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New Pathways and Metrics for Enhanced, Reversible Hydrogen Storage in Boron-Doped Carbon Nanospaces

This project, since its start in 2007—entitled “Networks of boron-doped carbon nanopores for low-pressure reversible hydrogen storage” (2007-10) and “New pathways and metrics for enhanced, reversible hydrogen storage in boron-doped carbon nanospaces” (2010-13)—is in support of the DOE's National Hydrogen Storage Project, as part of the DOE Hydrogen and Fuel Cells Program’s comprehensive efforts to enable the widespread commercialization of hydrogen and fuel cell technologies in diverse sectors of the economy. Hydrogen storage is widely recognized as a critical enabling technology for the successful commercialization and market acceptance of hydrogen powered vehicles. Storing sufficient hydrogen on board a wide range of vehicle platforms, at energy densities comparable to gasoline, without compromising passenger or cargo space, remains an outstanding technical challenge. Of the main three thrust areas in 2007—metal hydrides, chemical hydrogen storage, and sorption-based hydrogen storage—sorption-based storage, i.e., storage of molecular hydrogen by adsorption on high-surface-area materials (carbons, metal-organic frameworks, and other porous organic networks), has emerged as the most promising path toward achieving the 2017 DOE storage targets of 0.055 kg H2/kg system (“5.5 wt%”) and 0.040 kg H2/liter system.

08 HYDROGEN↗

Effects of Water Vapor on the Reactivity of Aluminosilicates in Vapor-Phase Propanal Aldol Condensation

Aluminosilicate materials have been extensively studied as efficient aldol catalysts for C-C coupling reactions due to their acidic nature, high surface area, thermal stability, and porous structure. This work investigated the impact of water vapor pressure on the catalytic reactivity of aluminosilicates for the aldol condensation of propanal to 2-methyl-2-pentenal (MP). The catalytic performance of amorphous SiO2-Al2O3 (A-Si-Al) and aluminated MCM-41 (Al-MCM-41) for the vapor-phase aldol condensation of propanal was evaluated at 200 degrees C as a function of vapor-phase water content at atmospheric pressure. Our findings demonstrate that co-feeding low water vapor pressures (1-18 kPa) with propanal enhances the rates of MP production at 200 degrees C on A-Si-Al. Conversely, water vapor pressures of 25 kPa result in a decrease in aldol dimer formation rates. The rate of MP production evaluated on Al-MCM-41 also increased in the presence of 5 kPa water compared to anhydrous conditions. Propylamine temperature-programmed desorption analyses revealed an increase in Bronsted acid site density when both catalysts were exposed to water, which likely accounts for the observed enhancement in aldol condensation reactivity under hydrous conditions. Reversibility testing of the water vapor effect under reaction conditions, combined with X-ray diffraction analysis of fresh, spent, and regenerated catalysts, revealed no structural changes in either aluminosilicate upon exposure to water or reaction conditions. The rates of aldol condensation and the impact of water vapor were highly consistent across both materials, suggesting that zeolite crystallinity has minimal influence on the catalytic performance.

acid catalysts↗

Towards reverse mode automatic differentiation of Kokkos-based codes

Derivative computation is a key component of optimization, sensitivity analysis, uncertainty quantification, and the solving of nonlinear problems. Automatic differentiation (AD) is a powerful technique for evaluating such derivatives, and in recent years, has been integrated into programming environments such as Jax, PyTorch, and TensorFlow to support derivative computations needed for training of machine learning models, facilitating wide-spread use of these technologies. The C++ language has become the de facto standard for scientific computing due to numerous factors, yet language complexity has made the wide-spread adoption of AD technologies for C++ difficult, hampering the incorporation of powerful differentiable programming approaches into C++ scientific simulations. This is exacerbated by the increasing emergence of architectures, such as GPUs, with limited memory capabilities and requiring massive thread-level concurrency. C++ AD tools must effectively use these environments to bring novel scientific simulations to next-generation DOE experimental and observational facilities. In this project, we investigated source transformation-based automatic differentiation using LLVM compiler infrastructure to automatically generate portable and efficient gradient computations of Kokkos-based code. We have demonstrated that our proposed strategy is feasible by investigating the usage of a prototype LLVM-based source transformation tool to generate gradients of simple functions made of sequences of simple Kokkos parallel regions. Speedups of up to 500x compared to Sacado were observed on NVIDIA V100 GPU.

