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All sourcesNASA NTRSDOE OSTI
NASA NTRS2021

Effect of Soldering on Polymer and MnO2 Tantalum Capacitors

Soldering might have a strong effect on performance and reliability of most surface mount technology components, including tantalum capacitors. High quality tantalum capacitors are likely the only type of components where soldering simulation is the first step during screening. Nevertheless, post-soldering failures of tantalum capacitors happen and require additional analysis. Popcorning is a well-known effect in plastic encapsulated microcircuits (PEM) and it occurs also in chip tantalum capacitors. The sensitivity of parts to the presence of moisture during soldering is characterized by the moisture sensitivity level (MSL); however, contrary to PEMs, there is no standard procedure for establishing MSL for tantalum capacitors. The effect of absorbed moisture on soldering related degradation and failures in tantalum capacitors have not been studied properly yet, and there is no sufficient information regarding the difference in the sensitivity to soldering between polymer and MnO2 tantalum capacitors. In this work, 16 types of polymer and 9 types of MnO2 cathodes tantalum capacitors with different moisture content have been tested before and after reflow soldering. The level of moisture release after soldering has been estimated and thermo-mechanical analysis used to assess deformation of capacitors during soldering simulations. Results show that moisture uptake in similar parts is approximately two times greater in polymer than in MnO2 capacitors. Cracking of the case and degradation of parameters can occur in both types of parts, but MnO2 capacitors are much more likely to fail catastrophically with a short circuit and possible ignition during the first power-on cycle. This type of failure in MnO2 capacitors is lot-related, can occur even at derated voltages and relatively low levels of moisture sorption corresponding to room conditions. Baking before soldering is an effective measure to prevent failures even in lots susceptible to popcorning damage. Recommendations for baking and testing to establish MSL are suggested.

Alexander Teverovsky↗
NASA NTRS2021

Effect of Preconditioning on Post-Soldering Failures in Tantalum Capacitors

Soldering have a strong effect on performance and reliability of most surface mount technology components, including tantalum capacitors. High quality tantalum capacitors are likely the only type of components where soldering simulation is the first step during screening. Nevertheless, post-soldering failures of tantalum capacitors do happen and require additional analysis. Popcorning is a well-known effect in plastic encapsulated microcircuits (PEM) and it occurs also in chip tantalum capacitors. The sensitivity of parts to the presence of moisture during soldering is characterized by the moisture sensitivity level (MSL); however, contrary to PEMs, there is no standard procedure for establishing MSL for tantalum capacitors, and standard J-STD-020 is applicable partially only. In this work, the effect of absorbed moisture on soldering related degradation and failures in tantalum capacitors have been studied using 22 types of polymer and 11 types of MnO2 cathodes tantalum capacitors including single and multianode parts. The amount of moisture released during soldering has been estimated by measurements of mass and capacitance variations. Results show that moisture uptake in similar parts is approximately two times greater in polymer than in MnO2 capacitors. Cracking of the case and degradation of parameters can occur in both types of parts, but MnO2 capacitors are much more susceptible to catastrophic short circuit failures and their ignition is possible during the first power-on cycle. This type of failure in MnO2 capacitors is lot-related, can occur even at derated voltages and relatively low levels of moisture sorption corresponding to room conditions. Baking before soldering is an effective measure to prevent failures even in lots susceptible to popcorning damage. Recommendations for testing to establish MSL and for baking to reduce the probability of failures are suggested.

tantalum polymer capacitors↗
NASA NTRS2022

Effect of Ni2+, Zn2+, and Co2+ on green rust transformation to magnetite

In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/ co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleoproxies of Precambrian ocean chemistry are discussed.

