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At least 1,405 records · Page 78

Multi-Source Machine Learning and Thermoplastics Enhanced Aerostructure Manufacturing (mTEAM)

RTX Technology Research Center (RTRC), together with Collins Aerospace (Collins) and Oak Ridge National Laboratory (ORNL) has developed an Artificial Intelligence (AI) / Machine Learning (ML) guided solution to advance the manufacturing and assembly of high performance and lightweight thermoplastic composite (TPC) aerospace products. The solution aims to lower risk, cost and lead time for induction heating based welding and consolidation processes for TPC structure. The cost and lead time of part and material specific process development for induction welding (IW) and induction consolidation will be reduced by replacing traditional empirical methods with optimization methods that merge AI/ML and physics-based process simulations and process experiments with sensing and controls. TPC-IW process development is empirical in nature, and uncertainties in material & process behavior exist near & far from the induction coil. Physics-based simulations can be leveraged directly for process optimization but can be too computationally expensive to run in high fidelity and real time to do robust process optimization. The key impact of successful TPC induction consolidation and welding is cost & lead time reduction for part & material specific consolidation and welding recipes. This is an enabler for more rapid deployment of TPC structures via joining assembly, which can reduce energy & cost intensive usage of autoclaves & ovens. The solution aimed to advance the U.S. Department of Energy’s interests in using thermoplastics and automation in composite manufacturing for improvement of products for existing markets via increased production speeds, reduced costs, and lowered use of energy. Welded TPC structures can offer significant weight & energy savings for high-value commercial aerospace & industrial applications compared to metal & thermoset composite structures assembled by mechanical fastening and/or adhesive bonding. The project was organized into two Budget Periods. Budget Period 1 (BP1) was 15 months and its goal was to perform ML process optimization framework development & deployment on lab-coupon aerostructure components. A Go/No-Go Review was performed at the end of BP1 to verify fulfilment of key tasks & milestones to justify a Go Decision to move into the next Budget Period. Budget Period 2 (BP2) was 12 months and its goal was the deployment of the ML framework for ML process optimization of pilot industrial scale aerostructure components. The overall project aim was to develop & demonstrate ML-enhanced modeling framework that learns process-property mapping from multiple data sources at different fidelities. During BP1, the team accomplished key tasks & milestones to demonstrate the concept of multi-source ML for TPC aerostructure consolidation and assembly. First, the team completed documentation of induction based TPC heating requirements including baseline metrics to compare measured results against. Next the team completed demonstration of data generation from physics-based simulations for ML surrogate model generation and demonstrated the integration of physics-based simulation data into multi-source AI/ML algorithms. In parallel, the team established the lab-coupon scale induction welding system and completed a process to label and reduce generated data from physics-based simulation and experiments for ML surrogate models to enable multi-source ML model training & testing. To complete BP1, the team integrated physics-based simulation data and experimental data into multi-source ML algorithms. This was based on the team completing ML deployment of the induction welding on a lab system at RTRC and AI/ML deployment on existing induction welding line at Collins. ORNL visited both Collins and RTRC sites to witness the TPC induction welding process. Then, ORNL designed and constructed a new version of their vision-based sensing system better adapted to acquire process signals of the TPC induction welding process for process anomaly and defect detection. In BP2, the team accomplished key tasks & milestones to scale up multi-source ML for TPC aerostructure consolidation and assembly from the lab-coupon scale to the pilot-industrial scale. In BP2, the team demonstrated real time anomaly & defect detection via experiments performed by ORNL & RTRC. The team completed ML-optimization heating trials for TPC induction consolidation at Collins, and the team confirmed pilot industrial scale experimental data from Collins was compatible with the developed ML pipeline from RTRC. The team completed sub-element scale ML process optimization demonstration at RTRC, where the team leveraged RTRC’s robotic TPC welding setup to de-risk the ML process optimization by performing ML analysis of recorded temperatures to account for complex part features. Then, the team applied its ML-derived control strategies and ML process optimization framework at Collins to the pilot-industrial scale on a demo skin-stiffener part representative of a nacelle aerostructure fan cowl section. The key innovation is the AI/ML framework enabling effective process development of high performance, lightweight, energy efficient TPCs for composite aircraft structures.

