 400 samples were exposed on POSA-I, which included materials such as thermal control coatings polymeric films, optical materials, and multi-layer insulation blankets. A previous paper discussed the effects of the space environment exposure and contaminant deposition on candidate materials for ISS, including Z93P inorganic thermal control coating, various anodizes, and multi-layer insulation blankets. This paper details the investigation of environmental effects on the remainder of POSA-I samples, particularly the innovative conductive thermal control coatings developed by AZ Technology of Huntsville, AL and HT Research Institute of Chicago, IL. The silicone/silicate contamination had a significant impact on the solar absorptance of white inorganic thermal control coatings on the space-facing side of POSA-I. The effect of contamination on electrical conductivity is discussed. Samples of conductive anodized aluminum developed by Boundary Technologies of Buffalo Grove, IL were also exposed on POSA-I. The effects of the space environment and contaminant deposition on the optical and electrical properties of the conductive anodized aluminum are discussed.

Finckenor, Miria M.↗
DOE OSTI2024

A multiscale anisotropic polymer network model coupled with phase field fracture

The study of polymers has continued to gain substantial attention due to their expanding range of applications, spanning essential engineering fields to emerging domains like stretchable electronics, soft robotics, and implantable sensors. These materials exhibit remarkable properties, primarily stemming from their intricate polymer chain network, which, in turn, increases the complexity of precisely modeling their behavior. Especially for modeling elastomers and their fracture behavior, accurately accounting for the deformations of the polymer chains is vital for predicting the rupture in highly stretched chains. Despite the importance, many robust multiscale continuum frameworks for modeling elastomer fracture tend to simplify network deformations by assuming uniform behavior among chains in all directions. Recognizing this limitation, our study proposes a multiscale fracture model that accounts for the anisotropic nature of elastomer network responses. At the microscale, damage in the chains is assumed to be driven by both the chain's entropy and the internal energy due to molecular bond distortions. In order to bridge the stretching in the chains to the macroscale deformation, we employ the maximal advance path constraint network model, inherently accommodating anisotropic network responses. As a result, chains oriented differently can be predicted to exhibit varying stretch and, consequently, different damage levels. To drive macroscale fracture based on damages in these chains, we utilize the micromorphic regularization theory, which involves the introduction of dual local-global damage variables at the macroscale. The macroscale local damage variable is obtained through the homogenization of the chain damage values, resulting in the prediction of an isotropic material response. The macroscale global damage variable is subjected to nonlocal effects and boundary conditions in a thermodynamically consistent phase field continuum formulation. Moreover, the total dissipation in the system is considered to be mainly due to the breaking of the molecular bonds at the microscale. To validate our model, we employ the double-edge notched tensile test as a benchmark, comparing simulation predictions with existing experimental data. Additionally, to enhance our understanding of the fracturing process, we conduct uniaxial tensile experiments on a square film made up of polydimethylsiloxane (PDMS) rubber embedded with a hole and notches and then compare our simulation predictions with the experimental observations. Furthermore, we visualize the evolution of stretch and damage values in chains oriented along different directions to assess the predictive capacity of the model. In conclusion, the results are also compared with another existing model to evaluate the utility of our model in accurately simulating the fracture behavior of rubber-like materials.

42 ENGINEERING↗
DOE OSTI2023

Degradation in interfacial shear strength of carbon fiber/ vinyl ester composites due to long-term exposure to seawater using push-out tests

Here, in this study, single fiber (~7-μm diameter) push-out tests are conducted to evaluate hygrothermal effects on the interfacial shear strength (IFSS) of carbon fiber/vinyl ester (CF/VE) composites. Hygrothermal conditioning is achieved by saturating samples in simulated seawater at 40 °C for two years. An investigation has been conducted on the preparation, validity, and interpretation of the push-out test results. First, the authors present a polishing methodology that results in thin films of CF/VE composites in the thickness range of 15–120 μm and produces an average 41.2% drop in IFSS due to long-term hygrothermal exposure. Using scanning electron microscopy (SEM), we show that during the push-out tests, the failure initiates locally at the zone of minimum bond strength at the bottom (away from the indenter), then propagates along the length of the interface. The influence of radial tensile stresses originating due to bending is found to be negligible. Using the SEM imaging of the pushed-out fibers, we validate the failure of the interface to be the primary source of failure. The associated results are found to depend on the thickness of the interface. We then reevaluate the results using the Weibull distribution, knowing that the failure mechanism is analogous to the weakest link theory. The results show a 25.5% drop in the IFSS of the CFVE composite, measured at an infinitesimal scale due to long-term to hygrothermal conditioning at 40 °C. A significant drop in IFSS was observed after reheating above glass transition temperature (T g ) and cooling.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Salts as Additives: A Route to Improve Performance and Stability of n-Type Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are becoming increasingly ubiquitous in various applications at the interface with biological systems. However, their widespread use is hampered by the scarcity of electron-conducting (n-type) backbones and the poor performance and stability of the existing n-OECTs. Here, we introduce organic salts as a solution additive to improve the transduction capability, shelf life, and operational stability of n-OECTs. We demonstrate that the salt-cast devices present a 10-fold increase in transconductance and achieve at least one year-long stability, while the pristine devices degrade within four months of storage. The salt-added films show improved backbone planarity and greater charge delocalization, leading to higher electronic charge carrier mobility. These films show a distinctly porous morphology where the interconnectivity is affected by the salt type, responsible for OECT speed. The salt-based films display limited changes in morphology and show lower water uptake upon electrochemical doping, a possible reason for the improved device cycling stability. Our work provides a new and easy route to improve n-type OECT performance and stability, which can be adapted for other electrochemical devices with n-type films operating at the aqueous electrolyte interface.

