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At least 451 records · Page 25

Optimized Carbon Fiber Intermediate Development to Enable High-Volume Manufacturing of Lightweight Automotive Composites

The ongoing pursuit of improved fuel economy and reduced greenhouse gas emissions has resulted in sustained interest for lightweight materials technologies. In this context, carbon fiber composites have captured the imagination of automotive engineers due to the potential to achieve substantial mass reduction when compared to traditional steel construction. That stated, the use of carbon fiber composites in automotive has been limited for the most part to premium supercars and other derivative platforms. In these cases, manufacturing costs are less of an obstacle to implementation, and the performance benefits of carbon fiber have enabled production of structures offering more than 50% weight savings. In practice, translating these low-volume demonstrations onto high-volume vehicle platforms has remained challenging. This can be attributed to several factors, with the absence of suitable high throughput production methodologies being a key impediment. To date, structural, crash critical components have relied upon manufacturing techniques born out of the aerospace industry. This has created a disconnect between automotive production systems that are accustomed to manufacturing multiple parts per minute and the aerospace technologies that have cycle times in the order of hours. Consequently, the focus of this project is the development of manufacturing process technology for carbon fiber composites that can support a mainstream vehicle program at an assumed throughput of 100,000 vehicles per year. In practice, this translates to a part-to-part cycle time of less than 3 minutes. Project participation included contributions from a broad range of academic, industrial and national lab partners. The primary scope of work, being the development of new carbon fiber epoxy compounds that are stable at room temperature and suited to high throughput automated processing. For project management, the work streams were divided into six key areas, with the lead organization in parentheses. • Carbon fiber/epoxy materials formulation development and scale up (Dow) • Simulation of discontinuous near isotropic meso-structure intermediates (Purdue) • Simulation of mechanical performance of compression molded components (Purdue) • Meso-Scale morphological analysis and correlation with structural performance (UTK) • Paint and adhesion durability analysis (MSU) • Demonstrator part design, prototype production, and validation testing (Ford). The primary goal at the commencement of the project was development of a chopped carbon fiber sheet molding compound (SMC) that offered a three times improvement in tensile modulus over a comparable glass-based SMC. In addition to meeting mechanical performance targets, the resin kinetics were modified to achieve a processing cycle time of less than 3 minutes. Other critical-to-quality (CTQ) specifications were also stipulated to account for a broad range of materials and processing characteristics. To achieve the above, staff scientists at Dow Chemical created an extensive series of new epoxy blends for testing and validation. Throughout this development, a key challenge was attaining material performance goals without impacting processing behavior and paintability of finished components. The latter required a new internal mold release system being developed by Dow that was designed to complement the kinetics of the rapid cure epoxy. As a complement to work studies at the industrial partners, the teams from academia executed a series of analytical and experimental studies to investigate potential factors influencing CF-SMC performance. Unit cell models were developed to capture the meso-scale representations of the fiber matrix architecture. Results of this analysis and subsequent morphological investigations led to the design of a novel composite derivative comprising carbon fiber platelets embedded in an epoxy matrix; the platelet size and aspect ratio playing significant role in final composite properties. This approach was a departure from previous research in CF-SMC development whereby bulk filamentization or disassembly of the carbon fiber rovings had been considered the most effective means of achieving both fiber wet through and wet-out. As the course of the academia studies progressed, the aspect ratio of the fiber constituents was further optimized before finalizing material attributes and processing conditions. For the purposes of technology validation, the Ford team led a work stream devoted to the design, fabrication and testing of demonstration components. The carbon fiber SMC material has the potential to displace numerous stampings and castings on an automotive structure but ultimately vehicle closure applications were selected to showcase the abilities of the CF-SMC to achieve both mass reduction and business case for large complex structures. Using target properties established by the Dow staff scientists, the complete closure system for a full-size sedan decklid and a mid-size wagon liftgate were engineered. Prototypes for both applications were fabricated using production representative processing methods to allow for physical testing and performance validation of the CF-SMC structures. Following completion of a testing program that concluded with a FMVSS301 55 mph offset rear crash, the CF-SMC formulation was declared by the Ford team to have met all engineering requirements. To summarize, the joint development activities during this project led to significant technical breakthroughs and achievement of all milestones. The result was the development of a novel, tack-free carbon fiber molding compound that is suited to automated processing. This combined room temperature stability, fast cure kinetics, and internal mold release system facilitates cycle times that are conducive to high-volume production. The VORAFUSE M6400 successfully passed technology validation at Ford and is now eligible for consideration on future production commercial vehicle programs.