97 MATHEMATICS AND COMPUTING↗

Assessing Energy Infrastructure Devices for Vulnerabilities

Industrial control systems prove to be vital to the health and security of the nation in our critical infrastructure. Critical infrastructure includes the most foundational systems to support modern civilization which includes water and wastewater systems, communications, and the electricity we use to name a few sectors. However, these devices' overall composition remains largely unknown and are untested from a cyber security perspective. As part of the Cyber Testing for Resilient Industrial Control Systems (CyTRICS) program, I analyzed one such energy infrastructure device to better understand how it functions, what hardware and software components are present within it, and assess it for security vulnerabilities. To achieve this, I reverse engineered binary files using Ghidra to understand system functionality and learned more about how to collaborate with other researchers on a shared Ghidra project. I learned more about how web sockets function and how to interact with them through Python to test if they are secure or not. This work led me to assess possible vulnerabilities in this device and provide a better understanding of its composition and function, which are essential to INL's mission of securing our nation's energy infrastructure.

99 - GENERAL AND MISCELLANEOUS↗

REBOUND: Reverse Engineering Bidirectional Outflow Under Non-Equilibrium Diffusion

Rare-earth elements (REEs) are essential for electronics, renewable energy, and defense technologies. However, the current supply of REEs relies on mining concentrated in a few countries and energy-intensive separations. DOE’s Basic Energy Sciences (BES) program has launched a grand challenge which aims to ensure a sustainable supply of critical REEs by developing innovative and environmentally friendly separation methods. As an alternative to costly and harmful traditional methods, the Non-Equilibrium Transport Driven Separations (NETS) initiative has created a microfluidic Y-channel co-flow method that applies external fields to exploit magneto- and electrohydrodynamic effects for separating dilute REE ions from complex feedstocks. Computational fluid dynamics (CFD) studies have identified a few operating conditions with promising ion selectivity and separation efficiency. However, challenges remain regarding Y-channel versatility across feedstocks and accurate incorporation of physical phenomena into CFD models. In this work, we develop a multi-fidelity modelling approach which integrates experimental results with CFD simulation to build a surrogate model for the dependence of separation efficiency to variation of design parameters. The surrogate model enables a reinforcement learning (RL) method to adaptively launch CFD and experimental runs, improving model fidelity around optimal Y-channel parameters.

36 MATERIALS SCIENCE↗

MRP3 is a sex determining gene in the diatom Pseudo-nitzschia multistriata

A broad diversity of sex-determining systems has evolved in eukaryotes. However, information on the mechanisms of sex determination for unicellular microalgae is limited, including for diatoms, key-players of ocean food webs. Here we report the identification of a mating type (MT) determining gene for the diatom Pseudo-nitzschia multistriata . By comparing the expression profile of the two MTs, we find five MT-biased genes, of which one, MRP3 , is expressed exclusively in MT+ strains in a monoallelic manner. A short tandem repeat of specific length in the region upstream of MRP3 is consistently present in MT+ and absent in MT– strains. MRP3 overexpression in an MT– strain induces sex reversal: the transgenic MT– can mate with another MT– strain and displays altered regulation of the other MT-biased genes, indicating that they lie downstream. Our data show that a relatively simple genetic program is involved in defining the MT in P. multistriata.