36 MATERIALS SCIENCE↗
NASA NTRS2015

On The Development of Additive Construction Technologies for Application to Development of Lunar/Martian Surface Structures Using In-Situ Materials

For long-duration missions on other planetary bodies, the use of in-situ materials will become increasingly critical. As man's presence on these bodies expands, so must the breadth of the structures required to accommodate them including habitats, laboratories, berms, radiation shielding for natural radiation and surface reactors, garages, solar storm shelters, greenhouses, etc. Planetary surface structure manufacturing and assembly technologies that incorporate in-situ resources provide options for autonomous, affordable, pre-positioned environments with radiation shielding features and protection from micrometeorites, exhaust plume debris, and other hazards. This is important because gamma and particle radiation constitute a serious but reducible threat to long-term survival of human beings, electronics, and other materials in space environments. Also, it is anticipated that surface structures will constitute the primary mass element of lunar or Martian launch requirements. The ability to use in-situ materials to construct these structures will provide a benefit in the reduction of up-mass that would otherwise make long-term Moon or Mars structures cost prohibitive. The ability to fabricate structures in situ brings with it the ability to repair these structures, which allows for self-sufficiency necessary for long-duration habitation. Previously, under the auspices of the MSFC In Situ Fabrication and Repair (ISFR) project and more recently, under the joint MSFC/KSC Additive Construction with Mobile Emplacement (ACME) project, the MSFC Surface Structures Group has been developing materials and construction technologies to support future planetary habitats with in situ resources. One such technology, known as Contour Crafting (additive construction), is shown in Figure 1, along with a typical structure fabricated using this technology. This paper will present the results to date of these efforts, including development of novel nozzle concepts for advanced layer deposition using the Contour Crafting process. This process, conceived initially for rapid development of cementitious structures on Earth, also lends itself exceptionally well to the automated fabrication of planetary surface structures using minimally processed regolith as aggregate, and imported binder material or binders developed from in situ materials. This process has been used successfully in the fabrication of construction elements using lunar regolith simulant and Mars regolith simulant, both with various binder materials. These binder materials have resulted from extensive evaluation and include both "imported" binder materials that might be launched from Earth as well as some binder materials that can theoretically also be derived from existing regolith materials. They were chosen to 1) reduce penetrating radiation as much as possible, primarily with hydrogen-bearing polymers, 2) attempt to provide an air-tight structure, 3) sufficiently mix and adsorb to regolith grains for strength, 4) maximize tolerance to day-night thermal cycling, 5) possibly increase electrical conductivity to dissipate any accumulated static charge, and 6) ease their application on planetary surfaces (specifically, the accommodation of reduced atmosphere and lack of heat sinks). Some of these materials have been tested with respect to radiation mitigation, micrometeorite resistance, and resistance to larger, slower-traveling pieces of regolith impinging on the surface, simulating nearby launch and landing activities. Conceptual designs for a Continuous Feedstock Delivery/Mixing System (CFDMS) will also be presented and future planned activities will be discussed as well.

Werkheiser, Niki↗
DOE OSTI2025

Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Shock compression experiments using the DiPOLE 100-X laser on the high energy density instrument at the European x-ray free electron laser: Quantitative structural analysis of liquid Sn

X-ray free electron laser (XFEL) sources coupled to high-power laser systems offer an avenue to study the structural dynamics of materials at extreme pressures and temperatures. The recent commissioning of the DiPOLE 100-X laser on the high energy density (HED) instrument at the European XFEL represents the state-of-the-art in combining x-ray diffraction with laser compression, allowing for compressed materials to be probed in unprecedented detail. Here, we report quantitative structural measurements of molten Sn compressed to 85(5) GPa and ~3500 K. The capabilities of the HED instrument enable liquid density measurements with an uncertainty of ~1% at conditions which are extremely challenging to reach via static compression methods. We discuss best practices for conducting liquid diffraction dynamic compression experiments and the necessary intensity corrections which allow for accurate quantitative analysis. We also provide a polyimide ablation pressure vs input laser energy for the DiPOLE 100-X drive laser which will serve future users of the HED instrument.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Retrospective on Recent DOE-Funded Studies Concerning the Extraction of Rare Earth Elements & Lithium from Geothermal Brines (Final Report)

