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At least 937 records · Page 52

Laser diagnostics to characterize the in-flame growth of platinum nanoparticles manufactured by the reactive spray deposition technology

Reactive Spray Deposition Technology (RSDT) is an atmospheric pressure, flame-based advanced manufacturing method used to fabricate Membrane Electrode Assemblies (MEAs) for proton exchange fuel cells and water electrolyzers. RSDT combines the flame synthesis of catalyst nanoparticles and their deposition onto the membrane in one step. The properties of the synthesized nanoparticles, such as their Size Distribution Function (SDF), determine the manufactured electrodes’ performance, which can be evaluated when the deposition is complete via ex-situ characterization of the products. Efforts to improve RSDT for manufacturing state-of-the-art MEAs can be significantly enhanced with integrated laser diagnostics that enable in situ measurement of the synthesized catalyst nanoparticles. This paper reports the implementation of laser diagnostics in an RSDT facility and evaluates their potential to assist the manufacturing process. Laser Light Scattering (LS) and Laser-Induced Incandescence (LII) measurements are performed in the oxygen-rich zone of the flame at various distances from the flame fuel jet nozzle downstream of its luminous region. The measurements quantitatively track the evolution in size and volume fraction of platinum-based nanoparticles in two flames that yield different catalytic properties in the manufactured electrodes. The profiles of the measured nanoparticles’ volume fraction along the flame axis can be estimated a priori so that the average nanoparticle sizes can be measured in quasi-real time via LS. Nanoparticles experience an extremely slow growth rate while being convected at distances from 150 nm to 300 nm from the fuel nozzle. Complementary characterizations of the synthesized nanoparticles are performed ex-situ via High-Angle Annular Darkfield Scanning Transmission Electron Microscopy (HAADF-STEM) image analyses of samples collected on grids at a fixed distance from the fuel jet nozzle. Comparing the results from laser and microscopy techniques not only cross-validates the findings but also provides the parameters to infer the bimodal SDF in-situ and yields evidence that the coagulation efficiency of the synthesized nanoparticles has extremely low values in the investigated zone of the flames.

Rayleigh Light Scattering (LS)↗

Optimizing high energy density sulfur cathodes: A multivariate approach to electrode formulation and processing

Lithium-sulfur (Li-S) batteries involve complex solid-liquid-solid phase transformations during both discharging and charging processes, where cathode materials, formulation, and structure play a crucial role. Here, a design of experiments (DoE) methodology and an empirical model are developed to systematically explore the interactions and trade-offs among cathode factors and process variables, and to obtain generalizable effects estimates for the multivariate system. Compared to the conventional one-factor-at-a-time (OFAT) approach, this work demonstrates advantages in both efficiency and accuracy by allowing the data to guide future research and decisions. Further, an optimized cathode formulation and processing parameters are predicted and validated experimentally, achieving over 1000 mAh g -1 in discharge capacity and improved cycling under practical lean electrolyte (4 µL mg -1 S) and high S-loading cathodes (>4 mg cm -2 ) conditions. The optimized cathode was scaled up and assembled into Li-S pouch cells, achieving 316 Wh kg -1 in cell-level energy, proving that the comprehensive and rigorous framework for optimizing complex systems with DoE leads to improved performance in a practical pouch cell system.

25 ENERGY STORAGE↗

A durable polyvinyl butyral-CsH 2 PO 4 composite electrolyte for solid acid fuel cells

We report a composite electrolyte membrane composed of polyvinyl butyral (PVB) and CsH 2 PO 4 has been prepared via a facile and cost-effective method for solid acid fuel cells. The effect of PVB content on conductivity, mechanical integrity, and fuel cell performance is investigated. A minimum amount of 3 wt% PVB in the CsH 2 PO 4 -based composite electrolyte not only offers the required mechanical integrity but also allows high conductivity (~28 mS cm -1 at 260 °C). Single cells based on the composite electrolytes demonstrate a peak power density of 108 mW cm -2 at 260 °C. Almost no degradation in electrochemical performance could be observed during the stability test for 10 h and three thermal-cycling test in H 2 /O 2 fuel cell, indicating the promising application of the composite electrolyte in solid acid fuel cells.