36 MATERIALS SCIENCE↗

Optimization of Processing, Microstructure, and Hardness of an Al–Ce–Ni–Mn–Zr Alloy With Laser Additive Manufacturing

Here, this study examines the processing behavior, microstructure, surface roughness, and hardness properties of an aluminum alloy containing 8.2 Ce, 4.5 Ni, 0.5 Mn, and 0.7 Zr (wt%) fabricated using laser powder bed fusion. Sixty samples were produced across a range of laser powers, scan speeds, and hatch spacings to evaluate their effect on porosity, hardness, and microstructural features. Porosity was measured using X-ray computed tomography, while microstructure and surface roughness were characterized by scanning electron (SEM) and laser confocal microscopy. High dense and cracking-free Al–Ni–Ce alloy was successfully manufactured. Porosity showed a U-shaped dependence on energy input, increasing under both insufficient and excessive melting conditions. Hardness increased with cooling rate due to finer cellular structures and solute redistribution. A general statistical model was developed to capture the relationships between processing parameters and material response. Results identify a narrow processing window defined by laser powers between 350 and 370 W, scan speeds from 1400 to 1800 mm/s, and hatch distances between 0.14 and 0.18 mm. Within this window, porosity is minimized (below 0.01%) and hardness is maximized (up to 160 HV), demonstrating that careful control of these parameters enables dense, high strength aluminum components suitable for demanding structural applications.

Aluminum alloys↗

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons

Abstract This Review addresses the use of X‐ray and neutron scattering as well as X‐ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub‐Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal‐organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small‐ and wide‐angle X‐ray or neutron scattering), 2) PDF (pair‐distribution function analysis of X‐ray total scattering), and 3) XANES and EXAFS (X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure, respectively). While the scattering techniques provide structural information, X‐ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

Yin, Jia‐Fu↗

A Hybrid Experimental and Theoretical Approach to Optimize Recovery of Rare Earth Elements from Acid Mine Drainage Precipitates by Oxalic Acid Precipitation

The development of processing techniques for the extraction of rare earth elements and critical minerals (REE/CM) from acid mine drainage precipitates (AMDp) has attracted increased interest in recent years. Processes under development often utilize a standard hydrometallurgical approach that includes leaching and solvent extraction followed by oxalic acid precipitation and calcination to produce a final rare earth oxide product. Impurities such as Ca, Al, Mn, Fe and Mg can be detrimental in the oxalate precipitation step and a survey of the literature showed limited data pertaining to the REE precipitation efficiency in solutions with high impurity concentrations. As such, a systematic laboratory-scale precipitation study was performed on a strip solution generated by the acid leaching and solvent extraction of an AMDp feedstock to identify the optimal processing conditions that maximize REE precipitation efficiency and product purity while minimizing the oxalic acid dosage. Given the unique chemical characteristics of AMDp, the feed solution utilized in this study contained a moderate concentration of REEs (440 mg/L) as well a significant concentration (>7000 mg/L total) of non-REE contaminants such as Ca, Al, Mn, Fe and Mg. Initially, a theoretical basis for the required oxalic acid dose, optimal pH and predicted precipitation efficiency was established by solution equilibrium calculations. Following the solution chemistry calculations, bench-scale precipitation experiments were conducted and these test results indicate that a pH of 1.5 to 2, a reaction time of more than 2 h and an oxalic acid dosage of 30 to 40 g/L optimized the REEs recovery of at ~95% to nearly 100% for individual REE species. The test results validated the optimal pH predicted by the solution chemistry calculations (1.5 to 5); however, the predicted dosage needed for complete REE recovery (10 g/L) was significantly lower than the experimentally-determined dosage of 30 to 40 g/L. The reason for this discrepancy was determined to be due to the large concentration of impurities and large number of potential metal complexes that cause inaccuracies in the solution equilibrium calculations. Based on these findings, a hybrid experimental and theoretical approach is proposed for future oxalic acid precipitation optimization studies.

oxalic acid precipitation↗

3D printing of lignin: Challenges, opportunities and roads onward

Abstract As the second most abundant biopolymer on earth, and as a resource recently becoming more available in separated and purified form on an industrial scale due to the development of new isolation technologies, lignin has a key role to play in transitioning our material industry towards sustainability. Additive manufacturing (AM), the most efficient‐material processing technology to date, has likewise made great strides to promote sustainable industrial solutions to our needs in engineered products. Bringing lignin research to AM has prompted the emergence of the nascent “lignin 3D printing” field. This review presents the recent state of art of this promising field and highlights its challenges and opportunities. Following a review of the industrial availability, molecular attributes, and associated properties of technical lignins, we review R&D efforts at implementing lignin systems in extrusion‐based and stereolithography (SLA) printing technologies. Doing so underlines the adage of lignin research that “all lignins are not created equal,” and stresses the opportunity nested in this chemical diversity created mostly by differences in isolation conditions to molecularly select and tune the attributes of technical lignin systems towards desirable properties, be it by modification or polymer blending. Considering the AM design process in its entirety, we finally propose onward routes to bring the full potential to this emerging field. We hope that this review can help promote the unique value and overdue industrial role of lignin in sustainable engineered materials and products.