Hydrosulfate green rust↗
NASA NTRS2023

Optimizing Surfactant Templating of Yttria-Stabilized Zirconia Aerogels for High-Temperature Applications: Effect of Anionic and Nonionic Surfactant

Aerogels, mesoporous materials with extreme material properties including high specific surface area, low density, and low thermal conductivity, can be useful for applications including catalysis, sorption media, and drug delivery. The low thermal conductivity and high surface area of aerogels makes them advantageous as thermal management systems, specifically for aerospace or aeronautics applications. However, the pore collapse and subsequent surface area decrease of aerogels following exposure to high temperatures must be mitigated to allow aerogels to be effectively used in thermal management applications. This work investigates the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Pluronic® P-123 as surfactant templates in yttria-stabilized zirconia (YSZ) aerogels. By utilizing surfactant templates, known to influence pore structure, it is anticipated that sintering and densification of the aerogels following high-temperature exposure will be mitigated. It was determined that the addition of SDS and P-123 increased the surface area and pore volume of as-dried aerogels and suppressed crystallite growth at high temperatures. However, the impact of surfactant templates on the surface area and pore volume of heat-treated aerogels was negligible, potentially due to low concentrations of surfactant and the removal of the surfactant following high-temperature exposure.

Yttria-stabilized zirconia aerogels↗
NASA NTRSDate not supplied

Experimental Results of a Rapidly Cycled Temperature Swing Adsorption Pump in a Terrestrial Environment

To improve the increasing CO 2 levels on Earth, technology for carbon capture and utilization must be efficient and cost effective. One major contributor of atmospheric CO 2 is post-combustion flue gas, which can contain up to 20% CO 2 . Scrubbing this CO 2 could reduce the environmental impact of this common industrial process. In off-Earth environments, capturing and utilizing CO 2 from space resources is useful for crewed spaceflight life support. Specifically, the Bosch process, which produces water and carbon powder by reacting CO 2 and hydrogen, is a possible in-situ resource utilization (ISRU) architecture for the Moon and Mars. The Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump is an innovative technology designed to capture CO 2 efficiently. The RC-TSA leverages a stacked plate geometry to cycle multiple zeolite-coated beds. The thin layers allow for rapid heat transfer of the zeolite coating, which improves performance over previously tested pump designs. The design is favorable for scalability and manufacturability, which are forward work. Initial testing of the sorption pump using a simulated flue gas environment shows favorable breakthrough capacities and reduced cycle times. Results show promise for on- and off-Earth applications, such as a Martian surface and crewed spaceflight environments.