25 ENERGY STORAGE↗

Effect of temperature on capacity fade in silicon-rich anodes

Coin half-cells containing 80 wt% silicon electrodes are assembled and cycled at the similar to C/10 rate in the temperature range of 25-55 degrees C. To the best of our knowledge, this is the first time that the effect of temperature is reported for such high-silicon-containing cells. Two different electrolytes are used in this study, a baseline electrolyte and the baseline electrolyte +10 wt% fluoroethylene carbonate (FEC). Analysis of the capacity vs. cycle count data by curve fitting reveals that the addition of FEC markedly affects the capacity loss mechanism. Without FEC, the kinetic rate law for the capacity loss mechanism can be described as the sum of two logistic growth models. With the addition of FEC, the rate law depends on ln(t). Clearly, the addition of FEC has a profound effect on the mechanism of capacity loss. Interestingly, X-ray photoelectron spectroscopy (XPS) shows that the composition of the solid electrolyte interphase (SEI) layer changes markedly from mostly organic to mostly inorganic in the presence of FEC and how it varies at the different temperatures tested, especially in the absence of FEC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressurized Gas-Driven Elemental Redistribution Enables Ultrastable PtNi Catalysts for Heavy-Duty Vehicles

Gas-driven element redistribution, characterized by the preferential enrichment of one element at the surface relative to the bulk, is frequently observed in multicomponent alloys. Using L1 0 -ordered PtNi as a model system, we reveal that gas pressure plays a critical role in governing adsorption-driven surface composition during annealing in reducing gases: low pressure favors Pt surface segregation, while high pressure facilitates Ni surface enrichment. In this study, we developed a high-pressure nitriding (HPN) strategy that modulates the surface structure and composition of PtNi catalysts. The resulting HPN-PtNi exhibits enhanced performance and durability in membrane electrode assemblies for heavy-duty fuel cell applications, maintaining a high current density of 1.19 A cm −2 at 0.7 V after 90,000 voltage cycles. Through a combination of experimental and theoretical analyses, we reveal that the HPN process forms additional stabilizing Ni−N bonds and induces elemental redistribution with Ni surface enrichment and a Ni-deficient Pt subsurface. These modifications alter the atomic coordination environment of the ordered PtNi phase. This work presents a generalizable strategy to design robust and high-performing Pt-based catalysts by controlling gas-pressure-driven elemental redistribution and dopant incorporation.

30 DIRECT ENERGY CONVERSION↗

New Rh 2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

In this work, the new heteroleptic paddlewheel complexes cis-[Rh 2 (μ-form) 2 (μ-np) 2 ][BF 4 ] 2 , where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2 (μ-form) 2 (μ-npCOO) 2 (npCOO – = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M –1 cm –1 ) and visible regions (λ max = 640 nm ε = 3500 M –1 cm –1 ), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were used to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2 /form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO – complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3 ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.

14 SOLAR ENERGY↗

Catastrophic disassembly of actin filaments via Mical-mediated oxidation

Actin filament assembly and disassembly are vital for cell functions. MICAL Redox enzymes are important post-translational effectors of actin that stereo-specifically oxidize actin’s M44 and M47 residues to induce cellular F-actin disassembly. Here we show that Mical-oxidized (Mox) actin can undergo extremely fast (84 subunits/s) disassembly, which depends on F-actin’s nucleotide-bound state. Using near-atomic resolution cryoEM reconstruction and single filament TIRF microscopy we identify two dynamic and structural states of Mox-actin. Modeling actin’s D-loop region based on our 3.9 Å cryoEM reconstruction suggests that oxidation by Mical reorients the side chain of M44 and induces a new intermolecular interaction of actin residue M47 (M47-O-T351). Site-directed mutagenesis reveals that this interaction promotes Mox-actin instability. Moreover, we find that Mical oxidation of actin allows for cofilin-mediated severing even in the presence of inorganic phosphate. Thus, in conjunction with cofilin, Mical oxidation of actin promotes F-actin disassembly independent of the nucleotide-bound state.

Science & Technology - Other Topics↗

Nanosecond cryogenic Yb:YAG disk laser

A cryogenic Yb:YAG disk laser is modernised to increase its average and peak power. The master oscillator unit of the laser is considerably modified so that the pulse duration decreases to several nanoseconds with the same pulse energy. A cryogenic disk laser head with a flow-through cooling system is developed. Based on two such laser heads, a new main amplifier is assembled according to an active multipass cell scheme. The total small-signal gain of cryogenic cascades is ∼10{sup 8}. (lasers)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

