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At least 1,171 records · Page 65

Optical Properties of Semiconductor-Metal Composite Thin Films in the Infrared Region

Germanium:Silver (Ge:Ag) composite thin films having different concentrations of Ag, ranging from 7% to 40% have been prepared by dc co-sputtering of Ge an Ag and the films' surface morphology and optical properties have been characterized using transmission electron microscopy (TEM) and infrared spectrophotometry. It is seen that while the films containing lower concentrations of Ag have island-like morphology (i.e. Ag particles distributed in a Ge matrix), the higher metallic concentration films tend to have symmetric distribution of Ag and Ge.

Films Germanium Silver↗

Semiconductor- Metal Graded Index Composite Thin Films for Infrared Applications

Theoretical/experimental studies have been carried out on Germanium:Silver (Ge:Ag) graded index composite thin films, which demonstrate that graded coatings, consisting of varied concentrations of Ag with respect to the Ge film thickness, exhibit different optica properties ranging from selective infrared (IR) reflectance to broadband IR absorptance.

Inhomogeneous↗

DirectINJECT: Dosing Systems for Concentrated Liquid Biocides

Reliable and mass-efficient techniques for biocide dosing are necessary to enable residual microbial control in spacecraft potable water systems. DirectINJECT is an approach to provide ultra-low flow rate injection of stable aqueous biocide concentrate solution (e.g., highly soluble silver salt). This method has the benefit of low consumable mass and is insensitive to the chemistry of the target water. With a 40 g Ag+/liter solution, required dosing rates would be ~1 μl/minute during water processing (for a system similar to the ISS WPA), requiring only approximately 20 ml/crew-year of concentrate. The performance of three dosing systems were identified and characterized: pressure-driven flow through a robust micro-capillary tube with a solenoid valve shut-off, a miniature peristaltic pump, and a multi-piston pump with integrated valving. Several potential system reliability concerns are addressed including prevention or segregation of gas bubbles in the concentrate reservoirs as well as long-term materials compatibility and mechanical life.

silver↗

Development and characterization of the Capillary DirectINJECT System

The DirectINJECT Project was initiated to create a reliable in-line dosing system for delivering a concentrated silver ion biocide solution into spacecraft potable water. Three dosing systems, including a miniature peristaltic pump, a multi-piston pump, and a differential pressure-driven capillary tube, were quickly prototyped and tested. Although the peristaltic and multi-piston pump systems met the desired flow rate range, the capillary system showed the most promise and was chosen for further development. In FY23, the Capillary DirectINJECT dosing system underwent extensive testing with a nominal injection rate of 1.0 μl/min into varying backpressure conditions. A Primary DirectINJECT System with triplicate testbeds was employed for long-term testing, and auxiliary systems like the Secondary DirectINJECT System and Leak Testbed were developed to characterize specific components and investigate various phenomena related to the dosing system. Parameters such as flow rates, reservoir pressures, and temperature were monitored throughout the testing campaigns.

DirectINJECT↗

Bonded Interfaces for High-Temperature Power Electronics

Wide-bandgap devices have pushed the operational limit of semiconductor devices in automotive power electronics packages to higher temperatures (>200 degrees C). While a higher efficiency can be achieved through the use of wide-bandgap devices, the entire package must be re-designed with components that can withstand the higher temperature limits. Sintered silver and transient liquid phase bonds are potential candidates as bonded materials for use in higher temperatures however, the underlying mechanics of deformation under thermal loads and the resulting failure mechanisms in these materials are not well understood. Furthermore, thermomechanical modeling plays a key role in understanding the degradation behavior of bonded interface materials and for design optimization of power electronics packages.