36 MATERIALS SCIENCE↗

Reanalysis Activities at the NASA Global Modeling and Assimilation Office

This talk presents an overview of recent reanalysis activities at the NASA Global Modeling and Assimilation Office (GMAO) as part of a multi-faceted strategy towards an Integrated Earth System retrospective analysis, coupling components of the atmosphere, ocean, chemistry, land, and ice. While elements of the atmosphere-ocean coupled Goddard Earth Observing System (GEOS) model and data assimilation are being actively developed, a suite of reanalysis products is designed to provide further understanding of key aspects of Earth system coupling in a reanalysis context: The baseline atmospheric reanalysis, the GEOS Retrospective analysis for the early 21st Century (GEOS-R21C), features recent advances in the GEOS model and data assimilation, and targets the NASA’s Earth Observing System EOS and post-EOS satellite observations; GEOS-IT, a user-tailored low-resolution atmospheric reanalysis, serves as a second baseline to the NASA Instrument Teams for validation and calibration and drives a one-way coupled ocean reanalysis, GEOSIT-Ocean; PolarMERRA, a high-resolution downscaled product for the polar regions, focuses on improving the representation of polar atmospheric processes with an assessment of current cryospheric biases, and targeted improvements to surface sea ice and glacier conditions; Finally, R21C-Chem, an off-line atmospheric chemistry and composition reanalysis, includes both tropospheric and stratospheric trace gases. The diversity of these reanalysis activities presents unique opportunities for collaborations cross-teams/institutions, with new commercial data partners, and with end-user groups. This talk will discuss these opportunities and explore leveraging the lessons learned along the way on key drivers in Earth system interactions as we converge towards the next generation of the Modern-Era Retrospective analysis for Research and Applications (MERRA) suite.

Amal El Akkraoui↗

Efficient production of a high-performance dispersion strengthened, multi-principal element alloy

Additive manufacturing currently facilitates new avenues for materials discovery that have not been fully explored. In this study we reveal how additive manufacturing can be leveraged to produce dispersion strengthened (DS), multi-principal element alloys (MPEA) without the use of traditional mechanical alloying or chemical reactions. This new processing technique employed resonant acoustic mixing to coat an equiatomic NiCoCr powder with nano-scale yttrium oxides. Then, through laser powder bed fusion (L-PBF), the coated powder was successfully consolidated into 99.9% dense parts. Microstructural analysis confirmed the successful incorporation and dispersion of nano-scale oxides throughout the build volume. Furthermore, high temperature mechanical testing of the DS alloys showed significant improvements in strength and ductility over the baseline NiCoCr. As a result, this recently discovered processing route opens a new alloy design and production path that is synergistic between additive manufacturing and dispersion strengthening, possibly enabling a new generation of high-performance alloys.

T.M. Smith↗

Simulation of the Impact of New Aircraft- and Satellite-Based Ocean Surface Wind Measurements on H*Wind Analyses and Numerical Forecasts

The Hurricane Imaging Radiometer (HIRAD) is a new airborne microwave remote sensor for hurricane observations that is currently under development by NASA Marshall Space Flight Center, NOAA Hurricane Research Division, the University of Central Florida and the University of Michigan. HIRAD is being designed to enhance the realtime airborne ocean surface winds observation capabilities of NOAA and USAF Weather Squadron hurricane hunter aircraft using the operational airborne Stepped Frequency Microwave Radiometer (SFMR). Unlike SFMR, which measures wind speed and rain rate along the ground track directly beneath the aircraft, HIRAD will provide images of the surface wind and rain field over a wide swath (~ 3 x the aircraft altitude). The present paper describes a set of Observing System Simulation Experiments (OSSEs) in which measurements from the new instrument as well as those from existing instruments (air, surface, and space-based) are simulated from the output of a detailed numerical model, and those results are used to construct H*Wind analyses. The H*Wind analysis, a product of the Hurricane Research Division of NOAA s Atlantic Oceanographic and Meteorological Laboratory, brings together wind measurements from a variety of observation platforms into an objective analysis of the distribution of wind speeds in a tropical cyclone. This product is designed to improve understanding of the extent and strength of the wind field, and to improve the assessment of hurricane intensity. See http://www.aoml.noaa.gov/hrd/data_sub/wind.html. Evaluations will be presented on the impact of the HIRAD instrument on H*Wind analyses, both in terms of adding it to the full suite of current measurements, as well as using it to replace instrument(s) that may not be functioning at the future time the HIRAD instrument is deployed. Plans to demonstrate the potential for HIRAD to improve numerical weather prediction of hurricanes will also be presented.

