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At least 577 records · Page 32

Open-Source Data Analysis Tool for Spectral Small-Angle X-ray Scattering Using Spectroscopic Photon-Counting Detector

Spectral small-angle X-ray scattering (sSAXS) is a powerful technique for material characterization from thicker samples by capturing elastic X-ray scattering data in angle- and energy-dispersive modes at small angles. This approach is enabled by the use of a 2D spectroscopic photon-counting detector that provides energy and position information of scattered photons when a sample is irradiated by a polychromatic X-ray beam. Here, we describe an open-source tool with a graphical interface for analyzing sSAXS data obtained from a 2D spectroscopic photon-counting detector with a large number of energy bins. The tool takes system geometry parameters and raw detector data to output 1D scattering patterns and a 2D spatially-resolved scattering map in the energy range of interest. We validated these features using data from samples of caffeine powder with well-known scattering peaks. This open-source tool will facilitate sSAXS data analysis for various material characterization applications.

Chemistry↗

Laser Powder Bed Fusion Additive Manufacture Nb1Zr Development

Next generation fission and fusion nuclear reactors require materials that can withstand operating temperatures greater than 500 °C, neutron irradiation doses of up to 200 displacements per atom (dpa), and potentially corrosive coolants such as the alkali liquid metals sodium, lithium, and NaK (Na33K eutectic alloy). Refractory alloys, such as Nb1Zr (Nb-1wt%Zr) and Molybdenum alloy TZM (Mo-0.5wt%Ti-0.08wt%Zr) have been traditionally considered viable candidates for advanced fission and fusion reactor concepts. However, it is relatively difficult to generate complex geometries of interest from these alloys using traditional manufacturing methods. In addition, there needs to be a concentrated effort to address refractory metal challenges at elevated temperature operation. In order to generate complex geometries of interest, modern manufacturing techniques are considered to increase the technological readiness level (TRL), cost-effectiveness, and schedule savings. This work focused on the continued development of laser powder bed fusion (L-PBF) additive manufacturing (AM) to improve both design flexibility, evaluate microstructure and properties, and ultimately accelerate the TRL and qualification of these processes and alloys for components to potentially be put into service. Niobium alloy Nb1Zr was identified through a down-selection process outlined in previous reports as a candidate to develop in L-PBF AM. Historically, Nb1Zr had been explored for high temperature fast spectrum fission reactors for both terrestrial and space applications. Molybdenum alloy TZM has also been considered for these reactor concepts due to exceptional high-temperature strength, creep resistance, and stability under irradiation. L-PBF AM of TZM has previously been investigated at LANL under the Microreactor program, NASA, ORNL, and in academia. However, due to the crack prone nature of TZM, L-PBF AM of TZM resulted in significant microcracking and additional development is required to pursue viable maturation. Other AM methods have been found to be more successful in printing TZM, and those alternatives approaches are discussed in this effort. The efforts detailed in this report focused on continued development of Nb1Zr through L-PBF and development of TZM via L-PBF and electron powder bed fusion (E-PBF). The objective of this work was to further the development of these AM techniques for the chosen refractory alloys, elucidating and addressing associated challenges through characterization of several demonstration builds. At LANL, Nb1Zr builds were completed using an EOS M290 and M400 machines, and a refractory alloy-dedicated L-PBF system, the Xact Metal XM200G, was installed. The XM200G primary purpose was to do the Nb1Zr parameter development process; however, due to difficulties associated with the machine installation and qualification process, it was decided to pivot development to the larger M400 and M290 machines. Although the supply of Nb1Zr powder was limited, it was sufficient to generate sub-scale metallographic specimens for the purpose of parameter development. This was first accomplished on the EOS M400 then the M290 due to machine schedule availability. Further development of TZM has been initiated at the University of Texas El Paso (UTEP) under contract with LANL to use both a heated build envelope L-PBF machine and E-PBF machine that have been found in the literature to mitigate microcracking. UTEP was provided with TZM powder and build plates to support parallel TZM parameter development across both machines. As part of the contract, UTEP will also be conducting microstructural characterization once optimized process parameters have been identified. The optimized process parameters for each machine will be used to generate a series of metallographic, mechanical, and surface finish specimens for subsequent characterization and testing. In the next section, we provide a detailed discussion of the methodology used for investigating the feasibility of leveraging these alloys for use in advanced reactor applications.