ADVANCED PROPULSION SYSTEMS,DIRECT ENERGY CONVERSI↗

Investing in STEM Benefits Community, Company, and Industry - 20243

Like many organizations and groups, the Department of Energy Environmental Management program and the nuclear industry are facing an aging employee population and record numbers of employee retirements. This 'silver tsunami' of retirees means the industry as a whole is recruiting graduates at a fast pace. So, how do we ensure the nuclear industry has a robust pipeline of graduates with the necessary background? Fluor Idaho's investment in science, technology, engineering, and mathematics (STEM) education programs helps promote the next generation of technical professionals, benefiting both the company and the industry. Through community outreach initiatives and student mentoring programs, Fluor Idaho promotes kids' interest in STEM. The programs are designed to spark STEM interest in grade school and then foster and grow that interest through high school and higher education. After igniting student excitement about STEM topics in school, Fluor Idaho focuses on providing work-specific opportunities including mentoring and intern programs. These programs give students a better look at real-world job opportunities while still stimulating their interest in STEM. These programs ultimately provide career opportunities for the students and a pipeline of workers. Fluor Idaho's strategy for its summer interns has been to place students in a wide variety of projects - from the commissioning of a first-of-a-kind nuclear processing facility, to operating nuclear waste management facilities, to developing computer programs and applications - and give them responsibilities that make them feel like valued contributors. This approach has created a positive and rewarding summer-intern program experience for the students. Fluor Idaho's investment in its future today is reducing the knowledge gap - or cliff - that many contractors in the nuclear industry are facing. It's a worthwhile investment that is readily visible within its many cleanup projects. The next generation of technical professionals is making an impact now - benefiting both the company and the nuclear industry. This paper will review Fluor Idaho's programs, including STEM community outreach and education and mentoring programs. It will also present statistics about the reach of those programs and their successes. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Predicting Deposition Rate and Closing the Loop on Aerosol Jet Printing with In‐Line Light Scattering Measurements

Aerosol jet printing is a compelling noncontact, digital manufacturing technology for flexible, hybrid, and conformal electronics, but batch‐to‐batch variability and process drift inhibit systematic study and translation to production environments. Emerging measurement techniques for the aerosol volume fraction, a key parameter governing deposition rate, have shown promise for real‐time response, including a recent demonstration of human‐in‐the‐loop control. By integrating improved light scattering measurements with custom software, a robust environment for real‐time monitoring is established and fully automated closed‐loop control over the deposition rate during printing is enabled. The physical basis for scattering measurements as a feedback source is examined and the quantitative insight this provides for ink development and fundamental process studies is highlighted. Three candidate process variables for closed‐loop control, namely the atomizer voltage, carrier gas flow rate, and print speed, are then evaluated. The atomizer voltage demonstrates the best extended duration validity because it addresses atomization variability directly, but carrier gas flow rate and print speed provide faster and more deterministic responses. This methodology is then demonstrated for electrical properties using a silver nanoparticle ink, maintaining 98% of printed patterns within 10% of the mean resistance value over 3 h of printing.

36 MATERIALS SCIENCE↗

Highly Tunable Syngas Product Ratios Enabled by Novel Nanoscale Hybrid Electrolytes Designed for Combined CO 2 Capture and Electrochemical Conversion

Coupling renewable energy with the electrochemical conversion of CO 2 to chemicals and fuels has been proposed as a strategy to achieve a new circular carbon economy and help mitigate the effects of anthropogenic CO 2 emissions. Liquid-like Nanoparticle Organic Hybrid Materials (NOHMs) are composed of polymers tethered to nanoparticles and are previously explored as CO 2 capture materials and electrolyte additives. Here, in this study, two types of aqueous NOHM-based electrolytes are prepared to explore the effect of CO 2 binding energy (i.e., chemisorption versus physisorption) on CO 2 electroreduction over a silver nanoparticle catalyst for syngas production. Poly(ethylenimine) (PEI) and Jeffamine M2070 (HPE) are ionically tethered to SiO 2 nanoparticles to form the amine-containing NOHM-I-PEI and ether-containing NOHM-I-HPE, respectively. At less negative cathode potentials, PEI and NOHM-I-PEI-based electrolytes produce CO at higher rates than 0.1 molal. KHCO 3 due to favorable catalyst-electrolyte interactions. Whereas at more negative potentials, H 2 production is favored because of the carbamate electrochemical inactivity. Conversely, HPE and NOHM-I-HPE-based electrolytes display poor CO 2 reduction performance at less negative potentials. At more negative potentials, their performance approached that of 0.1 molal. KHCO 3 , highlighting how the polymer functional groups of NOHMs can be strategically selected to produce value-added products from CO 2 with highly tunable compositions.