adsorption pump↗
NASA NTRSDate not supplied

Integrated Bosch Process System Models for In-Situ Oxygen and Carbon Production

In-Situ Resource Utilization (ISRU) technology is a vital component to NASA’s mission of a sustainable presence on the Moon and Mars. Local resources can be leveraged to reduce resupply frequency and mass. Elements of the Bosch process, combined with the carbothermal reduction process, can produce oxygen on the lunar surface with minimal consumables. The Bosch process can also produce oxygen on the Martian surface by using the CO 2 -rich environment. Between both systems, adsorption pump, solar thermal energy, carbon formation reactor, and water recovery subsystems are modeled and integrated to create a functional model in MATLAB software. The model is used to simulate performance of the system and reduce mass, power, and volume requirements. This integrated system model provides a tool to scale ISRU technologies for oxygen and carbon production. The MATLAB model is created by developing a system of independent subsystem models that are solved for their quasi-steady state values which can be integrated with respect to time to determine the change in current states. A flexible time stepping method is used to ensure a high level of accuracy during periods of rapid change while still making use of a simple explicit integration method. The flexible time step is calculated for each independent subsystem and the minimum value from those is used as the overall time step. A flexible time step is calculated by dividing a resolution value, or the maximum change per time step, by the variables current rate of change. The maximum value from all points in space is used for subsystem models that contain multiple values. The process is done for every variable that is being monitored in each subsystem and the global minimum is used as that iteration’s timestep. Several assumptions used in the MATLAB model for fluid flow dynamics, such as 1-D gas flow through the sorption pump, are supported by modeling in Ansys Fluent software. The Lunar oxygen production system is outlined in Fig. 1. The carbothermal reduction subsystem uses solar energy to heat a mixture of lunar regolith and carbon powder to produce carbon monoxide. To begin, the carbon monoxide feeds to the modified Bosch subsystem along with hydrogen gas. The reactants then enter the carbon formation reactor where water and carbon powder are produced. Solar thermal energy is used to add energy to the reactor, but waste heat from the carbothermal process is another potential heat source. The water is collected and electrolyzed to produce hydrogen which reenters the Bosch subsystem, and the oxygen is stored for downstream use. The carbon powder is collected and feeds back into the carbothermal subsystem. The Martian oxygen production system uses the full Bosch process and is outlined in Fig 2. A CO 2 adsorption pump thermally cycles to scrub and pressurize CO 2 from the environment. Along with an initial supply of hydrogen, the reactants enter the Reverse Water Gas Shift Reactor (RWGSR) which produces carbon monoxide and water. Carbon monoxide and unreacted hydrogen enter the carbon formation reactor to produce water and carbon powder. The water is collected from both reactors and electrolyzed to reintroduce hydrogen and store oxygen for propellant production or life support. Carbon is removed from the carbon formation reactor and stored. The adsorption pump utilizes rapid cycle temperature swings within a stack of zeolite coated surfaces. The subsystem model solves 1-D quasi-steady conservation laws of the quasi-steady form, shown in Eq. 1, for the gas stream and heat exchange liquid to predict performance parameters such as breakthrough capacity and optimum cycle time. The source term S is used to capture interactions between the fluid flows and the sorbent. A quasi-steady-state scheme is used where no time derivatives appear in the governing equations, except for those in the source terms. This results in an autonomous system, where ∂F/∂x = ƒ(F). The fluxes F are provided at the inlet, and an explicit method is used to solve for the spatial distribution of F. The heat and mass flows to the sorbent are then extracted from the source terms. These flows are numerically integrated to produce a 1-D solution for the system’s state as a function of both time and space. The body of the adsorption pump is separated into two semi-independent models: the heat exchanger fluid flow and gas flow through the zeolite coated surfaces. Both models are solved using the above-described method to find a 1-D solution as a function of space and interact only once a timestep is taken. The interaction point is the sorbent through which all heat transfer between the two models must occur. Sorbent mass adsorption is calculated using the Lagergren model, shown in Eq. 2, where the transfer coefficient, λ D , is found by solving a system of nondimensionalized equations derived by using the heat and mass transfer analogy for transport phenomena. Using Grade 544 Type 13X zeolite as the sorbent material, the equilibrium concentration, θ eq , is calculated using the k-site Langmuir isotherm and fit parameters. Additionally, the enthalpy of adsorption used in the model is computed by interpolation of available data [1]. The subsystem model was validated using the Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump. The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC). The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC).

In situ Resource Utilization↗
NASA NTRSDate not supplied

On Predicting Transient Pressure in Vacuum Systems Featuring Getter Materials

Getter materials have been used to reduce pressure or partial pressures in a variety of vacuum applications ranging from vacuum tubes to space flight science instruments. Testing of getter materials has tended to emphasize the capacity of candidate materials to collect specific gas species in sufficient quantities to size them in these applications. When determining a getter material’s capacity, it is typically subjected to enough excess target gas to ensure it sorbs as quickly as possible. However, when both the gas source strength and the getter’s sorption rate exhibit transient decay behavior, such data is not sufficient to predict the targeted species’ partial pressure within a vacuum system as a function of time.

M. S. Woronowicz↗
NASA NTRSDate not supplied

On Predicting Transient Pressure in Vacuum Systems Featuring Getter Materials

Getter materials have been used to reduce pressure or partial pressures in a variety of vacuum applications ranging from vacuum tubes to space flight science instruments. Testing of getter materials has tended to emphasize the capacity of candidate materials to collect specific gas species in sufficient quantities to size them in these applications. When determining a getter material’s capacity, it is typically subjected to enough excess target gas to ensure it sorbs as quickly as possible. However, when both the gas source strength and the getter’s sorption rate exhibit transient decay behavior, such data is not sufficient to predict the targeted species’ partial pressure within a vacuum system as a function of time.