36 MATERIALS SCIENCE↗

Evaluation of In-Situ AM Process Monitoring Techniques and Potential for Detecting Process Anomalies and Undesirable Microstructures

The US Department of Energy’s Advanced Materials and Manufacturing Technologies (AMMT) program is pursuing rapid qualification of new materials for fabrication of nuclear relevant components using advanced manufacturing techniques. Particular interest is placed on code-qualifying stainless steel (SS) 316H processed by laser powder bed fusion (LPBF) additive manufacturing. A paradigm that incorporates data from in-situ sensing during the printing, ex-situ characterization, and advanced artificial intelligence–based models was established under the Transformation Challenge Reactor (TCR) program to develop a pedigree for each fabricated component that could be tracked from the feedstock to the component’s release for application. Under the TCR program, the Peregrine software was developed as a tool for incorporating the vast amounts of in-situ and ex-situ characterization data collected; all data stored on a rapidly growing digital platform. The digital platform allows for users to link site-specific process anomalies to the macro- and microstructure. The platform will eventually be able to predict component performance, which will be crucial to qualifying materials and components in risk-averse industries such as those supporting and building nuclear reactors. Current in-situ process monitoring techniques that are already integrated with software like Peregrine are advantageous for identifying process anomalies including powder spatter, component edge swelling, recoating-build interactions, and so on. However, additional data are required to fully predict the resulting microstructures needed for identifying relationships to component performance. The rapid cooling rates observed in LPBF are some of the highest of any bulk manufacturing process, resulting in heterogenous microstructures and typically causing anisotropy in mechanical properties. Moreover, evolved residual thermal stresses are high, which can cause severe defects such as delamination or cracking. Therefore, other in-situ monitoring methods are warranted for exploration to measure and map the thermal history, and potentially the stress state, of each build. This report summarizes different in-situ monitoring strategies proposed for LPBF with a focus on the more developed sensor systems. Novel capabilities for measuring melt pool temperatures are also addressed to better inform modeling efforts.

36 MATERIALS SCIENCE↗

Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites

Spinel iron oxide nanoparticles of different mean sizes in the range 10–25 nm have been prepared by surfactant-free up-scalable near- and super-critical hydrothermal synthesis pathways and characterized using a wide range of advanced structural characterization methods to provide a highly detailed structural description. The atomic structure is examined by combined Rietveld analysis of synchrotron powder X-ray diffraction (PXRD) data and time-of-flight neutron powder-diffraction (NPD) data. The local atomic ordering is further analysed by pair distribution function (PDF) analysis of both X-ray and neutron total-scattering data. It is observed that a non-stoichiometric structural model based on a tetragonal γ-Fe 2 O 3 phase with vacancy ordering in the structure (space group P 4 3 2 1 2) yields the best fit to the PXRD and total-scattering data. Detailed peak-profile analysis reveals a shorter coherence length for the superstructure, which may be attributed to the vacancy-ordered domains being smaller than the size of the crystallites and/or the presence of anti-phase boundaries, faulting or other disorder effects. The intermediate stoichiometry between that of γ-Fe 2 O 3 and Fe 3 O 4 is confirmed by refinement of the Fe/O stoichiometry in the scattering data and quantitative analysis of Mössbauer spectra. The structural characterization is complemented by nano/micro-structural analysis using transmission electron microscopy (TEM), elemental mapping using scanning TEM, energy-dispersive X-ray spectroscopy and the measurement of macroscopic magnetic properties using vibrating sample magnetometry. Notably, no evidence is found of a Fe 3 O 4 /γ-Fe 2 O 3 core-shell nanostructure being present, which had previously been suggested for non-stoichiometric spinel iron oxide nanoparticles. Finally, the study is concluded using the magnetic PDF (mPDF) method to model the neutron total-scattering data and determine the local magnetic ordering and magnetic domain sizes in the iron oxide nanoparticles. The mPDF data analysis reveals ferrimagnetic collinear ordering of the spins in the structure and the magnetic domain sizes to be ∼60–70% of the total nanoparticle sizes. The present study is the first in which mPDF analysis has been applied to magnetic nanoparticles, establishing a successful precedent for future studies of magnetic nanoparticles using this technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cold Testing for Characterization of Oxide Feed Impurities in Support of the ARIES Program