Miller, Timothy↗

Simulation of the Impact of New Aircraft- and Satellite-Based Ocean Surface Wind Measurements on H*Wind Analyses and Numerical Forecasts

The Hurricane Imaging Radiometer (HIRAD) is a new airborne microwave remote sensor for hurricane observations that is currently under development by NASA Marshall Space Flight Center, NOAA Hurricane Research Division, the University of Central Florida and the University of Michigan. HIRAD is being designed to enhance the realtime airborne ocean surface winds observation capabilities of NOAA and USAF Weather Squadron hurricane hunter aircraft using the operational airborne Stepped Frequency Microwave Radiometer (SFMR). Unlike SFMR, which measures wind speed and rain rate along the ground track directly beneath the aircraft, HIRAD will provide images of the surface wind and rain field over a wide swath (~ 3 x the aircraft altitude). The present paper describes a set of Observing System Simulation Experiments (OSSEs) in which measurements from the new instrument as well as those from existing instruments (air, surface, and space-based) are simulated from the output of a detailed numerical model, and those results are used to construct H*Wind analyses. The H*Wind analysis, a product of the Hurricane Research Division of NOAA s Atlantic Oceanographic and Meteorological Laboratory, brings together wind measurements from a variety of observation platforms into an objective analysis of the distribution of wind speeds in a tropical cyclone. This product is designed to improve understanding of the extent and strength of the wind field, and to improve the assessment of hurricane intensity. See http://www.aoml.noaa.gov/hrd/data_sub/wind.html. Evaluations will be presented on the impact of the HIRAD instrument on H*Wind analyses, both in terms of adding it to the full suite of current measurements, as well as using it to replace instrument(s) that may not be functioning at the future time the HIRAD instrument is implemented. Also shown will be preliminary results of numerical weather prediction OSSEs in which the impact of the addition of HIRAD observations to the initial state on numerical forecasts of the hurricane intensity and structure is assessed.

Miller, Timothy↗

Assessment of and standardization for quantitative nondestructive test

Present capabilities and limitations of nondestructive testing (NDT) as applied to aerospace structures during design, development, production, and operational phases are assessed. It will help determine what useful structural quantitative and qualitative data may be provided from raw materials to vehicle refurbishment. This assessment considers metal alloys systems and bonded composites presently applied in active NASA programs or strong contenders for future use. Quantitative and qualitative data has been summarized from recent literature, and in-house information, and presented along with a description of those structures or standards where the information was obtained. Examples, in tabular form, of NDT technique capabilities and limitations have been provided. NDT techniques discussed and assessed were radiography, ultrasonics, penetrants, thermal, acoustic, and electromagnetic. Quantitative data is sparse; therefore, obtaining statistically reliable flaw detection data must be strongly emphasized. The new requirements for reusable space vehicles have resulted in highly efficient design concepts operating in severe environments. This increases the need for quantitative NDT evaluation of selected structural components, the end item structure, and during refurbishment operations.

Neuschaefer, R. W.↗

Radiation Dose Modeling for Niowave’s Accelerator Driven Uranium Target Assembly 3

Molybdenum-99 is a high-value radionuclide commonly used for medical purposes within the United States. The National Nuclear Security Administration (NNSA) seeks to reliably produce the radioisotope 99 Mo without the use of highly enriched uranium. NNSA’s Office of Material Management and Minimization (M3) provides funding and government laboratory expertise to private companies to expedite the production process domestically and currently funds designs that use low-enriched uranium or other 99 Mo production pathways. Several production designs are being explored across the industry, including uranium fission and photonuclear conversion of 100 Mo targets. Niowave Inc. seeks to produce 99 Mo via a high-energy electron accelerator that strikes a lead-bismuth eutectic target that ultimately produces a consistent neutron flux. The neutron flux then interacts in a subcritical reactor core configuration to produce fission in low-enriched or natural uranium targets. These fissionable targets are then processed to extract 99 Mo. The purpose of this work is to estimate the neutron and photon dose response across Niowave’s proposed facility for worker safety during operation. Owing to the size of the proposed Niowave facility and necessary shielding, unbiased Monte Carlo radiation transport is impractical, and variance reduction methods are required. This work focuses on the weight window variance reduction method to produce high confidence dose response results within a Monte Carlo radiation transport code. Specifically, an adjoint-informed weight window methodology was created to improve the dose response estimates for accelerator-driven subcritical reactor designs. This adjoint-informed methodology was implemented for Niowave’s proposed design and improved dose results at far-field locations across the facility. Acceptable dose rate contours for the proposed facility were generated across the facility and are presented in this work.