M. S. Woronowicz↗
NASA NTRSDate not supplied

On Predicting Transient Pressure in Vacuum Systems Featuring Getter Materials

Getter materials have been used to reduce pressure or partial pressures in a variety of vacuum applications ranging from vacuum tubes to space flight science instruments. Testing of getter materials has tended to emphasize the capacity of candidate materials to collect specific gas species in sufficient quantities to size them in these applications. When determining a getter material’s capacity, it is typically subjected to enough excess target gas to ensure it sorbs as quickly as possible. However, when both the gas source strength and the getter’s sorption rate exhibit transient decay behavior, such data is not sufficient to predict the targeted species’ partial pressure within a vacuum system as a function of time.

Michael Woronowicz↗
NASA NTRS2024

Superfluid-Tight Cryogenic Receiver With Continuous Sub-Kelvin Cooling for EXCLAIM

The EXperiment for Cryogenic Large-Aperture Intensity Mapping (EXCLAIM) is a balloon-borne telescope designed to survey star formation over cosmological time scales using intensity mapping in the 420 – 540 GHz frequency range. EXCLAIM uses a fully cryogenic telescope coupled to six on-chip spectrometers featuring kinetic inductance detectors (KIDs) to achieve high sensitivity, allowing for fast integration in dark atmospheric windows. The telescope receiver is cooled to ≈ 1.7 K by immersion in a superfluid helium bath and enclosed in a superfluid-tight shell with a meta-material anti-reflection coated silicon window. In addition to the optics and the spectrometer package, the receiver contains the magnetic shielding, the cryogenic segment of the spectrometer readout, and the sub-Kelvin cooling system. A three-stage continuous adiabatic demagnetization refrigerator (CADR) keeps the detectors at 100 mK while a 4He sorption cooler provides a 900 mK thermal intercept for mechanical suspensions and coaxial cables. We present the design of the EXCLAIM receiver and report on the flight-like testing of major receiver components, including the superfluid-tight receiver window and the sub-Kelvin coolers.

continuous adiabatic demagnetization refrigerator↗
DOE OSTI2020

An advanced membrane-based HMX model and its application in utilizing sensible and latent heat removed in space cooling

This paper presents a comprehensive simulation model for advanced membrane-based heat and mass exchanger (HMX) components which account for three separate fluid streams with complex flow patterns. The model was implemented with various liquid desiccants and their properties (including LiCl, CaCl and ionic liquid (IL)). Preliminary model validation is presented using data from a laboratory prototype absorber. The paper also presents implementation of the model into a sorption system modeling platform and analyzes potential benefit analysis of the HMX component in utilizing the sensible and latent heat removed in space cooling to heat water. The developed model and codes are expected to enable detailed optimization studies and identify novel configurations for the three-fluid HMX maximum performance and cost effectiveness.

Gao, Zhiming↗
DOE OSTI2020

Solid, hydrophobic aggregators and methods of making and using the same

Disclosed herein are aggregators that can be cellulosic particles having high oil sorption capacity, high hydrophobicity, high buoyancy in water, and an aggregation quality that can support environmental remediation of hydrocarbon spills (e.g., crude oil spills) by various cleanup strategies including burning, skimming, or bioremediation. Also disclosed are methods of making the materials and methods of using the materials for environmental remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Crystalline Aluminosilicates for Radionuclide Remediation