The Advanced Recovery and Integrated Extraction System (ARIES) Program converts surplus plutonium metal components into an oxide powder form and packages the material for final disposition. In support of the ARIES program, over a metric ton (MT) of plutonium has been removed from surplus nuclear weapons since 1998 and packaged for long-term storage in 3013 cans. The oxide production rate is anticipated to increase substantially over the next decade in support of dilute and dispose goals. Analytical chemistry data from destructive analysis of the resulting 70+ blend lots to date has been reported for contaminants in the product oxide. Changes in the Pu product specification for Pu oxide product, induced by a different pit mix, the LANL swap program and processing Alternate (non-Pit Pu) Feed Stock (AFS) metals, will affect the level and the mix of these contaminants in the upcoming years. With these changes in feed material, it will be important to provide fast and efficient measurement of elemental impurities in the oxide to be certain that the process is under control and to monitor the anticipated changes from the historical blend lot data. Non-destructive methods need to be evaluated for the characterization of the plutonium oxide product and the quantification of the impurities at the current and anticipated levels. A feasibility study has begun to investigate the applicability of new spectroscopic methods for oxide impurity characterization. To this end, here we describe the preparation of surrogate materials to support these investigations, and the results of a feasibility study investigating the use of LIBS (Laser Induced Breakdown Spectroscopy) to characterize the surrogate materials as calibration standards.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Localized orientation gradients in additively manufactured stainless steel 316H structures

The high solidification rates during additive manufacturing cause highly localized thermal and strain gradients. The effect of these gradients on the evolution of local orientation misorientations within a grain is not well understood. In this study, stainless steel 316H parts were fabricated via laser powder bed fusion using three different energy densities: 43, 71, and 135 J/mm 3 . Electron backscatter diffraction showed that the maximum misorientations of the grains can be up to 25° along the build direction. Misorientation gradients (RM g ) within grains are process-dependent and can change from 0.036°/μm to 0.015°/μm with increased volumetric energy densities. In conclusion, the characterized misorientation gradients are an indication of the level of dislocations and, to an extent, the plastic deformation resulting from the rapid solidification during laser powder bed fusion.

316H↗

GSAS-II (GENERAL STRUCTURE AND ALAYSIS SYSTEM-II)

GSAS-II is a comprehensive data analysis and simulation software package for determining atomistic structures from single-crystal and powder diffraction data. X-ray, neutron and electron data may be used. Constant-wavelength, time-of-flight and pink-beam sources may be employed and analyses may combine different types of data. The package is oriented towards materials characterization problems, but protein crystallography, pair-distribution function analysis, small-angle scattering and reflectometry analysis are all included. GSAS-II provides tools for indexing and solving structures from powder diffraction data, in addition to structure, data and results visualization tools

TOBY, BRIANH↗

On the thermal coarsening and transformation of nanoscale oxide inclusions in 316L stainless steel manufactured by laser powder bed fusion and its influence on impact toughness