07 ISOTOPE AND RADIATION SOURCES↗

R&D toward design for a pion-production target for Mu2e-II

The Mu2e experiment at Fermilab will search for evidence of charged lepton flavor violation by observing the conversion of a negative muon into an electron in the Coulomb field of a nucleus without emission of neutrinos and will probe effective new-physics mass scales in the 103-104 TeV range. One of the main parts of the Mu2e experimental setup is its target station in which negative pions are generated in interactions of the 8 GeV primary proton beam with a tungsten target, which will be capable of producing $2\times10^{17}$ negative muons per year. Mu2e can be extended by a next generation experiment, Mu2e-II, with a sensitivity improved by another factor of 10 or more as enabled by the PIP-II accelerator upgrade project. PIP-II is a 250-meter-long linac capable of accelerating a 2 mA proton beam to a kinetic energy of 800 MeV corresponding to 1.6 MW of power. To achieve another factor of ten improvement in sensitivity, Mu2e-II will require about 100 kW of proton beam on target, and the added power requires a new target design. We will present our progress in RD of a target station conceptual design for Mu2e-II, using the MARS15 and G4beamline Monte-Carlo codes toward a selection between granular, conveyor, and rotating cylindrical target options.

Lynch, Kevin Richard↗

Characterization of a Haematococcus pluvialis Diacylglycerol Acyltransferase 1 and Its Potential in Unsaturated Fatty Acid-Rich Triacylglycerol Production

The unicellular green alga Haematococcus pluvialis has been recognized as an industry strain to produce simultaneously esterified astaxanthin (EAST) and triacylglycerol (TAG) under stress induction. It is necessary to identify the key enzymes involving in synergistic accumulation of EAST and TAG in H. pluvialis . In this study, a novel diacylglycerol acyltransferase 1 was systematically characterized by in vivo and in silico assays. The upregulated expression of HpDGAT1 gene was positively associated with the significant increase of TAG and EAST contents under stress conditions. Functional complementation by overexpressing HpDGAT1 in a TAG-deficient yeast strain H1246 revealed that HpDGAT1 could restore TAG biosynthesis and exhibited a high substrate preference for monounsaturated fatty acyl-CoAs (MUFAs) and polyunsaturated fatty acyl-CoAs (PUFAs). Notably, heterogeneous expression of HpDGAT1 in Chlamydomonas reinhardtii and Arabidopsis thaliana resulted in a significant enhancement of total oils and concurrently a high accumulation of MUFAs- and PUFAs-rich TAGs. Furthermore, molecular docking analysis indicated that HpDGAT1 contained AST-binding sites. These findings evidence a possible dual-function role for HpDGAT1 involving in TAG and EAST synthesis, demonstrating that it is a potential target gene to enrich AST accumulation in this alga and to design oil production in both commercial algae and oil crops.

Cui, Hongli↗

Test program, helium II orbital resupply coupling

The full scope of this program was to have included development tests, design and production of custom test equipment and acceptance and qualification testing of prototype and protoflight coupling hardware. This program was performed by Ball Aerospace Systems Division, Boulder, Colorado until its premature termination in May 1991. Development tests were performed on cryogenic face seals and flow control devices at superfluid helium (He II) conditions. Special equipment was developed to allow quantified leak detection at large leak rates up to 8.4 x 10(exp -4) SCCS. Two major fixtures were developed and characterized: The Cryogenic Test Fixture (CTF) and the Thermal Mismatch Fixture (Glovebox). The CTF allows the coupling hardware to be filled with liquid nitrogen (LN2), liquid helium (LHe) or sub-cooled liquid helium when hardware flow control valves are either open or closed. Heat leak measurements, internal and external helium leakage measurements, cryogenic proof pressure tests and external load applications are performed in this fixture. Special reusable MLI closures were developed to provide repeatable installations in the CTF. The Thermal Mismatch Fixture allows all design configurations of coupling hardware to be engaged and disengaged while measuring applied forces and torques. Any two hardware components may be individually thermally preconditioned within the range of 117 deg K to 350 deg K prior to engage/disengage cycling. This verifies dimensional compatibility and operation when thermally mismatched. A clean, dry GN2 atmosphere is maintained in the fixture at all times. The first shipset of hardware was received, inspected and cycled at room temperature just prior to program termination.