Crystalline aluminosilicates have a wide range of applications such as media for the capture and/or immobilization of radionuclides. Several different types of metal-exchanged zeolites have been successfully demonstrated as effective sorbents for gaseous, aqueous, or solid-state capture and immobilization of radionuclides including iodine [e.g., I2(g), CH3I(g)], xenon, krypton, radium (e.g., 226Ra and 228Ra), selenium (e.g., 79Se6+), technetium (e.g., 99TcO4-), strontium (e.g., 90Sr2+), cesium (e.g., 135Cs+, 137Cs+), mixed alkali halide streams (i.e., iodide and chloride salts), and actinides (e.g., U6+, Th4+). These zeolites include sodalite (SOD), mordenite (MOR or Z-type), faujasite (FAU), Linde type-A (LTA), cancrinite (CAN), gismondine (GIS), and heulandite (or clinoptilolite) (HEU). The structural building blocks of these seven materials vary from cages (e.g., a-cages, ß-cages, e-cages) to channels linking various cage types and these are mostly comprised of aluminosilicates. This chapter will delve into the crystallographic differences between these framework materials and provide a brief overview of literature data where these seven crystalline aluminosilicates have been utilized for the capture and/or immobilization of radionuclides. Metal-exchanged zeolites (e.g., MOR, FAU, LTA) have often been the source of study for gaseous capture of iodine where the more promising compositions include Ag-exchanged sorbents; these types of materials can be made in a variety of robust forms including berl saddles and extrudates. Sodalite can be used as an immobilization strategy for halide waste streams (e.g., Cl, I), including those from electrochemical reprocessing of used nuclear fuel, as well as TcO4–. Cancrinite has been demonstrated to enhance sorption capacity of sediments for several problematic ionic radionuclides including Cs+, SeO42–, and TcO4–. Actinides such as U6+ and Th4+ have been successfully captured from solutions using MOR, FAU, LTA, and HEU-type aluminosilicates. Finally, mixtures of aluminosilicates have been included in a set of zeolite materials that show promise as sorbents for 226Ra and 228Ra removal from mine waters.

zeolites, aluminosilicates, radionuclide remediati↗
DOE OSTI2022

Comparison of Fission Product Release Predictions using PARFUME and BISON with Results from the AGR-3/4 Irradiation Experiment

The PARFUME (PARticle Fuel ModEl) fuel performance modeling code and the BISON nuclear fuel performance application built on the Multiphysics Object-Oriented Simulation Environment (MOOSE) finite element library were used to predict the fission product release from tristructural isotropic (TRISO) coated fuel particles and compacts during the third and fourth irradiation experiment of the Advanced Gas Reactor (AGR-3/4) Fuel Development and Qualification Program. The fuel performance modeling codes PARFUME and BISON modeled the AGR-3/4 irradiation experiment using the fuel compact time-averaged volume averaged (TAVA) daily temperatures for a total irradiation duration of 369.1 effective full power days (EFPD) to predict the release fraction of the fission product silver (Ag-110m) from a representative TRISO-coated fuel particle from AGR-3/4 compacts. Post-irradiation examination (PIE) measurements provided data on the release of these fission products in the compacts outside of the silicon carbide (SIC) layer. The PARFUME and BISON results were then compared to the silver release measured from compact gamma scanning. The results showed good agreement between PARFUME and BISON but both codes under-predicted the silver release fraction for all the compacts. In addition, BISON was used to model and predict the fission product concentration radial profile outside of the compacts in capsules’ inner and outer rings. These rings were either comprised of matrix and/or structural graphite. To obtain the concentration profiles of silver, cesium, and strontium, a sorption isotherm model was developed in BISON to capture the effects of fission product transport across the gaps between the concentric rings. The general shape of the concentration radial profiles as calculated by BISON were similar in the inner ring (IR) but varied in the outer ring (OR) depending on the fission product of interest or capsule temperature. Using this methodology and model, BISON now has the capability to aid in developing new fission product diffusion coefficients for matrix or structural graphite materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Comparison of AGR-3/4 Fission Product Transport Model to Measurements and Extraction of Diffusivities via Analytical Fits