The thermal evolution of nanoscale oxide inclusions in 316L stainless steel (SS) manufactured by laser powder bed fusion additive manufacturing (AM) was explored. The size, chemical composition, morphology, and distribution of the oxides were characterized as the function of heat treatment conditions. The study revealed the mechanistic driving force of the rapid oxide coarsening during recrystallization. Ostwald ripening governs oxide coarsening. The active grain boundary-oxide interaction at the early stage of recrystallization accelerated oxide coarsening via enhanced solute diffusion along grain boundaries. Pipe diffusion along dislocation cellular boundaries has a negligible contribution to oxide coarsening. At high temperatures (T> 1065 °C), although lattice diffusion primarily controlled the oxide growth, the contribution from the grain-boundary diffusion was necessary. The transformation from MnSiO 3 to CrMn 2 O 4 took place in the un-recrystallized grains but was not observed when recrystallization started. The interaction of grain boundary and oxides during recrystallization resulted in a high fraction of oxides accumulated at grain boundaries. While oxide coarsening does not significantly alter the toughness value, grain-boundary oxides promote microvoid formation and intergranular fracture under Charpy impact in the recrystallized AM 316L SS.

36 MATERIALS SCIENCE↗

Chloride Reduction of Mn 3+ in Mild Hydrothermal Synthesis of a Charge Ordered Defect Pyrochlore, CsMn 2+ Mn 3+ F 6 , a Canted Antiferromagnet with a Hard Ferromagnetic Component

Geometrically frustrated systems play an important role in studying new physical phenomena and unconventional thermodynamics. Charge ordered defect pyrochlores AM 2+ M 3+ F 6 offer a convenient platform for probing the interplay between electron distribution over M 2+ and M 3+ sites and structural distortions; however, they are limited to compounds with M 2+/3+ = V, Fe, Ni, and Cu due to difficulties in the simultaneous stabilization of other 3d elements in the +2 and +3 oxidation states. Herein, we employ Cl– anions under hydrothermal conditions for the mild reduction of Mn 2 O 3 in concentrated HF to obtain the CsMn 2+ Mn 3+ F 6 composition as a phase pure sample and study its properties. The magnetism of CsMn 2 F 6 was characterized by measuring the magnetic susceptibility and isothermal magnetization data, and a magnetic transition to a canted antiferromagnet state was found at 24.1 K. We determined the magnetic structure of CsMn 2 F 6 using powder neutron diffraction, which revealed successive long-range ordering of the Mn 2+ and Mn 3+ sites that is accompanied by a second transition. As a result, the role and strength of magnetic exchange interactions were characterized using DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid Additive Manufacturing and Electric Field-Assisted Sintering of High-temperature Heat Exchangers via Sacrificial Channel Molds

A hybrid manufacturing approach, integrating additive manufacturing (AM) with powder methodology via electric field-assisted sintering (EFAS), was developed for the fabrication of high-temperature compact heat exchangers (CHX) from refractory metals. The methodology employed additively manufactured sacrificial channel molds (SCMs) as shapeholders for CHX channels, which were embedded in metal powders using EFAS. Following embedding, the SCMs were chemically dissolved to form the internal channel network. SCMs were fabricated using both digital light processing (DLP) and direct ink writing (DIW) from chemically reactive, calcium-based ceramic feedstocks with varying ratios of Al2O3 reinforcement. The microstructure, phase composition, and dissolution behavior of both as-printed and embedded SCMs were investigated. The shrinkage behavior of the SCMs embedded in refractory metals, as well as the interfacial characteristics between the SCMs and metal matrix, were studied. The results showed that the SCMs containing sufficient chemical reactive ceramics dissolved effectively before and after embedding. The as-printed SCMs retained the phase composition of their feedstocks, but the embedded SCMs containing calcium-based ceramics and Al2O3 exhibited the formation of calcium aluminates due to high temperature exposure during embedding. Most SCMs exhibited a cellular Al2O3 network filled with Ca-rich ceramics. Shrinkage after embedding was strongly dependent on SCM density, with lower density SCMs exhibiting greater shrinkage. A thin SCM-affected zone was observed at the metal matrix surface, characterized by increased porosity compared to the bulk matrix. This effect was attributed to infiltration of the SCM materials into powder particle boundaries under pressure, followed by their removal during dissolution. This study demonstrates the feasibility of manufacturing CHXs from hard-to-process refractory metals for use in harsh environments.