Hyatt, William S.↗

A new non-diffusional gas bubble production route in used nuclear fuel: Implications for fission gas release, cladding corrosion, and next generation fuel design

The relationship between noble metal phase particles and fission gas bubble production in used nuclear fuel is described. The majority of Te atoms within noble metal phase undergo radioactive decay to form stable Xe within a few hours after particle formation. This results in the production of clusters of Xe atoms contained within the solid metal matrix exhibiting an equivalent gas bubble pressure approaching 1 GPa. These high pressure bubbles are stabilized by the UO2 within the bulk of the fuel. However, when these bubbles form near the fuel / cladding interface, in combination with local and temporal damage caused by fission recoil, they are capable of overcoming the fracture strength of the UO2 and rupturing catastrophically. The force of the resulting bubble rupture is sufficient to eject noble metal phase particles several microns into the cladding. This proposed mechanism explains the observance of noble metal phase in cladding and is consistent with a host of morphological features found near the fuel / cladding interface.

Schwantes, Jon M.↗

Simulation of the Impact of New Aircraft and Satellite-Based Ocean Surface Wind Measurements on H*Wind Analyses

Accurate observations of surface ocean vector winds (OVW) with high spatial and temporal resolution are required for understanding and predicting tropical cyclones. As NASA's QuikSCAT and Navy's WindSat operate beyond their design life, many members of the weather and climate science communities recognize the importance of developing new observational technologies and strategies to meet the essential need for OVW information to improve hurricane intensity and location forecasts. The Hurricane Imaging Radiometer (HIRAD) is an innovative technology development which offers new and unique remotely sensed satellite observations of both extreme oceanic wind events and strong precipitation. It is based on the airborne Stepped Frequency Microwave Radiometer (SFMR), which is the only proven remote sensing technique for observing tropical cyclone (TC) ocean surface wind speeds and rain rates. The proposed HIRAD instrument advances beyond the current nadir viewing SFMR to an equivalent wide-swath SFMR imager using passive microwave synthetic thinned aperture radiometer (STAR) technology. This sensor will operate over 4-7 GHz (C-band frequencies) where the required TC remote sensing physics has been validated by both SFMR and WindSat radiometers. The instrument is described in more detail in a paper by Jones et al. presented to the Tropical Meteorology Special Symposium at this AMS Annual Meeting. Simulated HIRAD passes through a simulation of hurricane Frances are being developed to demonstrate HIRAD estimation of surface wind speed over a wide swath in the presence of heavy rain. These are currently being used in "quick" OSSEs (Observing System Simulation Experiments) with H'Wind analyses as the discriminating tool. The H'Wind analysis, a product of the Hurricane Research Division of NOAA's Atlantic , Oceanographic and Meteorological Laboratory, brings together wind measurements from a variety of observation platforms into an objective analysis of the distribution of wind speeds in a tropical cyclone. This product is designed to improve understanding of the extent and strength of the wind field, and to improve the assessment of hurricane intensity. See http://www.aoml.noaa._ov/hrd/data sub/wind.html. Observations have been simulated from both aircraft altitudes and space. The simulated flight patterns for the aircraft platform cases have been designed to duplicate the timing and flight patterns used in routine NOAA and USAF hurricane surveillance flights, and the spaceborne case simulates a TRMM orbit and altitude.

