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At least 793 records · Page 44

Tunneling electroresistance effects in epitaxial complex oxides on silicon

Complex oxide-based ferroelectric tunnel junctions (FTJs) show excellent nonvolatile memory characteristics promising for emerging technology. However, integration of these epitaxially grown FTJs electrically with a silicon substrate remains challenging due to their incompatible lattice structures and poor electronic interfaces resulting from the direct synthesis techniques. Here, we present an epitaxial SrRuO 3 /PbZr 0.2 Ti 0.8 O 3 /SrRuO 3 FTJ integrated electrically with a doped silicon substrate after a layer transfer process. The tunnel currents of the FTJ on silicon show a large tunneling electroresistance (~1×10 5 %) effect, which is explained by a numerical FTJ model incorporating pinned dipoles at the interfaces. This proof of concept of the integration of functional oxide heterostructures with silicon opens a pathway to beyond-CMOS computing devices using unconventional materials.

36 MATERIALS SCIENCE↗

Cobalt-Free Cathodes for Next Generation Li-Ion Batteries

In this U.S. Department of Energy sponsored project Nexceris, in collaboration with project partners; The Ohio State University and Navitas Advanced Systems have advanced the technical maturity of a non-cobalt containing cathode for next-generation Li-ion batteries. The cathode is based on the lithium manganese nickel-titanium oxide, LiNi 0.5 Mn 1.5 TiO 4 (LNMTO) high voltage spinel. To address limitations with poor cycle and calendar life an microstucturally hierarchical LNMO/LNMTO core-shell cathode powder has been developed that enables the formation of a solid-electrolyte interface that effectively passivates the cathode surface. The microstructural enhancements of the cathode material focus on preferentially enriching the surface with titanium. In parallel, new, optimized binder and electrolyte chemistries have been incorporated to address degradation mechanisms associated with high-voltage systems. Single-layer pouch cell and large-format 2-Ah cell testing have shown that an optimized LNMO/LNMTO core-shell powder significantly improves initial cell capacity and cycle life compared to homogeneous LNMO powder. To support development and the fabrication of 2-Ah cells a novel Hybrid Alternative Wet-Chemical Synthesis (HAWCS) process have been developed. This low-cost, synthesis approach enables the excellent compositional and particle morphology control achieved with co-precipitation without the strict process controls and associated expensive process equipment.

25 ENERGY STORAGE↗

Studying light–matter interactions and energy transfer at the nanoscale with a trapped–ion quantum computer

A grand challenge in materials sciences is to control energy transduction, transfer and dissipation at the nanoscale. Meeting this challenge requires progress in nanoscale fabrication and synthesis, but equally importantly, also progress in our understanding of how nanoscale structure influences these phenomena. Although detailed quantum mechanical models exist that capture the structure and physics of materials and molecular species, solving these models to calculate the relevant emergent phenomena, which often occur over vastly different time and energy scales, has so far proven difficult. In this project, we studied how to model energy transfer and light-matter interactions using trapped-ion quantum computers. Our studies focused on emulation of critical processes in natural systems, such as the well-known photosynthetic pigment-protein complexes responsible for capturing and transducing light to electrons. In addition, we implemented proof-of-principle experiments demonstrating that such calculations are possible on trapped-ion quantum computing hardware. These studies and experiments pave the way to investigate energy transport and transduction in a detail not accessible with classical computing technologies. We expect that our studies will allow to extract important guiding principles on how to improve the efficiency of nano-scale light-harvesting and transduction devices.

36 MATERIALS SCIENCE↗

Cooperative Research and Development Agreement (CRADA) between National Energy Technology Laboratory and Susteon, Inc. (Final Report)

NETL developed a nanostructured Fe catalyst capable of converting syngas to olefins. Initial laboratory testing demonstrated this technology possessed high reactivity (~70% conversion), good olefin selectivity (~40 weight %), and a long-performance lifetime (greater than 500 h on stream with no degradation). Under CRADA Agreement 0988, NETL and Susteon collaborated to evaluate the commercial potential of this catalyst technology by scaling up the catalyst synthesis and collecting reactivity data to characterize the mass and energy balance associated with utilizing this catalyst in a Fischer Tropsch to Olefins (FTO) reactor. Research under CRADA Agreement 0988 illustrated there are technical barriers associated with synthesizing the catalyst that the team was not able to overcome. Reactivity testing with this material illustrated that the catalyst deactivated in less than 50 hours of time on stream. Due to this technical barrier, the team did not meet its Go/No-Go decision target of creating a FTO process that produces at least a 25% reduction in olefin production cost compared to the current state-of the-art technologies. As a result, the team has stopped all work on CRADA Agreement 0988.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermally stable and self-healable lignin-based polyester