36 - MATERIALS SCIENCE↗

Microstructure, fatigue, and impact toughness properties of additively manufactured nickel alloy 718

A complete understanding of processing-structure-property-performance relationship of additively manufactured (AM) components are critical from an application standpoint. Therefore, in the current investigation, a comprehensive microstructural characterization and mechanical properties (tensile, fatigue and impact toughness) evaluation of nickel alloy 718 AM by the laser powder bed fusion (L-PBF) technique have been performed. AM builds were made from powders manufactured via different atomization conditions. Although the standard post-heat treatment procedure led to the removal of severe interdendritic segregation both grain boundary and intra-grain precipitation of d phase occurred. Regardless of d phase presence, axial fatigue properties of both the AM builds were similar to design handbook wrought fatigue data. However, due to the d phase, impact toughness properties were comparable to the wrought material conditions that exhibited d phase. Fractured surfaces of Charpy impact samples exhibited crack propagation extensively along the boundaries decorated by d precipitates.

Komarasamy, Mageshwari↗

Carboxylic Group Rotation and Lattice Expansion in a Co 2 (Pyrazine-2,3-Dicarboxylate) 2 (4,4'-Bipyridine) Porous Coordination Polymer Induced by CO 2 Adsorption at Ambient Temperature

Here, a Co 2 (pzdc) 2 (bpy)(H 2 O) m (pzdc: pyrazine-2,3dicarboxylate; bpy: 4,4'-bipyridine) porous coordination polymer (PCP) was studied for CO 2 uptake and concomitant structural changes at ambient temperature. Extended structural characterization included evaluation of lattice parameter changes upon CO 2 adsorption and in situ synchrotron X-ray powder diffraction data. The PCP effective pore size increased by ~2% with gas uptake over the pressure range of 1-50 atm, allowing the adsorption capacity to double. Furthermore, the hysteretic behaviors seen during CO 2 adsorption at moderate pressures are commensurate with the structural changes from synchrotron data. The adsorption and hysteresis occur with rotation of the linking carboxylate groups, and yet only minor changes in unit cell volume (ΔV ≈ 6 Å 3 ) are observed. This contrasts the findings for [Cu 2 (pzdc) 2 (bpy)] n , where a combination of pillar bpy rotations and significant lattice expansion (ΔV ≈ 68 Å(3)) takes place upon hysteretic adsorption of CO 2 . In situ high-temperature X-ray diffraction revealed that the Co(II)-based material has good thermal stability up to ca. 200° C. Finally, the CO 2 uptake also appears to be at a physisorption level, with adsorbent-adsorbate interactions that are ca. 30% stronger than what has been reported for CO 2 adsorption onto [Cu 2 (pzdc) 2 (bpy)] n .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From Serendipity to Exploration: Synthesis and Properties of PtSiSb

PtSiSb is a compound with covalent Si–Sb bonds, which are relatively rare instances in solid-state materials. The original report on PtSiSb indicates synthetic challenges for the isolation of single-phase samples, as well as potential discrepancies in the predicted electronic structure and experimental transport properties. In this work, we considered PtSiSb as a case study with the objective of demonstrating the importance of synthesis as a bridge between theoretical predictions and experimental properties. Using guidance from in situ powder X-ray diffraction, the synthesis of single-phase polycrystalline samples was developed, allowing further experimental characterization of transport and catalytic properties. Thermal conductivity and heat capacity demonstrated anomalous behavior, indicating an unconventional phonon scattering mechanism in PtSiSb. Charge transport measurements indicated semimetallic behavior. Hydrogen evolution reaction (HER) tests in acidic electrolyte revealed that the PtSiSb cathode needs an overpotential η 10 = 120 mV to achieve a current density j = −10 mA/cm 2 . This is lower activity than elemental Pt but comparable to known and active transition-metal phosphide HER catalysts, such as CoP, with η 10 = 93 mV when measured at identical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A High-Speed Rotational Diamond Anvil Cell for In Situ Analysis of Hierarchical Microstructural Evolution of Metallic Alloys during Extreme Shear Deformation