Miller, TImothy L.↗

A Survey of Applications and Research in Integrated Design Systems Technology

The initial part of the study was begun with a combination of literature searches, World Wide Web searches, and contacts with individuals and companies who were known to members of our team to have an interest in topics that seemed to be related to our study. There is a long list of such topics, such as concurrent engineering, design for manufacture, life-cycle engineering, systems engineering, systems integration, systems design, design systems, integrated product and process approaches, enterprise integration, integrated product realization, and similar terms. These all capture, at least in part, the flavor of what we describe here as integrated design systems. An inhibiting factor in this inquiry was the absence of agreed terminology for the study of integrated design systems. It is common for the term to be applied to what are essentially augmented Computer-Aided Design (CAD) systems, which are integrated only to the extent that agreements have been reached to attach proprietary extensions to proprietary CAD programs. It is also common for some to use the term integrated design systems to mean a system that applies only, or mainly, to the design phase of a product life cycle. It is likewise common for many of the terms listed earlier to be used as synonyms for integrated design systems. We tried to avoid this ambiguity by adopting the definition of integrated design systems that is implied in the introductory notes that we provided to our contacts, cited earlier. We thus arrived at this definition: Integrated Design Systems refers to the integration of the different tools and processes that comprise the engineering, of complex systems. It takes a broad view of the engineering of systems, to include consideration of the entire product realization process and the product life cycle. An important aspect of integrated design systems is the extent to which they integrate existing, "islands of automation" into a comprehensive design and product realization environment. As the study progressed, we relied increasingly upon a networking approach to lead us to new information. The departure point for such searches often was a government-sponsored project or a company initiative. The advantage of this approach was that short conversations with knowledgeable persons would usually cut through confusion over differences of terminology, thereby somewhat reducing the search space of the study. Even so, it was not until late in our eight-month inquiry that we began to see signs of convergence of the search, in the sense that a number of the latest inquiries began to turn up references to earlier contacts. As suggested above, this convergence often occurred with respect to particular government or company projects.

Source record↗

The scintillator surface detector of the Pierre Auger observatory

Data collected so far by the Pierre Auger Observatory have enabled major advances in ultra-high energy cosmic ray physics and demonstrated that improved determination of masses of primary cosmic-ray particles, preferably on an event-by-event basis, is necessary for understanding their origin and nature. Improvement in primary mass measurements was the main motivation for the upgrade of the Pierre Auger Observatory, called AugerPrime. As part of this upgrade, scintillator detectors are added to the existing water-Cherenkov surface detector stations. By making use of the differences in detector response to the electromagnetic particles and muons between scintillator and water-Cherenkov detectors, the electromagnetic and muonic components of cosmic-ray air showers can be disentangled. Since the muonic component is sensitive to the primary mass, such combination of detectors provides a powerful way to improve primary mass composition measurements over the original Auger surface detector design. In this paper, the so-called Scintillator Surface Detectors are discussed, including their design characteristics, production process, testing procedure and deployment in the field.

Detector design and construction technologies and ↗

Cutting More than Metal: Breaking the Development Cycle

New technology is changing the way we do business at NASA. The ability to use these new tools is made possible by a learning culture able to embrace innovation, flexibility, and prudent risk tolerance, while retaining the hard-won lessons learned of other successes and failures. Technologies such as 3-D manufacturing and structured light scanning are re-shaping the entire product life cycle, from design and analysis, through production, verification, logistics and operations. New fabrication techniques, verification techniques, integrated analysis, and models that follow the hardware from initial concept through operation are reducing the cost and time of building space hardware. Using these technologies to be more efficient, reliable and affordable requires we bring them to a level safe for NASA systems, maintain appropriate rigor in testing and acceptance, and transition new technology. Maximizing these technologies also requires cultural acceptance and understanding and balancing rules with creativity. Evolved systems engineering processes at NASA are increasingly more flexible than they have been in the past, enabling the implementation of new techniques and approaches. This paper provides an overview of NASA Marshall Space Flight Center's new approach to development, as well as examples of how that approach has been incorporated into NASA's Space Launch System (SLS) Program, which counts among its key tenants - safety, affordability, and sustainability. One of the 3D technologies that will be discussed in this paper is the design and testing of various rocket engine components.

Singer, Chris↗

Atomically Revealing Bulk Point Defect Dynamics in Hydrogen‐Driven γ‐Fe 2 O 3 → Fe 3 O 4 → FeO Transformation