The increased use of plastics and the associated environmental impact has catalyzed research on the development of bio-derived polymers. Bio-based polyesters have gained increased attention due to the abundance of their starting materials and ease of processing. Lignin is naturally occurring in biomass with rich carbon content, whose functionality and rigidity make it an ideal bio-derived candidate for bio-based polyesters. Herein, a lignin-based polyester with good thermal stability and self-repairability was synthesized from carboxylated lignin and epoxidized soybean oil. The synthesized lignin/epoxidized soybean oil (ESO) vitrimer was brittle such that its mechanical performance could not be recorded. However, when polyethylene glycol (PEG) was incorporated as a plasticizer, polymer samples exhibited acceptable ductility. From thermomechanical analysis of the synthesized polyesters, the plasticizer did not impair thermal stability of polymers, but greatly enhanced mechanical properties. Notably, all samples exhibited stability at high temperatures, and good glass transition temperatures (51.0 ± 0.9–78.0 ± 1.2 °C). The highest tensile strength (3.983 ± 0.1 MPa) and storage modulus (1463.67 ± 12.6 MPa) were recorded for the polyester containing 6 % w/w PEG. Moreover, the polymer samples exhibited self-healing capability at 180 °C. This work expands on valorization of lignin through the synthesis of bio-derived materials.

36 MATERIALS SCIENCE↗

Ceramic–Metal (Cermet) Composites: A Review of Key Properties and Synthesis Methods Focused on Nuclear Waste Immobilization

Here this paper reviews key properties, applications, and examples of ceramic-metal composites (cermets), and metal matrix composites (MMC) with emphasis on their applicability as waste forms for immobilizing nuclear waste. While the literature is mature for vitrified and cementitious radioactive waste forms, cermet materials have not received adequate attention as potential candidates for immobilizing nuclear waste. To promulgate this effort, this review connects cermet and MMC design, such as hardened tools, with the chemistry of radioactive waste streams. A discussion on certification and qualification standards for cermet waste forms, literature gaps, and “how-to” sections on cermet processing techniques. Key parameters discussed include thermal conductivity, chemical durability, and waste loading, as well as examples for metal-containing waste forms. As cermet waste forms gain momentum within the community, this review paper aims ensure the end-of-life nuclear fuel cycle is addressed from a materials and waste disposition perspective.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-Operando Study of Shape Retention and Microstructure Development in a Hydrolyzing Sol–Gel Ink during 3D-Printing

3D printing of amorphous and crystalline ceramics is of paramount importance for the fabrication of a wide range of devices with applications across different technology fields. Printed ceramics are remarkably enabled by the sol-gel synthesis method in conjunction with continuous filament direct ink writing. During printing, multiple processes contribute to the evolution of inks including shape retention, chemical conversion, solidification, and microstructure formation. Traditionally, depending on the ink composition and printing environment, several mechanisms have been associated with the shape retention and solidification of 3D printed structures: gelation, rapid solvent evaporation, energy-driven phase transformation, and chemical-driven phase transformation. Understanding the fundamental differences between these mechanisms becomes key since they strongly influence the spatiotemporal evolution of the materials, as the out-of-equilibrium processes inherent to the extrusion, relaxation, and solidification of printed materials have significant effects on the materials properties. Herein, we investigate the shape retention mechanism and the hydrolysis-induced material conversion and microstructure formation during the 3D printing of a water reactive sol-gel ink that transforms into titanium dioxide-based ceramic. This study aims at identifying characteristic mechanisms associated with the material transformation, establishing connections between the microstructure development and the timescales associated with solidification under operando 3D-printing conditions. The investigation of this material's out-of-equilibrium pathways under processing conditions is enabled by time-resolved coherent X-ray scattering, providing simultaneous access to temporospatially resolved microstructural and dynamics information. Furthermore, we explore X-ray speckle tracking as a tool to resolve deformations of the microstructure in a printed filament associated with the deposition of consecutive filaments. Through this work, we aim at providing a fundamental understanding of the relationships behind these transformative processes in 3D printing and their timescales as the basis for achieving unprecedented control over printed materials microstructure.