36 MATERIALS SCIENCE↗

Developing rapid electrochemical relithiation protocols for scalable relithiation of lithium-ion battery cathode materials

The recent and ongoing boom in electric vehicle sales has caused the circularity of the supply chain for electric vehicle battery materials to come under a great deal of scrutiny. Innovative recycling processes, or direct recycling, that offer the possibility of reducing the cost of recycling are one possible solution to regaining resources from end-of-life (EoL) electric vehicle batteries. Electrochemically shuttling lithium back into the cathode, or electrochemical relithiation, is a possible technique for restoring lithium content to NMC materials (EoL) in a direct recycling process. This study provides essential understanding towards developing an electrochemical relithiation protocol that will restore lithium loss in intercalation cathode materials that reach EoL by loss of lithium inventory (LLI) as opposed to other degradation mechanisms like loss of active material (LAM), cation mixing or phase transition. Electrochemically aged NMC cathode materials have been prepared and characterized to establish the extent of EoL material structural degradation and lithium loss. A model-informed experimental process is used to identify the optimal electrochemical relithiation protocol to minimize the time taken to relithiate EoL materials and maximize the amount of lithium restored. Protocols were evaluated based on their ability to enable rapid lithium intercalation, maintain structural uniformity in the EoL material and fully restore lithium content. An optimal protocol was identified at elevated temperatures utilizing a novel scanning voltage step.

25 ENERGY STORAGE↗

Numerical Study of Mineral Nucleation and Growth on a Substrate

We report nucleation and growth processes of minerals and other crystals can significantly affect one another due to the transport limitations and local depletion of reactive ions in the solution. Most numerical models and experimental measurements have typically focused on either growth or nucleation, but not both. In this work, we incorporate a heterogeneous nucleation process based on classical nucleation theory into a microcontinuum model that implements the Darcy–Brinkman–Stokes approach to study the interplay between nucleation and crystal growth on a substrate in diffusive systems. We demonstrate how the Damköhler number (reaction rate) and nucleation rate prefactor change the effective nucleation rate on a substrate. Higher surface growth rates deplete the solute concentration around the nuclei that appear initially on the substrate, creating islands that screen against further nucleation. The model predicts that measured nucleation rates may be affected by the history of crystal nucleation on the substrate. In the extreme case of high growth rates relative to diffusion, it predicts that the rate of subsequent nucleation is limited by reactant depletion. We introduce a nondimensional number α to represent the relation between surface propagation rate during growth and the heterogeneous nucleation rate. We show that it is important to control Damköhler number and α to achieve similar precipitation regimes at different reaction and nucleation rates. We suggest that the observed universality can guide the interpretation of experimental results on nucleation rates, since matching experiment can be achieved by tuning transport, reaction, and nucleation parameters simultaneously. In addition, we show how the bulk solution concentration affects the structure and topology of precipitation on a substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Nanocrystal-Ligand Boundaries: Reversible Photoinduced Ligand Detachment from Quantum Dots in Solution

The porosity of ligand shells of colloidal quantum dots (QDs) can influence the overall rate and yield of charge transfer processes occurring at their surfaces. However, the density of ligand shells on QDs can also influence their colloidal and photochemical stability. We used time-resolved infrared spectroscopy to show that photoinduced ligand detachment, the tendency for certain ligands to detach from QD surfaces when the nanocrystals are promoted to their excitonic excited states, can be used to transiently enhance the porosity of oleic acidpassivated CdSe QDs in solution. Furthermore, we synthesized CdSe QDs with varying ligand shell densities to examine the corresponding influence that van der Waals interactions among ligands have on the yield of photoinduced ligand detachment and the time scale on which ligands return to QD surfaces. We observed that oleic acid ligands on CdSe QDs with lower shell densities have a higher probability of escape for longer periods of time. Despite this, oleic acid ligands on fully passivated CdSe QDs are still able to photodetach, resulting in a transient increase of their ligand shell porosity. In contrast, QDs with multilayer ligand coronas exhibit negligible photoinduced ligand detachment because the outer molecular layers introduce a type of cage effect, preventing the escape of the interior ligands. Our findings suggest the intriguing possibility that photoinduced ligand detachment can be used to transiently decrease the density of ligand shells of QDs to facilitate charge transfer processes while still allowing them to be fully passivated between excitation events for photochemical and colloidal stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor

Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Development of HPC based phase field simulations tool for modification of alloy morphology to enhance material properties during additive manufacturing (AM) process

Currently, additive manufacturing (AM) technology is extensively used to manufacture aerospace components because of the unique advantages of the technique in producing custom designs, complex geometries in a near-net fashion that significantly reduces the manufacturing cost, and improved energy efficiency. However, the thermodynamic properties of existing aerospace alloys and the thermal conditions that prevail in most of the powder-bed based additive manufacturing processes lead to undesirable columnar / columnar-dendritic microstructures that promote solidification cracking during the process, and the development of anisotropy in the mechanical properties of the as-built components. Time consuming, energy-intensive post AM treatments are required to recover the mechanical properties of the wrought components for which the existing alloy compositions were designed for. However, novel alloy compositions, that exploit the AM thermal conditions to produce fine, equiaxed grain structures in the as-built condition, with mechanical properties equal to or exceeding those of the wrought work-horse alloy, Ti-6Al-4V has recently been demonstrated in Ti-Cu alloys. Significant energy savings up to 66% can be obtained for a typical aerospace component through digitally designing the AM process, process parameters, and alloy composition. The current project focused on developing a fundamental understanding of the evolution of the columnar to equiaxed transition (CET) occurring during solidification under AM thermal conditions in Ti-Cu and Ti-Cu-X alloys using high-fidelity phase field (PF) simulations using the leadership class computing facilities that exist in the national laboratories. The simulations were able to capture the effect of alloy and process conditions on CET, and clearly showed the beneficial effect of a ternary solute addition to Ti-Cu binary alloys on CET. The simulations indicated that bulk nucleation in the liquid ahead of the solidifying epitaxial front was promoted by a large, transient, thermal undercooling promoted by the mismatch between the growth rate of the dendrite tips in the epitaxial front and the imposed solidification rate. AM experiments performed at Raytheon Technologies Research Center using the same thermal conditions used in the PF simulations indicated the formation of equiaxed grains, although the grain size was bigger than the ones reported in the literature. On the other hand, the equiaxed grain size predicted by PF simulations were smaller than the grain size of Ti-Cu alloys reported in the literature. The industry will follow up the existing work in a future program that would involve further optimization of the process for the Ti-Cu-X alloys to demonstrate the application of the process and the alloy to a specific aerospace component.

36 MATERIALS SCIENCE↗

Disulfonamide Ligands as f-Element Extractants from Alkaline High-Level Waste

Almost 100 million gallons of high level waste (HLW) has been generated from defense reprocessing programs to support nuclear weapons production. HLW is currently stored at the Hanford and Savannah River Sites (SRS) [1]. It contains radioactive components, such as {sup 137}Cs, {sup 99}Tc and {sup 90}Sr, as well as large amounts of non-radioactive species, including solvated cations and insoluble metal hydroxides. HLW has high concentration of soluble hydroxides ([OH{sup -}] = 2 M at SRS [2]), complexing inorganic anions ([NO{sub 3}{sup -}] ∼ 0.65 - 3.7 M at SRS [2]) and a high ionic strength. Even though the majority of actinide component in alkaline HLW is precipitated, studies of An(III) and Ln(III) complexation in highly alkaline solutions in the presence of high nitrate concentrations have showed that soluble nitrate complexes can be formed [3]. The current treatment of HLW at SRS currently consists of two processes: The Actinide Removal Process (ARP) and the Next-Generation Caustic-Side Solvent Extraction process (NG-CSSX). Strontium and actinides are removed by sorption on monosodium titanate through the Actinide Removal Process (ARP) commonly referred to as the alpha-strike step [4]. Then, cesium is selectively extracted from the alkaline media via the Caustic-Side Solvent Extraction (CSSX) process [5]. The CSSX solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix containing i) a solvent modifier (alkylphenoxy alcohol) which increases extractant solubility and prevents third phase formation, and ii) a suppressor (trioctylamine or guanidine) - that mitigates surfactant effects. The CSSX process removes {sup 137}Cs selectively and rapidly, yet the post- CSSX aqueous stream may still contain high amounts of An, thus requiring a second ARP treatment (referred to as 'alpha-finishing') for some tanks. Despite the success of the ARP process in removing Sr and An, it often represents the kinetic bottleneck of integrated processing, as it is slower than solvent extraction. Understanding the complexation of actinides by organic ligands that are compatible with the CSSX process could eventually lead to a combined caustic-side Cs/Sr/actinide extraction process with better economics due to a reduced amount of monosodium titanate and/or a shorter required contact time with titanate during ARP. This would ensure a low-activity waste (LAW) stream with no actinides without additional ARP processing post-CSSX. Disulfonamides were studied for extraction of Sm(III) from alkaline aqueous media of pH 10-14 into dichloromethane. Up to 82% of Sm(III) was extracted from solutions of pH 12.5 -13.5 and up to 84% from solutions of pH 10.5 - 11.5. These results show some resemblance with Am extraction results by calixarene ligands previously reported [10]. Kinetic studies demonstrated that even 5 min is enough to complete stripping, whereas extraction is time-limiting process and requires up to 20 h for efficient removal of Sm(III) from alkaline aqueous media. Determination of composition of complexes in solution after extraction by the equilibrium shift method showed a 1:1 Sm(III):dsa-2 complexation ratio for the extracted species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons

This Review addresses the use of X-ray and neutron scattering as well as X-ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub-Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal-organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small- and wide-angle X-ray or neutron scattering), 2) PDF (pair-distribution function analysis of X-ray total scattering), and 3) XANES and EXAFS (X-ray absorption near-edge structure and extended X-ray absorption fine structure, respectively). While the scattering techniques provide structural information, X-ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adapting In Situ Accelerators for Sparsity With Granular Matrix Reordering

Neural network (NN) inference is an essential part of modern systems and is found at the heart of numerous applications ranging from image recognition to natural language processing. In situ NN accelerators can efficiently perform NN inference using resistive crossbars, which makes them a promising solution to the data movement challenges faced by conventional architectures. Although such accelerators demonstrate significant potential for dense NNs, they often do not benefit from sparse NNs, which contain relatively few non-zero weights. Processing sparse NNs on in situ accelerators results in wasted energy to charge the entire crossbar where most elements are zeros. To address this limitation, this paper proposes Granular Matrix Reordering (GMR): a preprocessing technique that enables an energy-efficient computation of sparse NNs on in situ accelerators. GMR reorders the rows and columns of sparse weight matrices to maximize the crossbars' utilization and minimize the total number of crossbars needed to be charged. The reordering process does not rely on sparsity patterns and incurs no accuracy loss. Finally, GMR achieves an average of 28% and up to 34% reduction in energy consumption over seven pruned NNs across four different pruning methods and network architectures.

97 MATHEMATICS AND COMPUTING↗

A green closed-loop process for selective recycling of lithium from spent lithium-ion batteries

As the economy started to recover from the COVID pandemic, the price of Li 2 CO 3 skyrocketed to its highest. This situation has aggravated concerns about the supply chain for lithium-ion batteries (LIBs). Recycling spent LIBs is a potential solution to alleviate the bottleneck of the supply chain and prevent environmental pollution, and has attracted lots of attention. However, lithium recycling is generally disregarded because of the complex recycling process and its low recycling efficiency. Here, in this work we developed a sustainable lithium recovery process, which can selectively leach and recover lithium with formic acid before recycling valuable metals. With the reported method, lithium can be 99.8% recovered from layered oxide cathode materials with 99.994% purity. In addition, this lithium recovery process is affordable, compared to the typical hydrometallurgical process, by saving 11.15% per kilogram of spent LIBs. Therefore, this research provided a new solution to eliminating the effects of lithium ions on valuable metal separation and the co-precipitation reaction and precluding the influence of other metal ions on lithium recovery. Finally, this simplified lithium recovery process provides new opportunities for sustainable recycling of LIBs and economical restoration of the lithium supply chain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalized models for inflationary preheating: Oscillations and symmetries

The paradigm of the inflationary universe provides a possible explanation for several observed cosmological properties. In order for such solutions to be successful, the universe must convert the energy stored in the inflaton potential into standard model particles through a process known as reheating. In this paper, we reconsider the reheating process for the case where the inflaton potential respects an approximate (but spontaneously broken) conformal symmetry during the reheating epoch. After reviewing the Effective Field Theory of Reheating, we present solutions for the nonlinear oscillations of the inflaton field, derive the corresponding Hill’s equation for the coupled reheating field, and determine the stability diagram for parametric resonance. For this class of models —the simplest realization being a scalar field with a quartic term—the expansion of the universe drives the coupled field toward a more unstable part of parameter space, in contrast to the standard case. We also generalize this class of models to include quadratic breaking terms in the potential during the reheating epoch and address the process of stability in that universality class of models.