59 BASIC BIOLOGICAL SCIENCES↗

The Princeton Field-Reversed Configuration for Compact Nuclear Fusion Power Plants

The Princeton Field-Reversed Configuration (PFRC) nuclear fusion reactor concept is an innovative approach to fusion power generation prioritizing low neutron production and small size. Here, a combination of analytical modeling and numerical simulation shows that the novel heating approach generates an FRC with closed field lines. Simulation data from a single-particle Hamiltonian code predicts ms-scale plasma heating in reactor-scale conditions while PIC codes predict formation of warm FRC plasmas from initial mirror fields. The PFRC-1 and PFRC-2 experiments have heated electrons to energies well in excess of 100 eV and plasma durations to 300 ms, more than 10 4 times longer than the predicted tilt instability growth time. From these data, we have created a development plan and anticipated performance metrics for a fusion reactor based on the PFRC concept. The resulting 1–10 MW PFRC reactors would be suitable for diverse applications, from submarines to urban environments to space propulsion. PFRC is a steady-state, driven magnetic confinement device. Plasma, inside a cylindrical array of coils, is confined and heated by external RF antennae. PFRC would be ultra-low radiation due to both its fuel and small size. The choice of advanced fuels, deuterium and helium-3 (D– 3 He), may be enabled by the high-β FRC configuration. The small size of the reactor would enable rapid exhaust of the dangerous tritium ash. Low radiation would make the reactor safer to operate and, in combination with simple geometry and small size, dramatically lowers development and maintenance costs. This review paper gives an introduction to the physics of the PFRC and a summary of the PFRC-2 experiment results to date. It then discusses the future program plan and how PFRC reactors would be commercialized.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Prefabricated High-Strength Rebar Systems with High-Performance Concrete for Accelerated Construction of Nuclear Concrete Structures