Understanding how point defects in the bulk govern redox transformations is essential for advancing hydrogen-based metal production and designing high-performance oxide materials. This study reveals the atomic-scale mechanisms driving hydrogen-induced reduction of γ-Fe 2 O 3 to Fe 3 O 4 , focusing on how bulk vacancy dynamics dictate structural evolution and reaction kinetics. A key finding is the pronounced contrast in defect behavior between the two oxides: in γ-Fe 2 O 3 , intrinsic Fe vacancies promote oxygen vacancy clustering, destabilizing the local lattice and driving nanopore formation. In contrast, Fe 3 O 4 exhibits a higher oxygen vacancy formation energy and lacks intrinsic Fe vacancies, suppressing vacancy aggregation and maintaining a dense, pore-free structure. This divergence governs distinct reduction pathways—γ-Fe 2 O 3 undergoes an interface-reaction-limited transformation confined to the γ-Fe 2 O 3 /Fe 3 O 4 boundary, while Fe 3 O 4 supports a uniform increase in oxygen vacancy concentration, enabling bulk-phase reduction to lower-oxide FeO. Integrated in situ electron microscopy and density functional theory modeling uncover a vacancy-mediated mechanism, where synergistic cation-anion vacancy dynamics steer microstructure evolution and phase progression. These insights highlight the critical role of vacancy dynamics in controlling oxide reactivity and offer a pathway toward vacancy engineering to enhance reduction kinetics in hydrogen metallurgy and to tailor porosity, reactivity, and structural resilience in oxide-based catalysts and energy materials.

36 MATERIALS SCIENCE↗

Structural Basis of Sequential Enantioselective Epoxidation by a Flavin‐Dependent Monooxygenase in Lasalocid A Biosynthesis

Abstract Polyether polyketides are a structurally diverse group of natural products known for their antimicrobial and antiproliferative activities. Lasalocid A is a canonical natural polyether produced by the soil bacteriumStreptomyces lasalocidi. In lasalocid A biosynthesis, a polyene polyketide intermediate is converted into a bisepoxide by the flavin‐dependent monooxygenase enzyme Lsd18. Remarkably, Lsd18 acts on two distinct C═C groups in the substrate molecule, forming two (R,R) epoxides. We have determined the X‐ray crystal structures of Lsd18 in the substrate‐free, substrate‐bound, and product‐bound forms. Our work has revealed that Lsd18 has an extra‐large substrate‐binding pocket that allows the polyene to adopt different conformations within the enzyme pocket. This feature enables Lsd18 to epoxidate both of the C═C groups. Additionally, a subpocket located near the Lsd18 active site controls stereoselectivity by dictating which face of the C═C group is placed next to the flavin. Molecular understanding of how Lsd18 transforms a polyene into a bisepoxide during lasalocid A biosynthesis lays the foundation for the production of designer polyethers for drug development.

Chemistry↗

Impact of hydrophobic pendant phenyl groups on transport and co-transport of methanol and acetate in PEGDA-SPMAK cation exchange membranes

CO 2 reduction cells are innovative devices that reduce CO 2 into valuable chemicals (i.e. methanol (MeOH) and acetate (OAc – )) on the cathode. A major challenge with such devices is to develop ion exchange membranes that allow ion-selective transport (i.e., protons for cation exchange membranes, CEM) and suppress the crossover of CO 2 reduction products. To design such membranes, it is important to understand multi-solute transport behavior of these solutes. Previously, our group reported acetate diffusivities in co-transport with MeOH increase in sulfonated CEMs, where we speculated charge screening of the electrostatic interactions by co-diffusing MeOH has an impact. Here, crosslinked membranes fabricated by photopolymerization of poly(ethylene glycol) diacrylate (PEGDA), 3-sulfopropyl methacrylate potassium (SPMAK, SO 3 – -containing ionomer), and a phenyl-containing comonomer either phenoxyethyl acrylate (PEA) or poly(ethylene glycol) phenyl ether acrylate (PEGPEA)) are investigated. We observe OAc – diffusivities to both (1) PEGDA-SPMAK and (2) PEGDA-PEGPEA increase in co-diffusion with MeOH and those to (3) PEGDA-SPMAK/PEGPEA decrease. To rationalize this emergent co-transport behavior, we speculate (1) electrostatic interactions are interfered with by co-diffusing MeOH, (2) chain mobility (segmental dynamics) increases in the presence of MeOH and (3) for films with both hydrophobic (PEGPEA) and hydrophilic (SPMAK) comonomers chain mobility (segmental dynamics) decrease due to interactions between the comonomer sidechains depressing overall solute diffusivities. Finally, while further investigations are needed, this work contributes to improving our fundamental understanding of the relationships between polymer film chemistry, solute chemistry, and emergent cotransport behavior observed and described in this work (and others) towards enabling the design of improved membrane materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