Rare earth elements (REE) and lithium are non-toxic metals that are considered critical materials due to their use in electronics, magnets, batteries, and a wide variety of industrial processes important for the economy and military preparedness. Demand for REE and lithium is increasing and these critical materials are imported, so identifying and exploiting domestic sources of REE and lithium is a national priority. The U.S. Department of Energy (DOE) Geothermal Technologies Office (GTO) has been in the forefront of sponsoring research investigating the potential recovery of REE, lithium, and other critical minerals from geothermal brines. It has been proposed that the future of geothermal energy should include “hybrid systems” that combine electricity generation with other revenue-generating activities, such as recovery of valuable and critical minerals, including REE and lithium. Two recent GTO funding opportunities have focused on the recovery of REE and other valuable minerals from geothermal brines. The research supported by the GTO’s mineral recovery program is focused on three areas: resource characterization, technology for the extraction of REE, and technology for the extraction of lithium (Tables 1 and 2). This report is a retrospective study examining the outcome of GTO’s two recent mineral recovery programs (DE-FOA-0001016 in FY 2014 and DE-FOA-0001376 in FY 2016). In this report, the knowledge, technology, and techniques that were developed by researchers funded by GTO are summarized and discussed. Four projects were funded to assess the concentrations and amounts of REE found in geothermal brines and oil field produced waters. The GTO-funded studies compiled publically available data on REE concentrations from brines and produced water from all over the USA. In addition, new samples were collected and characterized from major geothermal and hydrocarbon basins in the Western USA. The studies examined the relationship between lithology and REE concentrations and developed models examining the influence of geology on REE concentrations in produced brines. It was determined that REE are frequently found at higher concentrations in oil field produced water than geothermal brines, but that some geothermal areas had significant REE resources. Significant reservoirs of REE were identified in the Western USA. In some cases, concentrations of REE were more than 1000 times the concentrations found in seawater. Collectively, these studies represent a comprehensive picture of REE resources associated with geothermal and hydrocarbon systems in the USA. The studies did not examine lithium resources, but in some cases, lithium concentration data was collected. Data from these studies are housed in the Geothermal Data Repository (GDR) and represent a significant information resource and it is recommended that these data be further analyzed in a future study. Eight projects were funded to develop new technology for REE extraction from geothermal fluids. These projects investigated sorption as an approach for removal and recovery of REE from geothermal brines. The projects investigated cutting-edge technology for selective sorption of ions from complex solutions, including the application of metal-organic frameworks and biosorbent proteins. The REE sorption studies tested different combinations of metal-binding ligands and solid supports. The most promising metal-binding ligands for REE included phosphonic acid, thiol, and carboxylic acid functional groups. Ligands were attached or incorporated into a wide variety of solid supports. In most cases, attachment was via covalent bonding to organic resins, polymers, or silica-based supports. Most of the REE projects were conducted at a low technology readiness level (TRL) and showed promise, but direct comparison between technologies was not possible based on the available information. It is recommended that testing and reporting be standardized to the extent possible to facilitate comparisons between technologies. Two projects were directed at novel lithium extraction technology. Both projects investigated the use of inorganic sorbents, including manganese oxides. One study also examined the use of metal- ion imprinted polymers as selective ion-exchange resins for the separation of lithium and manganese from brines. Both approaches showed promise for the selective extraction of lithium from brines, including potentially geothermal brines. Results from these GTO studies indicated that selective REE and lithium extraction is possible, but interference from co-occurring solutes, such as calcium, magnesium, or heavy metals, will interfere with process efficiency and negatively impact process economics. Techno-economic analysis conducted as part of the resource and technology studies suggest extraction of REE from geothermal brines is unlikely to be economically viable, especially since non-geothermal produced waters frequently have higher REE concentrations. It is recommended that benchmarks for techno-economic analysis be established to the extent possible for future studies, to facilitate direct comparison of various technologies. Based on the collective results of this program, it appears that hybrid geothermal power would benefit more from recovery of lithium and other metals, rather than REE. It is recommended that future studies be conducted at a higher- TRL and that sorbents be tested against actual geothermal fluid samples. Prior higher-TRL efforts to extract metals from geothermal brines should be further evaluated for lessons learned.

36 MATERIALS SCIENCE↗