36 MATERIALS SCIENCE↗

Solid state reduction of nickelate thin films

The square-planar nickelates are a class of superconductors analogous to the cuprates and promise to provide insight into the pairing mechanism in high-temperature superconducting oxides. The parent phase of doped superconducting films is NdNiO 2 , which is prepared by reducing 3 + Ni in NdNiO 3 films. In this paper, we develop an ultrahigh vacuum reduction method using aluminum deposited on top of the 3 + nickelates and monitor the reduction process in real time through in situ crystal truncation rod measurements and diffraction x-ray absorption near edge spectroscopy measurements across the Ni K edge. Further, we establish a relation between Ni valence and the lattice constant of NdNiO 3-x and show that the process can precisely control the oxygen content in the films. Finally, we extend the reduction process to quintuple square-planar nickelates.

36 MATERIALS SCIENCE↗

Rational Design of Novel Biomimetic Sequence-Defined Polymers for Mineralization Applications

Silica biomineralization is a naturally occurring process, wherein organisms use proteins and other biological structures to direct the formation of complex, hierarchical nanostructures. Discovery and characterization of such proteins and their underlying mechanisms spurred significant efforts to identify routes for biomimetic mineralization that reproduce the exquisite shapes and size selectivities found in nature. A common strategy has been the use of short peptide sequences with chemistry mimicking those found in natural systems, such as the use of the silaffin-derived R5 peptide. While progress has been made using this approach, there are many limitations that have prevented breakthroughs in biomimicry. To advance our ability to use charged macromolecules for silica formation, we propose to use sequence-defined synthetic polymers known as peptoids, or N-substituted polyglycines, which present significant capability for the precise tuning of sequence and structure beyond what can often be achieved with peptides alone. This study presents a computationally predicted design of these polymers that leads to the controlled formation of silica nanomaterials. We investigate surface adsorption and the mineralization process through analysis of binding mechanisms and energetics of the R5 system. Next, we synthesized two R5-inspired peptoids and validated our prediction in the design of mineralization polymers through characterization using surface plasmon resonance and electron microscopy. Here, this computationally guided study holds great promise for designing new sequences with unprecedented control of the placement of chemical functional groups, thus allowing for further unraveling of silicification mechanisms and the eventual design of sequence-defined synthetic polymers leading to the predictive synthesis of nanostructured functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Transition Metal Ion Contaminants on the Performance of Amine-Based Solid Sorbents in Direct Air Capture

Amine-functionalized solid sorbents are a class of sorbent materials proposed for direct air capture (DAC) of CO 2 , yet their long-term performance is susceptible to degradation under realistic operating conditions. Many amines are not thermodynamically stable in air, and amine sorbents oxidize while in use during DAC temperature swing adsorption processes. In this study, we investigate the role of transition metal ion contaminants, specifically Cu 2+ , Fe 2+ , and Ni 2+ , on the oxidative degradation of poly(ethylenimine) (PEI)-impregnated SBA-15 sorbents. By introducing metal ions via different modes mimicking both synthesis-related impurities and impurities derived from environmental exposure, we systematically evaluate sorbent stability after exposure to dry air at an elevated temperature. Thermogravimetric CO 2 uptake measurements reveal that even trace levels of Cu and Fe (as low as ∼4 ppm) can lead to measurable sorbent deactivation after oxidative aging, despite negligible loss in the performance of the control samples. In situ infrared, UV–vis, and X-ray photoelectron spectroscopies indicate that these metals catalyze radical-driven oxidation pathways, altering the chemical structure of the sorbent and accelerating degradation. Our findings underscore the need to account for trace metal contamination during DAC sorbent synthesis and deployment and highlight the importance of environmental contamination pathways.

CO2 capture↗

Chemical Robotics Enabled Exploration of Stability in Multicomponent Lead Halide Perovskites via Machine Learning

Metal halide perovskites have attracted immense interest as a promising material for a variety of optoelectronic and sensing applications. However, issues regarding long-term stability have emerged as the key bottleneck for commercialization. Here, we develop an automated experimental workflow based on combinatorial synthesis and rapid throughput characterization to explore long-term stability of these materials in ambient conditions. We apply it to four model perovskite systems: MA x FA y Cs 1–x–y PbBr 3 , MA x FA y Cs 1–x–y PbI 3 , Cs x FA y MA 1–x–y Pb(Br x+y I 1–x–y ) 3 , and Cs x MA y FA 1–x–y Pb(I x+y Br 1–x–y ) 3 . Non-negative matrix factorization and Gaussian process regression are used to interpolate the photoluminescent behavior of the phase diagram. This interpolative regression analysis helps to distinguish mixtures that form solid solutions from those that segregate into multiple materials, pointing out the most stable regions of the phase diagram. Here, we find stability dependence on composition to be nonuniform within the composition space, suggesting the presence of potential preferential compositional regions. This proposed workflow is universal and can be applied to other solution-processable materials.