This project aimed to reduce the field construction times and fabrication costs of reinforced concrete (RC) nuclear structures through the use of: 1) high-strength steel deformed reinforcing bar (rebar); 2) prefabricated high-strength rebar (HSR) assemblies with headed anchorages; and 3) high-strength concrete (HSC). The focus of the project was not to develop new innovations on materials, but rather to fill a major knowledge gap on the effectiveness, code conformity, and viability (i.e., practicality, commercial availability) of existing high-strength materials in nuclear structures, especially in shear walls, their connections/joints, and around penetrations. These advances promote the Nuclear Energy Enabling Technologies Advanced Methods for Manufacturing (NEET-1) goals of accelerating deployment schedules by at least 6 months and reducing component fabrication costs by 20% or more. Toward this vision, the following objectives were identified and completed: Develop limit-benefit and cost-benefit analysis frameworks: The structural and economic limits and benefits of HSR and HSC in nuclear walls were evaluated. Importantly, it was found that modest increases in concrete strength up to 10.0 ksi and rebar yield strength up to 100 ksi result in the most economic designs and improved structural performance (Barbachyn et al., 2017a and Barbachyn et al., 2017b). Also, an industry survey was distributed to determine the cost benefits associated with prefabrication. Importantly, on-site worker-hours are significantly reduced, allowing for significantly accelerated construction schedules (Devine et al. 2018b). Develop an optimization methodology for structural design: An optimization study was deemed not necessary since the trivial solution with maximized use of high-strength materials and prefabrication always resulted in the largest cost and time savings. Instead, the benefits (and limits) of high-strength materials and prefabrication on construction costs and on-site construction time were investigated through a parametric study. Cost-reductions through the use of HSR and HSC were found to be greater than 40%. Also, on-site construction time of nuclear shear walls can be reduced by up to 83% through the use of prefabricated rebar assemblies. Conduct experimental evaluations of nuclear shear walls and wall-foundation joints: A large scale experimental program was completed on shear-critical RC cantilever deep beams. From these experiments, it was demonstrated that increasing rebar yield strength had a greater effect on increasing lateral strength than increasing the concrete compressive strength. Further, using HSR together with HSC resulted in the highest lateral strength and displacement ductility (Devine et al. 2018a). Additionally, large-scale reversed-cyclic lateral load tests were conducted on RC shear walls. It was demonstrated that through the utilization of HSR and HSC, a wall with 55% reduced vertical and horizontal rebar area was able to achieve 91% of the peak lateral strength of a conventional wall using state-of-practice materials with the same geometry. Further, trim reinforcement with headed anchorages around the penetrations proved to be effective. Develop validated numerical simulation models: Numerical modeling was completed in two phases during this project using 3 different finite element software packages. The first phase used existing measured data from previous experimental studies on stocky RC walls to validate simplified predictive models. Models using two different programs were validated based on a database of 38 stocky walls (Barbachyn et al., 2017a). The second phase occurred after experimental testing using a third and more detailed finite element package. Prediction improvements for the initial stiffness, lateral deformations, damage propagation, and failure mechanisms were targeted. The resulting detailed models more accurately predicted the peak lateral strength, initial and secant stiffnesses, lateral deformations, and cracking patterns of the wall test specimens subjected to reversed-cyclic lateral loading as compared to the simplified pretest models. Develop validated design procedures, tools, and criteria: This project evaluated the accuracy of existing closed-form design equations from U.S. building design standards and previous research (Barbachyn et al. 2017a and Devine et al. 2018a). It was shown that the current predictive equations for shear strength capacity need to be revisited as they provide significant scatter and gross overestimates, indicating the potential for unconservative designs. Further, for both the deep beam and shear wall specimens, the numerical models and flexural capacity predictions provided the most accurate strength predictions. Develop cost-effective field construction procedures: To promote the use of prefabricated rebar assemblies, the following construction conditions where prefabrication would be used instead of in-place rebar tying were identified from an industry survey: 1) to save on construction schedule; 2) to improve safety and/or quality control; 3) for areas with heavy rebar congestion; and 4) for structures with significant repetition in rebar layout. All of these conditions directly apply and benefit nuclear construction where construction costs and schedules are extensive, safety and quality are of utmost importance, the reinforcement is extremely dense, and the reinforcement layout is repetitive in many regions of the shear walls. Additionally, an experimental study was conducted to investigate the changes in bar spacing (with respect to code-required rebar spacing and placement tolerances) when a horizontally assembled prefabricated two-dimensional (2D) rebar mat or three-dimensional (3D) rebar cage is lifted (or tripped) to a vertical position. It was found that the bars involved in both the lateral translation of the rebar assemblies (i.e., movement of the assembly in its horizontal position) and the tripping process were most susceptible to large spacing changes, and thus, their positions within the assembly would need to be checked after the placement of the assembly in place within the formwork. Importantly, the spacings of all of the other bars in the assembly were not affected significantly by the lateral translation and tripping process, thereby eliminating the need to recheck their positions within the assembly (Devine et al. 2018b).

36 MATERIALS SCIENCE↗

Measurement of Magnetic Field using Doppler-Free Saturation Spectroscopy (DFSS) in C-2W FRC Plasma

The Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and TAE Technologies (TAE) focused on implementing an existing mobile Doppler-free saturation spectroscopy (DFSS) diagnostic to determine the direction of the equilibrium magnetic field within TAE’s C-2W field-reversed configuration (FRC) fusion device. Non-perturbative measurements of magnetic fields in the core of FRCs can provide critical information needed to constrain equilibrium models and for the continued advancement of the fusion research program at TAE. DFSS is a well-established, laser-based absorption spectroscopy technique used to suppress inhomogeneous (Doppler) broadening and reveal the Zeeman fine structure of the target emission lines. The collaboration involved the use of ORNL’s recently constructed mobile DFSS diagnostic. The DFSS diagnostic was shipped and installed on C- 2W in February 2023. TAE’s expertise was used to design and construct the mechanic support structures required to mount the optical hardware on C-2W. Additionally TAE provide critical input to minimize the noise imposed on the DFSS signal by vibrations of the mechanic support structure during operations. DFSS data was obtained for over 500 C-2W shots and will continue until the expiration of this CRADA on September 30 th 2023. Over the course of this work, significant progress was made to maximize the signal to noise (SNR) ratio. Analysis of recently acquired data is on-going, however, initial indications are highly suggestive that a DFSS signal above background has been successfully acquired in C-2W.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Multifunctional Catalysts to Synthesize and Utilize Energy Carriers