A one-dimensional finite-element model based on the MOOSE framework has been constructed, and overall transport estimates are predicted based on available diffusivities and sorption isotherms in the extant literature. The predicted transport profiles are compared to experimental results, where such results are available, including total inventory analysis of gamma emitters, liquid scintillation results for Sr-90 concentrations, radial deconsolidation leach-burn-leach within compacts, tomographic reconstructions based on detailed gamma scanning and destructive physical sampling of several rings. The magnitude of expected transport to the sink ring is generally predicted by the model for silver and cesium, however, modeled detailed concentration profiles are not consistent with experimental results. Strontium and europium transport is not well characterized by model results.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2020

[Challenges and Opportunities in] Process Modeling of Intensified Chemical Processes

Before the benefits of process intensification can be fully realized, a multitude of advances in process modeling will be necessary. Process intensification (PI) has the potential to speed development of chemical engineering innovations. Among its many benefits, PI can increase the driving forces (physical and/or chemical) for transport phenomena, separations, and/or reactions in chemical processes, and inspire novel process configurations with major technical and economic benefits. Examples of PI applications include integrated process units such as heat exchange networks, sorption- or membrane-enhanced reactors, and dividing-wall distillation columns, among others [AIChE(2017)].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reveal of Uranium Bioremediation Mechanisms by Bacillus Species through Proteomics Studies

Radionuclides, such as Uranium (U) and heavy metals continue to pose threats to the ecosystem health and processes at the Department of Energy (DOE) managed, Savannah River Site (SRS), located along the Savannah River near Aiken, SC. Such co-contaminated environments are difficult to remediate using conventional excavation and disposal or pump-and-treat approaches. Globally, more than 109 tons of uranium contaminated areas pose a long term threat to human and ecological health. Even with presented low concentrations in the brain, central nervous effects are still observed. Uranium and depleted uranium (DU) have long term effects on the kidneys. Some small general health effects include severe headaches and breathing problems. Uranus ions are toxic to living cells because they inhibit metabolism of carbohydrates by blocking ATP binding sites. Bioremediation by microorganisms represents an alternative solution, which is advantageous because of the possibility of biosorbent regeneration, cost-effectiveness, increased metal removal and easy recovery of some valuable metals. Bacillus sp. bacterium was previously used in the bioremediation of heavy metals in coal mine run off waters of SRS. However, its ability to bioremediate uranium was unknown so far. Hence, in the present study, uranium bioremediation by Bacillus sp. bacterium was investigated. The mechanism of bioremediation was also revealed through proteomics studies. Heavy metals contamination poses a serious threat to water, soil and human health. Soil and water are contaminated due to excessive exploitation of uranium mines for generation of nuclear energy and weaponry. It is not degradable easily and persist in soil and water for a long period of time due to its long half- life. Savannah river site (SRS) is one of the uranium contaminated sites. The physical or chemical remediation techniques are costly and complex. Microbial system approaches with competent bacteria has received increased attention due to its adaptability in various environmental matrices and cost effectiveness. However, even though there are multiple suggested pathways (F1), the specific mechanisms that drive this behavior are still unclear, especially with popular microorganisms such as Bacillus species. In a previous research (Ibeanusi et al, 2003) Bacillus sp. was shown to detoxify and precipitate a variety of heavy metals in coal pile runoff waters of SRS site. Additionally, genomic analysis demonstrated that this microorganism posses multiple attributes for chemical transport regulation and metabolic pathways. U remediation occurs during the first 20 hours of exposure. During this time period, Bacillus sp. may work primarily under two mechanisms - sorption and accumulation. These two mechanisms simultaneously work to protect the microorganism from high concentrations. Figure 10 demonstrates that certain proteins are up regulated and down regulated under extreme stressful conditions. Membrane fraction proteins were up regulated. Cytosolic fraction proteins were down regulated. This protein information coincides with the adsorption behavior. Bacillus sp. is a good candidate for U remediation at various concentrations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Trace Chemical Detection Using Intercalated MXenes as a Signal Enhancing Substrate in Optical Probes