36 MATERIALS SCIENCE↗

Solid–state synthesis of multicomponent equiatomic rare–earth oxides

Phase formation in multicomponent rare–earth oxides is determined by a combination of composition, sintering atmosphere, and cooling rate. Polycrystalline ceramics comprising various combinations of Ce, Gd, La, Nd, Pr, Sm, and Y oxides in equiatomic proportions were synthesized using solid–state sintering. The effects of composition, sintering atmosphere, and cooling rate on phase formation were investigated. Single cubic or monoclinic structures were obtained with a slow cooling of 3.3°C/min, confirming that rare–earth oxides follow a different structure stabilization process than transition metal high–entropy oxides. In an oxidizing atmosphere, both Ce and Pr induce a cubic structure, while only Ce plays that role in an inert or reducing atmosphere. Samples without Ce or Pr develop a single monoclinic structure. The structures formed at initial synthesis may be converted to a different one, when the ceramics are annealed in an additional atmosphere. Phase evolution of a five–cation composition was also studied as a function of sintering temperature. In conclusion, the binary oxides used as raw materials completely dissolve into a single cubic structure at 1450°C in air.

36 MATERIALS SCIENCE↗

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

The Instability of Monolayer-Thick PbSe on VSe 2

Two-dimensional monolayers derived from 3D bulk structures remain a relatively unexplored class of materials because of the challenge of stabilizing non-epitaxial interfaces. Here, we report an unusual reconstruction during the deposition of precursors when targeting the synthesis of heterostructures with an odd number of PbSe monolayers. Multilayer elemental precursors of Pb|Se + V|Se were deposited to have correct number of atoms to form [(PbSe) 1+δ ] q (VSe 2 ) 1 where q is the number of PbSe monolayers in the heterostructure. Structural analysis of the self-assembled precursor via xray reflectivity, x-ray diffraction, and HAADF-STEM suggests three different behaviors upon deposition. Precursors with q 7 and even values of q have the targeted nanoarchitectures after deposition which are maintained as the products are selfassembled through a near diffusionless process. Significant lateral surface diffusion occurred during deposition of precursors with q = 1, 3, and 5 resulting in the precursor having a different nanoarchitecture than targeted. Additional perpendicular long range diffusion occurs during self-assembly of these precursors resulting in different final products than targeted. DFT calculations of PbSe blocks show that the odd numbered layers are less stable than even numbered layers, which suggests an energetic driving force for the observed rearrangement. This work highlights the importance of understanding the reaction mechanism when attempting to prepare 2D layers of constituents with bulk 3D structures.

36 MATERIALS SCIENCE↗

Recent Advances in the Application of Functionalized Lignin in Value-Added Polymeric Materials

The quest for converting lignin into high-value products has been continuously pursued in the past few decades. In its native form, lignin is a group of heterogeneous polymers comprised of phenylpropanoids. The major commercial lignin streams, including Kraft lignin, lignosulfonates, soda lignin and organosolv lignin, are produced from industrial processes including the paper and pulping industry and emerging lignocellulosic biorefineries. Although lignin has been viewed as a low-cost and renewable feedstock to replace petroleum-based materials, its utilization in polymeric materials has been suppressed due to the low reactivity and inherent physicochemical properties of lignin. Hence, various lignin modification strategies have been developed to overcome these problems. Herein, we review recent progress made in the utilization of functionalized lignins in commodity polymers including thermoset resins, blends/composites, grafted functionalized copolymers and carbon fiber precursors. In the synthesis of thermoset resins such as polyurethane, phenol-formaldehyde and epoxy, they are covalently incorporated into the polymer matrix, and the discussion is focused on chemical modifications improving the reactivity of technical lignins. In blends/composites, functionalization of technical lignins is based upon tuning the intermolecular forces between polymer components. In addition, grafted functional polymers have expanded the utilization of lignin-based copolymers to biomedical materials and value-added additives. Different modification approaches have also been applied to facilitate the application of lignin as carbon fiber precursors, heavy metal adsorbents and nanoparticles. These emerging fields will create new opportunities in cost-effectively integrating the lignin valorization into lignocellulosic biorefineries.