The central role and critical importance of catalysis in a future based on sustainability, together with the insight that developments have to be knowledge-based have motivated significant efforts to better understand catalyzed processes and to develop new catalytic routes from this knowledge. Overall, three main energy carriers are used worldwide, carbon (and hydrocarbons), hydrogen, and electrons. Conventionally, the stored energy is accessed by oxidizing carbon and hydrogen, forming O-H and C-O bonds and performing work with the produced heat or electricity. Conversely, to synthesize energy carriers sustainably, it is consequently required to reverse the direction, i.e., to break C-O and O-H bonds and form C-C, C-H and H-H bonds. To address these challenges, PNNL’s BES-sponsored program comprises three thrust areas with subtasks, focusing on the fundamentals of biomass conversion processes, direct and indirect CO2 reduction, and on elementary studies aimed at generating and using H2. Multi-functionality, i.e., the simultaneous interaction of more than one catalytically active site with the substrate is the key to achieving the atom and energy efficiency in individual steps. The combination of several types of these sites with carefully selected energetics and rate constants is used to generate complex catalysts able to enhance the rates of multistep processes. This short report summarizes recent results obtained in this BES-funded program.

Environmental Molecular Sciences Laboratory↗

POSTER: Automatic Differentiation of Parallel Loops with Formal Methods

The accompanying poster to this short paper presents a combination of reverse mode AD and formal methods to enable efficient differentiation of (or backpropagation through) shared-memory parallel code. Compared to the state of the art, our approach can more often avoid the need for atomic updates or private data copies during the parallel derivative computation, even in the presence of unstructured or data-dependent data access patterns. This is achieved by gathering information about the memory access patterns from the input program, which is assumed to be correctly parallelized. This information is then used to build a model of assertions in a theorem prover, which can be used to check the safety of shared memory accesses during the parallel derivative computation

Automatic Differentiation↗

Practical Implementation of Failure Mode and Effects Analysis for Safety and Efficiency in Stereotactic Radiosurgery

Purpose: To improve the safety and efficiency of a new stereotactic radiosurgery program with the application of failure mode and effects analysis (FMEA) performed by a multidisciplinary team of health care professionals. Methods and Materials: Representatives included physicists, therapists, dosimetrists, oncologists, and administrators. A detailed process tree was created from an initial high-level process tree to facilitate the identification of possible failure modes. Group members were asked to determine failure modes that they considered to be the highest risk before scoring failure modes. Risk priority numbers (RPNs) were determined by each group member individually and then averaged. Results: A total of 99 failure modes were identified. The 5 failure modes with an RPN above 150 were further analyzed to attempt to reduce these RPNs. Only 1 of the initial items that the group presumed to be high-risk (magnetic resonance imaging laterality reversed) was ranked in these top 5 items. New process controls were put in place to reduce the severity, occurrence, and detectability scores for all of the top 5 failure modes. Conclusions: FMEA is a valuable team activity that can assist in the creation or restructuring of a quality assurance program with the aim of improved safety, quality, and efficiency. Performing the FMEA helped group members to see how they fit into the bigger picture of the program, and it served to reduce biases and preconceived notions about which elements of the program were the riskiest.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Formation and sustainment of field reversed configuration (FRC) plasmas by spheromak merging and neutral beam injection