High speed shear deformation is ubiquitous in engineering applications, ranging from material processing methods such as friction stir processing/extrusion and in tribological contacts. However, analyzing the microstructural evolution of materials while they are undergoing high speed shear deformation have been a long-standing challenge. This led to predominant reliance on ex situ microscopy before and after shear deformation. But ex situ microscopy lacks the ability to analyze dynamic and transient hierarchical microstructural evolution mechanisms that could occur during shear deformation of materials. Therefore, to better understand the dynamic mechanisms of mass and energy transfer in materials under shear deformation, we developed a first of its kind high-speed rotational diamond anvil cell (HS-RDAC) for synchrotron-based in situ high-energy x-ray diffraction (XRD). We studied the time resolved lattice strain evolution, XRD peak broadening and changes in spatial variation of shear deformation induced alloying in pure metal and metal alloy sheets and powder mixture using the HS-RDAC. These in situ results were combined with detailed ex situ microstructural characterization before and after the shear deformation using transmission electron microscopy and atom probe tomography, which revealed the different stages of evolution of a shear deformation induced hierarchical nanostructure. Multiscale computational simulations including computational fluid dynamics, crystal plasticity, molecular dynamic simulation and density functional theory uncovered the mechanisms behind morphological changes, evolution of defect structures and changes in driving force for shear deformation induced intermixing. In conclusion, this in situ HS-RDAC capability, in combination with ex situ microstructural characterization and computational simulations, can provide new insights into the hierarchical microstructural evolution pathway during shear deformation.

36 MATERIALS SCIENCE↗

Overview of NETL’s Low Temperature CO2 Electrolysis Research

This keynote lecture will briefly overview diverse research areas of National Energy Technology Laboratory (NETL) to advance energy and environmental sustainability along with carbon management. Our electrochemistry efforts on carbon conversion directly support the US goal of achieving carbon-free power sector by 2035 and net zero emissions by 2050. Since CO2 electroreduction is highly structure-sensitive, NETL ongoing research has been focused on the rational design and engineering of electrocatalysts to facilitate the CO2 conversion to desirable products with good selectivity, activity, and durability. Different classes and types of electrocatalytic materials will be covered in this talk, from well-defined atomic-scale model catalysts to heterogenous, scalable powder systems at nano- and micro-scale for “real world” performance evaluation. Several spectroscopic, microscopic, and electrochemical characterization techniques along with computational findings will be additionally discussed to gain more insights into the structure-activity relation. The last part of this seminar will provide more detail on how NETL has transitioned from the most common aqueous H-type reactor for lab-scale validation to more realistic full electrolyzer cell in bench-scale prototype. The knowledge, electrocatalytic materials, and device validation achieved from NETL in-house research will be translated to industrial sector for large scale deployment and the anticipated outcome will help advance the development of low temperature CO2 electrolysis technologies.