36 MATERIALS SCIENCE↗

Trace-Level, Multi-Gas Detection for Food Quality Assessment Based on Decorated Silicon Transistor Arrays

Multiplexed gas detection at room temperature is critical for practical applications, such as for tracking the complex chemical environments associated with food decomposition and spoilage. Here, an integrated array of multiple silicon-based, chemical-sensitive field effect transistors (CSFETs) is presented to realize selective, sensitive, and simultaneous measurement of gases typically associated with food spoilage. CSFETs decorated with sensing materials based on ruthenium, silver, and silicon oxide are used to obtain stable room-temperature responses to ammonia (NH 3 ), hydrogen sulfide (H 2 S), and humidity, respectively. For example, one multi-CSFET sensor signal changes from its baseline by 13.34 in response to 1 ppm of NH 3 , 724.45 under 1 ppm H 2 S, and 23.46 under 80% relative humidity, with sensitive detection down to 10 ppb of NH 3 and H 2 S. To demonstrate this sensor for practical applications, the CSFET sensor array is combined with a custom-printed circuit board into a compact, fully integrated, and portable system to conduct real-time monitoring of gases generated by decomposing food. By using existing silicon-based manufacturing methodologies, this room-temperature gas sensing array can be fabricated reproducibly and at low cost, making it an attractive platform for ambient gas measurement needed in food safety applications.

36 MATERIALS SCIENCE↗

Reconfigurable Electrical Networks within a Conductive Hydrogel Composite

Soft materials that exhibit compliance, programmability, and reconfigurability can have a transformative impact as electronic skin for applications in wearable electronics/soft robotics. There has been significant progress in soft conductive materials; however, achieving electrically controlled and reversible changes in conductivity and circuit connectivity remains challenging. To overcome this limitation, a soft material architecture with reconfigurable conductive networks of silver flakes embedded within a hydrogel matrix is presented. The conductive networks can be reversibly created/disconnected through various stimuli, including current, humidity, or temperature. Such stimuli affect electrical connectivity of the hydrogel by controlling its water content, which can be modulated by evaporation under ambient conditions (passive dehydration), evaporation through electrical Joule heating (active dehydration), or absorption of additional water (rehydration). The resulting change in electrical conductivity is reversible and repeatable, endowing the composite with on-demand reconfigurable conductivity. To highlight this material's unique properties, it is shown that conductive traces can be reconfigured after severe damage and revert to lower conductivity after rehydration. Additionally, a quadruped robot is demonstrated that can respond to stimuli by changing direction following exposure to excess water, thereby achieving reprogrammable locomotion behaviors.

36 MATERIALS SCIENCE↗

Transparent and Conductive Inorganic/Polymer‐Composite Encapsulants for Long‐Term Perovskite Solar Cells Operation