This paper briefly reviews a compact toroid reactor concept that addresses critical issues for forming, stabilizing and sustaining a field reversed configuration (FRC) with the use of plasma merging, plasma shaping, conducting shells, neutral beam injection (NBI). In this concept, an FRC plasma is generated by the merging of counter-helicity spheromaks produced by inductive discharges and sustained by the use of neutral beam injection (NBI). Plasma shaping, conducting shells, and the NBI would provide stabilization to global MHD modes. Although a specific FRC reactor design is outside the scope of the present paper, an example of a promising FRC reactor program is summarized based on the previously developed SPIRIT (Self-organized Plasmas by Induction, Reconnection and Injection Techniques) concept in order to connect this concept to the recently achieved the High Performance FRC plasmas obtained by Tri Alpha Energy [Binderbauer et al, Phys. Plasmas 22,056110, (2015)]. This paper includes a brief summary of the previous concept paper by M. Yamada et al, Plasma Fusion Res. 2, 004 (2007) and the recent experimental results from MRX.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Doppler-Free Saturation Spectroscopy (DFSS) for Magnetic and Electric Field Measurements in an FRC plasma

The Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and TAE Technologies (TAE) focused on a feasibility study of Doppler-free saturation spectroscopy (DFSS) as a diagnostic strategy to measure the internal magnetic and electric fields of TAE’s C-2W field-reversed configuration (FRC) fusion device. Non-perturbative measurements of magnetic and electric fields in the core of FRCs can provide critical information needed to constrain equilibrium models and for the continued advancement of the fusion research program at TAE. DFSS is a well-established, laser-based absorption spectroscopy technique used to suppress inhomogeneous (Doppler) broadening linewidths and reveal Zeeman/Stark split hyperfine structures of target emission lines. The collaboration involved the use of ORNL’s suite of experimentally validated quantum mechanical modelling codes to simulate theoretical atomic spectra for a variety of machine parameters and laser beam configurations. TAE’s expertise was heavily used to provide measurements/models of the required machine parameters needed as inputs to the simulations. Results of an all-encompassing error analysis demonstrate the favourable capabilities of the diagnostic and provided invaluable insights as to how DFSS can be best used to accurately measure internal B/E-fields in C-2W.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Design, characterization and shape recovery behavior of 3D/4D printed shape memory polymers (SMPs)

Shape memory polymers (SMPs) represent a paradigm shift in material science, uniquely capable of undergoing reversible shape transformations triggered by external stimuli, positioning them as pivotal in developing next-generation biomedical devices, aerospace components, and adaptive structures. Extensive research has been done on SMPs with a major focus on high-temperature programming methods, which can limit energy efficiency and applicability with temperature-sensitive materials. Additionally, while various SMP blends have demonstrated great potential, limited work has been done on the suitability for 3D printing these materials, particularly under high-strain and ambient temperature programming conditions. In this study, a three-component optimized SMP composition was evaluated by 3D printing via the Material Extrusion (MEX) technique and investigating its ambient temperature-programming behavior at high strains. The SMP formulation studied was a tailored blend of thermoplastic polyurethane (TPU), polycaprolactone (PCL), and an octadecane diol-based copolymer (OBC) that exhibits robust shape memory behavior, high strain tolerance, and efficient force generation. Rigorous thermal, mechanical, and shape recovery analyses, along with optimized printing parameters and consistent shape recovery rates of up to 90%, were achieved under dynamic mechanical analysis (DMA), even under ambient programming conditions. This work demonstrates the SMP composition’s potential for adaptive, self-deployable systems with 4D printing characteristics ideal for bio-inspired structures and artificial muscle fibers.

Sudan, Kavish [University of Louisville, KY]↗

Qualitative and quantitative enhancement of parameter estimation for model-based diagnostics using automatic differentiation with an application to inertial fusion