36 MATERIALS SCIENCE↗

Synthesis and characterization of biobased copolyesters based on pentanediol: (1) Poly(pentylene dodecanoate–co–furandicarboxylate)

A series of biobased aliphatic-aromatic copolyesters, poly(pentylene dodecanoate-co-furandicarboxylates) (PPeDFs) were synthesized via an esterification and polycondensation melt process. The copolyesters were characterized using gel permeation chromatography, Fourier transform infrared spectroscopy, 1 H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, wide angle x-ray scattering, and tensile testing. The thermal transition behavior was strongly dependent on composition, with the melting and glass transition temperatures reaching a minimum at approximately equimolar ratio of D to F. All copolyesters were stable below 300°C with their R 600 (the weight of material remaining at 600°C) values increasing with F fraction. PPeD to PPeDF30 (e.g., mole ratio D/F = 7:3) show sharp PPeD crystalline reflections only while broad PPeF reflections are shown in PPeF and PPeDF90. PPeDF40 to PPeDF80 showed both crystal structures. The fractional crystallinity for the PPeD was much higher than PPeF and the fractional crystallinity of the copolymers showed a minimum at D/F ratios closer to the latter. Here, the stress at break and modulus both exhibited maxima at D/F ratios that were either high or low, but somewhat surprisingly a strong maximum in percent elongation at break of over 600% occurs at PPeDF40. For this composition, a typical plastic behavior curve was found including a yield point, high elongation at break, and strain hardening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

In this report, we describe the synthesis and electronic properties of small-molecule and polymeric [8]cycloparaphenylenes ([8]CPPs) with disjointed pi conjugated substituents. Arylene-ethynylene linkers were installed on opposite sides of the [8]CPP nanohoop as separated by three phenyl units on either side such that the monomer systems have syn (C2 symmetry) and anti (C1 symmetry) conformers with a small energy gap (0.1-0.6 kcal/mol). This disjoined substitution pattern necessarily forces delocalization through and around the CPP radial structure. We demonstrate new electronic states from this radial/linear mixing in both the small molecules and the pi extended polymers. Quantum chemical calculations reveal these electronic processes to arise from multiple operative radial/linear conjugation pathways, as the disjoint pattern results in both ortho and meta connections to the CPP ring. Furthermore, these results affirm the unique nature of hybrid radial and linear pi electron delocalization operative in these new conjugation pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aluminum Ultra-conductors for Energy-Efficient Aerospace Busbar Applications (Abstract)

In this project, we will develop aluminum ultra-conductors with graphene additives demonstrating enhanced electrical conductivity at 90 °C compared to electric grade aluminum alloy AA1100 (43% IACS at 90 °C). While ultra-conductivity has been developed in copper and copper alloys, it is yet to be reported extensively in aluminum-based materials. This project will scale initial work done at PNNL on aluminum ultra-conductors using shear-assisted processing and extrusion (ShAPETM), a novel solid phase processing technique. Ultra-conductors are an emerging class of composites, comprised of a metal substrate with small quantities of nanocrystalline additives such as graphene or carbon nanotubes that demonstrate enhanced conductivity at relevant operating temperatures. Aluminum ultra-conductors can improve efficiency and power density while reducing the demand for copper in a wide range of applications, such as power transmission cables and electric motors. Busbars are an important component in aerospace systems that require lightweight and high-current power distribution including both future electric vertical take-off and landing (eVTOL) aircrafts and current aircraft electrical systems. We will accelerate aluminum ultra-conductor composite formulation development using combinatorial synthesis and testing methods aided by process/microstructure modeling, developed previously at PNNL. Eaton will test the properties of the ShAPE aluminum ultra-conductor feedstock (used to make the busbars) in relevant operating conditions (20 – 90 °C), predict the improvement in busbar performance when manufactured with ultra-conductors over commercial conductors (such as AA1100), and perform technoeconomic analysis to evaluate the potential for commercialization of ShAPE aluminum ultra-conductors. The project is expected to have a budget of $\$375$K, with $\$300$K in federal funding and $\$75$K in-kind cost-share contribution from Eaton over a period of performance of 24 months. Of the $\$300$K of federal funds, $\$140$K is allocated for CRADA activities that generate intellectual property (IP), and the remaining $\$160$K is reserved for modeling, material testing, characterization, travel, and reporting-related activities.

36 MATERIALS SCIENCE↗