Nguyen Phan, Thuy Duong↗

Iodine Capture Studies of Copper- and Bismuth-Based Sorbents

The release of radioiodine, one of several radionuclides of concern when recycling used nuclear fuel (UNF), is an important consideration in the fuel cycle. In this study, two sorbent materials, Cu 0 -polyacrylonitrile (PAN) and Bi 0 -PAN, were tested as solid sorbent candidates for iodine capture. Experiments using a thin bed of sorbent material were exposed to vaporized iodine for over 300 hours (~2 weeks) under varied conditions in a dynamic flow environment. The overall performance was monitored in real-time using thermogravimetric analysis, and the materials were subsequently characterized for surface and bulk analysis using scanning electron microscopy – energy-dispersive spectroscopy (SEM-EDS) and powder x-ray diffraction (pXRD), respectively. Iodine (in the form of I 2 ) is expected to be released primarily in the dissolver off-gas (DOG) stream; therefore, this study demonstrates the effects of elemental iodine (I 2 ), water vapor (H 2 O), and nitrogen dioxide (NO 2 ). When exposed to ‘ideal’ conditions (in which I 2 is carried by dry air), Cu 0 -PAN and Bi 0 -PAN behave differently, with TGA analysis indicating that Cu 0 sorption performance is higher than that of Bi 0 , as evidenced by a larger mass change. Under ‘harsh’ conditions—such as a gaseous feed containing I 2 , H 2 O, and NO 2 vapors carried by air,—iodine capture performance for both Cu 0 - and Bi 0 -PAN are affected. SEM-EDS and pXRD analysis of these materials is discussed herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Zinc Oxide–Graphene Nanocomposite-Based Sensor for the Electrochemical Determination of Cetirizine

A nanocomposite electrode of graphene (Gr) and zinc oxide (ZnO) nanoparticles was fabricated to study the electrochemical oxidation behavior of an anti-inflammatory drug, i.e., cetirizine (CET). The voltametric response of CET for bare CPE, Gr/CPE, ZnO/CPE, and the ZnO-Gr nanocomposite electrode was studied. The modifier materials were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD) to comprehend the surface morphology of the utilized modifiers. The influence of pH, scan rate, and accumulation time on the electrooxidation of CET was examined. It was found that the electrochemical oxidation of CET was diffusion-controlled, in which two protons and two electrons participated. The detection limit was found to be 2.8 × 10 -8 M in a linearity range of 0.05–4.0 µM. Study of excipients was also performed, and it was found that they had negligible interference with the peak potential of CET. The validation and utility of the fabricated nanocomposite sensor material were examined by analyzing clinical and biological samples. Stability testing of the nanocomposite electrode was conducted to assess the reproducibility, determining that the developed biosensor has good stability and high efficiency in producing reproducible results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance of Polymer Electrolyte Membrane Water Electrolysis Systems: Configuration, Stack Materials, Turndown and Efficiency

A cell model is developed and validated to analyze the performance of polymer electrolyte membrane water electrolysis (PEMWE) stacks and systems. It is used to characterize the oxygen evolution reaction (OER) activity on a TiO2-supported IrO2 catalyst and an unsupported IrO2 powder catalyst. Electrochemical, stack, and system thermoneutral potentials are defined and determined for isothermal and non-isothermal stack operation. Conditions are determined under which the system thermoneutral potential or flammability of H2 in the O2 anode stream limits the stack turndown and operating temperature. Performance is analyzed of a complete PEMWE system with an electrolyzer stack containing an IrO2/TiO2 anode catalyst (2 mg/cm2 Ir loading) and N117-like membrane mitigated for H2 crossover, anode balance-of-plant (BOP) components, cathode BOP system with temperature swing adsorption for H2 purification, and electrical BOP system with transformer and rectifier. At the rated power condition, defined as 2 A/cm2 at 1.9 V, 80 °C, and 30 bar H2 pressure, the stack/system efficiency is 65.3%/60.3% at beginning of life (BOL), decreasing to 59.3%/53.9% at end of life (EOL). The peak stack/system efficiency is 76.3%/70.2% at BOL, decreasing to 71.2%/65.6% at EOL. Improvements in catalyst activity and membrane are identified for a 50% increase in current to 3 A/cm2 at 1.8 V.

36 MATERIALS SCIENCE↗