Parameter estimation using observables is a fundamental concept in the experimental sciences. Mathematical models that represent the physical processes can enable reconstructions of the experimental observables and greatly assist in parameter estimation by turning it into an optimization problem which can be solved by gradient-free or gradient-based methods. In this work, the recent rise in flexible frameworks for developing differentiable scientific computing programs is leveraged in order to dramatically accelerate data analysis of a common experimental diagnostic relevant to laser–plasma and inertial fusion experiments, Thomson scattering. A differentiable Thomson-scattering data analysis tool is developed that uses reverse-mode automatic differentiation (AD) to calculate gradients. By switching from finite differencing to reverse-mode AD, three distinct outcomes are achieved. First, gradient descent is accelerated dramatically to the extent that it enables near real-time usage in laser–plasma experiments. Second, qualitatively novel quantities which require $\mathcal{O}(10^3)$ parameters can now be included in the analysis of data which enables unprecedented measurements of small-scale laser–plasma phenomena. Third, uncertainty estimation approaches that leverage the value of the Hessian become accurate and efficient because reverse-mode AD can be used for calculating the Hessian.

97 MATHEMATICS AND COMPUTING↗

DEVELOPMENT OF INEXPENSIVE HIGH TEMPERATURE NITI-BASED SHAPE MEMORY ALLOYS FOR POWDER BED ADDITIVE MANUFACTURING

NiTi and NiTi-based Shape Memory Alloys (SMA) exhibit a reversible solid-state phase transformation from martensite to austenite driven by thermal energy. High temperature (Mf>100°C) SMAs are martensite at room temperature and can be fabricated into solid-state actuators that return to a pre-programmed shape against a designed load after heating to transformation threshold. Reactive as-fabricated additively manufactured parts (4-D printing) is the current state of the art in manufacturing of SMAs but requires compositions compliant to rapid solidification. Existing actuator designs are developed from commercially available, highly investigated material compositions. However, existing high temperature high performance (high actuation strain, low thermal hysteresis) shape memory alloys contain significant (>10% at.) portions of high-cost Platinum Group Metals (PGMs). It is of significant scientific interest to investigate material compositions that are peer performing or superior to PGMs whose constituent elements represent a significant cost savings. Shape memory alloy properties vary significantly with small (0.1% at.) compositional changes making robust investigative sample sets very large. Computational material design can be deployed to shrink the compositional space of possible alloy combinations and reduce the experimental load in material discovery. Investigating shape memory effect (SME) and validating process additive process parameters for a single novel composition is cost intensive in both time and consumed materials. Additionally, sub-optimal processing, oxygen, or solidification rate sensitivity could render additively manufacturing specimens without micro, macro cracks, or significant chemical variance impossible. Unfortunately, such failure susceptibility cannot be simulated. Therefore, a research pathway to validate novel shape memory alloy compositions for powder bed fusion additive manufacturing without the need for powdered feedstock is also proposed. This research investigates novel high temperature shape memory alloys for actuators without platinum group alloying elements to discover one that could be commercially viable as an additive manufacturing feedstock.

Sundermann, Tayler↗

Mixed-Metal, Structural, and Substitution Effects of Polyoxometalates on Electrochemical Behavior in a Redox Flow Battery

A pair of redox flow batteries containing polyoxometalates was tested as part of an ongoing program in stationary energy storage. The iron-containing dimer, (SiFe3W9(OH)3O34)2(OH)311-, cycled between (SiFe3W9(OH)3O34)2(OH)311-/(SiFe3W9(OH)3O34)2(OH)314-and (SiFe3W9(OH)3O34)2(OH)317-/(SiFe3W9(OH)3O34)2(OH)314- for the positive and negative electrode, respectively. This compound demonstrated a coulombic efficiency of 83% after 20 cycles with an electrochemical yield (measured discharge capacity as a percentage of theoretical capacity) of 55%. Cyclic voltammetry on the Lindqvist ion, cis-V2W4O194-, showed quasi-reversible vanadium electrochemistry, but tungsten reduction was mostly irreversible. In a flow cell configuration, cis-V2W4O194-had a coulombic efficiency of 45% (for a two-electron process) and an electrochemical yield of 16% after 20 cycles. The poor performance of cis-V2W4O194-was attributed primarily to its higher charge density. Collectively, the results showed that both polyoxometalate size and charge density are both important parameters to consider in battery material performance.

36 MATERIALS SCIENCE↗