MXenes are 2D materials composed of layered transition metal nitrides or carbides. These materials are synthesized by HF exfoliation from MAX phases (Ti{sub 3}AlC{sub 2}). The 2D nanomaterial was synthesized by the removal of the 'A' element, resulting in a Mxene product (Ti{sub 3}C{sub 2}). MXenes have the general formula M{sub n+1}X{sub n}T{sub x}, where M is an early transition metal, X is Carbon and/or Nitrogen, and T accounts for surface terminated functional groups such as Fluoride, hydroxyl, and oxygen. These materials have very unique properties, similar to graphene, that allows them to be applied in a variety of trace detection techniques including surface-enhanced Raman spectroscopy (SERS). MXenes have also been demonstrated to selectively uptake uranyl ion, UO{sub 2}{sup 2+}. If this property can be combined with SERS or fluorescence detection, it may be possible to use MXenes as the basis for an alternative method to kinetic phosphorescence analysis (KPA) for trace uranyl measurements. Objectives: To confirm that MXene Nano materials are suitable substrates for SERS and sensor development by enhancing Raman signaling. To determine if certain MXene preparation methods yield materials that are more suitable for trace sensing methods. To determine uranyl uptake properties of these MXene materials and test them for analytical signals. Sample Preparation: Preparation of Ti{sub 3}C{sub 2}MXene (at FSU). MXenes were prepared by etching Al from Ti{sub 3}AlC{sub 2} (MAX phase)material. Two etching techniques yield different MXene products: LiF/HCl: Milder reaction, larger MXene flakes. HF: Harsher reaction, smaller flakes, larger layer separation. Products washed to remove etchant, vacuum filtered, and dried. Dried MXene flakes are air-stable. Film preparation for sensor testing (at SRNL): Suspend powder in diH{sub 2}O, purge with Ar, sonicate for 30 min. Centrifuge and collect supernate with suspended particles. Observed LiF-etched Mxene yielded a higher density of particles and darker collected solution. Drop-cast (4 ml) supernate onto slides and dried with Ar. For Rhodamine B (RhB) testing, drop-cast 4 ml drops onto Mxene spots and dried with Ar. Scanning Electron Microscopy conditions: 10 kV Beam energy, high vacuum; Working distance of 8 mm; beam penetration depth appx. 4 microns, beam spot size appx. 2 nanometers. Results: Detection of aluminum correlates with bright spots on image. Presence of aluminum shows that LiF/HCl etching was less thorough than HF etching. Trace Cl detection in LiF images suggests incomplete rinsing. HF has smaller feature size, more layer structure, and increased homogeneity, consistent with expectations. Macroscopic Raman spectroscopy measurements: 532 nm excitation, ∼50 mW with a ∼100 micron spot size (InPhotonics RPB probe). Kaiser Optical Holospec f/1.8 spectrometer with cooled (-60 deg.C) Andor iDus OE420 CCD. LiF 1x supernate showed good signal for trace measurements of Rhodamine B. HF and 1/4x LiF supernates showed little Mxene or Rhodamine B signal. Low deposition densities led to excess background signal from glass slides. For LiF film, response is linear with Rhodamine B concentration over range tested. Will retest with Raman microscope (∼1 micron spot size) to characterize SERS of more dilute LiF and HF etched Mxenes. Conclusions: The LiF etched material was more suitable for macroscopic SERS measurements because it was more concentrated, resulting in a thicker film than the HF etched Mxene and diluted LiF sample. However, the other materials may give greater SERS enhancements, which we hope to determine from measurements with the Raman microscope. From characterization with SEM we concluded that the HF etched Mxene is more uniform/homogenous and has smaller particle size than the LiF etched Mxene. There is still aluminum present in both samples indicating that etching wasn't complete, but the removal of the aluminum was more efficient in the HF method. Path Forward: Observe SERS with Raman microscopy, to obtain better signals for the more diluted samples and be able to compare enhancement effects for the different MXenes. Characterize uranyl sorption into MXene films and test Raman and fluorescence signals. Revisit the etching conditions to improve removal of aluminum. FSU and SRNL will continue to collaborate to create and characterize different Mxene materials and test their usefulness for sensor applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