An innovative inorganic/polymer-composite encapsulation scheme comprising a polymer-based transparent conductive composite (TCC) coupled with a transparent conductive oxide is introduced to extend the lifetime of moisture-sensitive devices such as perovskite solar cells (PSC). The TCC comprises conductive silver-coated polymethyl methacrylate (Ag-PMMA) microsphere fillers protruding from a transparent non-conductive polymer matrix. TCC samples (5% Ag-PMMA by area) demonstrate high optical transparencies (%T approx. 85% in the 370–1200 nm region), low out-of-plane electrical resistivities (R < 0.2 Ω cm 2 ), and equilibrium permeabilities of less than 1 g mm/m 2 /day, all of which are well-maintained after 1,000 hours of environmental exposure. In practice, the TCC is employed between two indium zinc oxide (IZO) thin films, with the in-plane conductivity of IZO and the out-of-plane conductivity of TCC working collectively to function as a single encapsulating electrode. This encapsulation scheme is exemplified by benchmarking performances of PSCs subjected to accelerated aging conditions of quasi-maximum power point tracking under light soaking in air at 50 °C, 40% R.H. to 60% R.H. Notable improvements in operational lifetimes are observed, with a champion encapsulated PSC maintaining over 90% of its initial efficiency of 21.65% for up to 1,430 hours, compare to less than 300 hours for an unencapsulated control.

14 SOLAR ENERGY↗

Crossing the Oxo‐Peroxo Wall for Selective Electrochemical Epoxidation

Electrochemical oxidation in water requires the formation of reactive oxygen species to be able to oxidize unsaturated hydrocarbons to epoxides, aldehydes, and ketones. These reactions, broadly classified as alternative oxidation reactions (AOR), directly compete with the prevalent oxygen evolution reaction (OER). In molecular catalysis, the Oxo-Wall dictates a transition from a stable oxo intermediate (OER active) to a meta-stable metal-oxo (OER inactive) generally occurs. In this work on heterogeneous catalysis, the same Oxo-Wall applies, however, a meta-stable oxo preferentially coordinates with lattice oxygen to form a more stable surface peroxo intermediate. A universal free energy onset of this process is identified at 3.39 eV under electrochemical activation in water and show that it is completely decoupled from the OER oxo species. Such decoupling gives rise to a new region of oxygen reactivity relevant for AOR where a selective oxidation of the unsaturated C-C bonds is predicted to occur instead of OER. A distinct AOR overpotential volcano is constructed and identify recently reported electrocatalysts, including palladium-platinum for propylene epoxidation and silver-nickel for ethylene epoxidation, along with others such as TiO 2 and CuO. Broader implications and limitations of electrochemical AOR are discussed, highlighting their potential to enable electrochemically enhanced thermal catalysis.

Electrocatalysis↗

Structural Tuning of Self‐Conductive Polymer as Gas Diffusion Layer for Electrocatalytic Reactions at High Current

Electrocatalytic conversions offer a promising route for sustainable chemical production using renewable energy. Gas diffusion layers (GDLs) enable selective product formation at high current densities but suffer from electrolyte flooding, and polytetrafluoroethylene (PTFE)-based GDLs typically require metal conductive layers, which constrain catalyst development. A recently developed GDL configuration, electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT)-coated PTFE, demonstrates notable flooding resistance, but suffers from gas diffusion limitations at elevated currents due to limited gas diffusion through the PEDOT layer. Here, different dopants in PEDOT are exploited to modify the physical properties and enhance gas transport. ClO 4 − -doped PEDOT exhibits superior performance due to optimized physical structure, leading to increased gas permeance and faradaic efficiency (FE) for CO production during electrocatalytic CO 2 reduction. Further optimization of coverage and thickness achieved by adjusting charge density led to an optimal configuration at 33 mC cm −2 . This GDL supports various metal electrocatalysts and demonstrates FE CO of > 90% for over 150 h at −200 mA cm −2 using a commercial silver electrocatalyst. This work highlights the importance of GDL engineering in enhancing performance and durability for long-term electrocatalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes

Abstract Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H 2 and CO 2 .

Desnoyer, Addison N.↗

A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes

Abstract Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H 2 and CO 2 .

Desnoyer, Addison N.↗

Modeling Planar Electrodes and Zero–Gap Membrane Electrode Assemblies for CO 2 Electrolysis

Multiphysics modeling enables probing of conditions inside a CO 2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one-dimensional model for a zero-gap membrane electrode assembly (MEA) CO 2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO 3 concentration.

30 DIRECT ENERGY CONVERSION↗