EEPD1 evolved a unique DNA clamping dimer protecting reversed replication forks

Exonuclease/endonuclease/phosphatase (EEP)-fold hydrolases are canonically monomeric phosphodiesterases exemplified by APE1, DNase I, and TDP2 nucleases. While EEP family domain containing protein 1 (EEPD1) acts in DNA stress responses, its proposed nuclease activities are enigmatic. Here, we integrate hybrid structural methods, evolution, biochemistry, cancer genomics, plus molecular and cell biology to define EEPD1 structure, assembly, and function at stalled DNA replication forks. Results imply EEPD1 surprisingly requires both unique EEP domain dimer and distinctive tandem Helix-hairpin-Helix [(HhH) 2 ] domains to clamp double-stranded (ds) DNA at reversed DNA replication forks for fork protection. Small-angle X-ray Scattering (SAXS), crystal, and cryo-EM structures unveil an unprecedented tryptophan handshake dimer, conserved interface di-Trp-Pro pocket, and adjustable “wrist” enabling an open-closed conformational switch. EEPD1 dimer cooperatively binds complex dsDNA replication fork intermediates but alone lacks nuclease activity due to loss of key EEP catalytic residues during Metazoan evolution and atmospheric oxygen buildup. Instead, EEPD1 prevents nucleolytic degradation of reversed replication forks by MRE11. Furthermore, cancer bioinformatics support oxidative damage-dependent EEPD1 association as a significant modulator of overall patient survival. Collective findings uncover unexpected EEP dimer and fork protection function in clamping, not cleaving, reversed replication forks for metazoan oxidative stress responses controlling genome stability and cancer outcomes.

Shen, Runze [Univ. of Texas, Houston, TX (United S↗

A 4×4 electrooptic silicon photonic switch fabric with net neutral insertion loss

We present a strictly nonblocking 4×4 electrooptic silicon photonic switch fabric with on-chip gain. The switch integrates 12 Mach-Zehnder cells in a 3-stage topology equipped with fast electrooptic phase shifters, and thermooptic phase trimmers. To compensate for the losses of the fabric, a 4-channel GaInAsP/InP semiconductor optical amplifier array is flip-chip attached into an etched cavity in the silicon photonic chip with butt-coupled waveguide interfaces. The chip is wirebonded to a CMOS driver that provides push-pull drive to each elementary Mach-Zehnder cell. We demonstrate an optical switch assembly with net neutral insertion loss in the C-band together with nanosecond-scale reconfiguration time.

42 ENGINEERING↗

A High-Ceramic-Loading LATP–PVDF–Al 2 O 3 Composite Film for Lithium-Ion Batteries With Favorable Porous Microstructure and Enhanced Thermal Stability

A separator plays a crucial role in a Li-ion battery to carry liquid electrolytes while preventing short-circuiting between electrodes. Nevertheless, conventional commercial separators often exhibit poor wettability and are prone to shrink at elevated temperatures due to their limited thermal stability. Herein, we report a heat-resistant LATP–PVDF–Al 2 O 3 composite film with outstanding wetting performance. The thin film was prepared using ball mill mixing and tape-casting processes. Two solvents, NMP and glycerol, were applied to prepare the slurry, and a favorable microstructure in the film was created after drying. Here, the ionic conductivity of the film was tested at 1.39 mS cm –1 when paired with liquid electrolyte, almost double that of the commercial counterpart. The high ceramic loading of 70% improved both the thermal shrinkage resistance and dendrite inhibition of the membrane. When assembled in an NMC half-cell, the cycling capacity retentions of 92.8% and 92.1% are achieved after 50 cycles at 0.5 C and 1 C, demonstrating its capability to be used in Li-ion batteries.

25 ENERGY STORAGE↗

Positioning Accuracy in a Concurrent Robot-CNC Hybrid Manufacturing System

Abstract Additive manufacturing (AM) has gained notoriety for offering advantages over traditional manufacturing methods, such as increased design complexity and flexibility. However, it has not found widespread use beyond rapid prototyping. One hindrance to the acceptance of AM processes in industry is the time and cost of fabrication per component. While metal AM by itself can be inexpensive, extra manufacturing steps in the form of subtractive manufacturing (SM) may need to be performed to reach final part tolerances, leading to hybrid additive-subtractive manufacturing (HASM) of a part, which increases time and cost. A potential area to reduce cost is through increasing the efficiency of the HASM process by conducting additive and subtractive manufacturing simultaneously. Usually, HASM is performed in a process where AM is completed in one machine or cell and transferred to another machine or cell for SM in a sequential assembly line process. This efficiency decreases part cost, but high aspect ratio parts or parts with internal geometry that require interleaved additive deposition and machining cannot be produced. One unexplored solution to simultaneous HASM that allows for interleaved operations is to operate the deposition head and machining spindle concurrently within the same machine envelope, known as concurrent HASM (CHASM). In this type of process, both AM and SM occur simultaneously on a batch of small parts or a single large part, maintaining a high efficiency without sacrificing the full range of complex geometries that AM allows for. A potential approach to the single-machine method could be to combine a robot and mill within the same envelope. A challenge to this approach, however, is control of both systems. Most machine controllers have limited external communication or, if a robot has been integrated, only offer movement of either the robot or mill at any given time. As a result, systems must pause either the AM or SM process to switch between them rather than working simultaneously. The present work investigates the positional accuracy of such a CHASM system comprised of a robotic arm and a 3-axis mill. Open-loop tests with limited communication between machines are performed on the system to verify positional error during concurrent robot-mill movements. Under certain conditions, it is demonstrated that position error can stay within 2 mm for the duration of a single layer; however, these tests show that, generally, the open-loop positioning performance of the system is inadequate for CHASM without part-specific hand-tuning of parameters. Based on these results, a set of requirements for successful robot-CNC CHASM is proposed for future integrations.