Barrowes, Leia [University of Michigan, Ann Arbor]↗

IPL-Annealed Mixed-Cation Perovskites with Robust Coating Window toward Scalable Manufacturing of Commercial Perovskite Solar Cells

Perovskite solar cells (PSCs) are a promising alternative solar technology, but the technical challenges of (1) stability/durability, (2) efficiency at scale, and (3) manufacturability must be overcome to achieve widespread PSC commercialization. The challenge of balancing solution ink formulation and scalable manufacturing is often overlooked in the literature, where focus is on adopting inks from processes that will not scale. In this study, we apply a classical roll-to-roll manufacturing perspective, utilizing both compositional engineering and intense pulsed light (IPL) annealing, to develop a mixed-cation perovskite ink with a robust coating window that simultaneously solve issues of stability and manufacturability for PSCs. Our method resulted in blade-coated, flexible, mixed-cation PSCs on ITO-PET substrates with a champion power conversion efficiency (PCE) efficiency of 16.7% using IPL annealing of the absorber layer and, to our knowledge, is one of the fastest processing methods for the perovskite layer. This overall reduction in processing time with a stable ink represents an advance toward the scaled production of perovskite solar cells on flexible substrates.

flexible perovskite solar cells↗

Optimized manufacturing process for multilayer two-dimensional focusing mirrors in laboratory X-ray applications

Recent advances in laboratory X-ray applications require high-performance optical components that achieve exceptional imaging resolution and beam uniformity within compact experimental setups. Montel mirrors have become a preferred solution due to their unique dual-reflection focusing mechanism and a space-efficient design. Here, in this study, we present an effective manufacturing process for producing Montel mirrors tailored to focus laboratory X-ray beams. The mirrors were fabricated from single-crystal silicon substrates, chosen for their high mechanical stability and compatibility with precision polishing techniques. Our approach begins with the integration of a deterministic chemo-mechanical polishing (CMP)-based pre-shaping step followed by ion beam figuring (IBF), significantly improving manufacturing efficiency. Subsequently, our custom-developed advanced metrology and IBF techniques were employed for fabricating an off-axis, elliptical cylinder Montel mirror system with a 6-mrad total slope, with stringent optical specifications. While post-IBF processes, including multilayer coating, dicing, and gluing, introduced minor surface errors, yet their impact on performance remained negligible. The Montel mirrors manufactured with the optimized process exhibited significantly improved beam uniformity and a reduced focal spot size. These findings validate our approach as a viable solution for high-precision Montel mirror fabrication and facilitate further advancements in laboratory X-ray applications.

36 MATERIALS SCIENCE↗

Parametric study and speciation analysis of rare earth precipitation using oxalic acid in a chloride solution system

Oxalic acid precipitation is a common step in the purification of rare earth elements (REE) from a concentrated pregnant leach solution (PLS). However, the presence of contaminants such as Al, Fe, and Ca in given amounts decreases the REE precipitation efficiency and product purity while also increasing the amount of oxalic acid needed to maximize recovery. As such, a statistically designed test program was performed to identify the optimal conditions necessary for a relatively low REE content PLS containing elevated concentrations of contaminant ions. The performance objective was maximization of REE precipitation efficiency while minimizing the oxalic acid dosage. A central composite design was utilized to quantify performance impacts and identify the ultimate set of parameter values for oxalic acid dosage, Fe(III) contamination concentration, solution pH, and reaction temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicate that increasing the oxalic acid concentration from 0 g/L to 80 g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. Here, to further the understanding of the REE-oxalate system, a fundamental solution chemistry study was performed using the equilibrium constants of the reactions. The study resulted in the development of oxalate speciation diagrams and provided an analysis of the REE precipitation characteristics at various oxalate anion concentrations and Fe(III) contamination levels using MINTEQ software. The dominant Fe(III) species in the solution system were found to be Fe-(C 2 O 4 ) 3 3- , Fe-(C 2 O 4 ) 2- , and Fe-(C 2 O 4 ) + , which consume the majority of the oxalate anions. The simulated model was found to be in agreement with the experimental findings and helped to explain the adverse impact of increased iron concentrations on REE precipitation efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