Goodwin, Jesse↗

Unique organization and unprecedented diversity of the Bacteroides (Pseudobacteroides) cellulosolvens cellulosome system

The organization of the B. cellulosolvens cellulosome is unique compared to previously described cellulosome systems. In contrast to all other known cellulosomes, the cohesin types are reversed for all scaffoldins i.e., the type II cohesins are located on the enzyme-integrating primary scaffoldin, whereas the type I cohesins are located on the anchoring scaffoldins. Many of the type II dockerin-bearing ORFs include X60 modules, which are known to stabilize type II cohesin–dockerin interactions. In the present work, we focused on revealing the architectural arrangement of cellulosome structure in this bacterium by examining numerous interactions between the various cohesin and dockerin modules. In total, we cloned and expressed 43 representative cohesins and 27 dockerins. The results revealed various possible architectures of cell-anchored and cell-free cellulosomes, which serve to assemble distinctive cellulosome types via three distinct cohesin–dockerin specificities: type I, type II, and a novel-type designated R (distinct from type III interactions, predominant in ruminococcal cellulosomes). The results of this study provide novel insight into the architecture and function of the most intricate and extensive cellulosomal system known today, thereby extending significantly our overall knowledge base of cellulosome systems and their components. The robust cellulosome system of B. cellulosolvens, with its unique binding specificities and reversal of cohesin–dockerin types, has served to amend our view of the cellulosome paradigm. Revealing new cellulosomal interactions and arrangements is critical for designing high-efficiency artificial cellulosomes for conversion of plant-derived cellulosic biomass towards improved production of biofuels.

09 BIOMASS FUELS↗

A Versatile Click-Compatible Monolignol Probe to Study Lignin Deposition in Plant Cell Walls

Here, lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro -polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly.

59 BASIC BIOLOGICAL SCIENCES↗

A gas-loading system for LANL two-stage gas guns

A novel gas loading system was designed for the specific application of remotely loading high purity gases into targets for gas-gun driven plate impact experiments. The high purity gases are loaded into well-defined target configurations to obtain Hugoniot states in the gas phase at greater than ambient pressures.The small volume of the gas samples is challenging, as slight changing in the ambient temperature result in measurable pressure changes. Therefore, the ability to load a gas gun target and continually monitor the sample pressure prior to firing provides the most stable and reliable target fielding approach. We present the design and evaluation of a gas loading system built for the LANL 50 mm bore two-stage light gas gun. Targets for the gun are made of 6061 Al or OFHC Cu, and assembled to form a gas containment cell with a volume of approximately 1.38 cc. The compatibility of materials was a major consideration in the design of the system, particularly for its use with corrosive gases. Piping and valves are stainless steel with wetted seals made from Kalrez® and Teflon®. Preliminary testing was completed to ensure proper flow rate and that the proper safety controls were in place. The system has been used to successfully load Ar, Kr, Xe, and anhydrous ammonia with purities of up to 99.999 percent. The design of the system and example data from the plate impact experiments will be shown.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-throughput chemical imaging for optimizing biofuel synthesis using synthetic biology (Final Technical Report)

Fatty acids can be produced biosynthetically in microbes and these compounds can serve as precursors to biodiesels and other high value oleochemicals. However, progress on engineering fatty acid biosynthesis, and biofuel synthesis more generally, has been hindered by current quantification methods that are either indirect or not amenable to high-throughput or single-cell resolution screening. In this project, we assembled an interdisciplinary team with complimentary expertise in synthetic biology and microscopy, metabolic engineering, and chemical imaging to address these challenges. We used chemical imaging to directly measure lipid biosynthesis in Escherichia coli engineered to produce fatty acids, obtaining detailed single-cell resolution measurements. We deployed stimulated Raman scattering (SRS) microscopy in concert with multiplexed genome engineering and gene circuit design strategies from synthetic biology to optimize production of fatty acids. These results provided novel insight into cell-to-cell heterogeneity present in biofuel production strains. In addition, we introduced new chemical imaging methods which are label-free and do not require fluorescent reporters. These efforts were complemented by other studied developing foundational tools for regulation and control, which offer excellent potential for advancing researchers’ ability to rapidly design, build, and test strains for enhanced biofuel synthesis.

09 BIOMASS FUELS↗