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At least 685 records · Page 38

Ethylene polymerization with a crystallographically well-defined metal–organic framework supported catalyst

The inherent crystallinity of metal–organic framework (MOF) catalysts offers the possibility to understand the structure of the active site at the molecular level. This property is often lacking in traditional amorphous supports. Cr-SIM-NU-1000, a MOF-supported Cr 3+ heterogeneous catalyst, is shown to be competent for ethylene polymerization after activation with AlEt 2 Cl (DEAC), producing crystalline linear polyethylene (PE). The polymer produced has a low polydispersity (D = 2.0), in marked contrast to the Phillips supported chromium catalyst, Cr@SiO 2 (D ~ 8–65). Cr-SIM-NU-1000 achieves a turnover frequency of 2.6 × 10 3 h –1 under 40 bar ethylene pressure at room temperature, with corresponding PE productivity of 1.3 × 10 5 g PE mol –1 Cr per h. Single crystal X-ray diffraction (SC-XRD) of the pre-catalyst was conducted by collecting a structure of alkyl aluminum (DEAC) co-catalyst treated Cr-SIM-NU-1000. This crystal structure provides insight into the interactions between DEAC co-catalyst and Cr active site, revealing a Cr–C bond after treatment with DEAC. Furthermore, DEAC is crystallographically resolved at the terminal oxy-ligands of the node and likely also exists within the window pores of the framework between nodes, based on electron density mapping. Cr-SIM-NU-1000 offers the opportunity to study a structurally well-defined olefin polymerization system, with atomically precise characterization of the pre-catalyst structure. Furthermore, this allows the proposal of a mechanism and feeds into future development of next-generation heterogeneous catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and Characterization of Densified Biomass-plastic Blend for Entrained Flow Gasification (Final Technical Report)

Supported by the U.S. DOE NETL Award DE-FE0032043, this project was a collaborative effort. Project participants included the University of Kentucky Institute for Decarbonization and Energy Advancement (UK IDEA), Biosystems and Agricultural Engineering department (UK BAE), and Wabash Valley Resources, LLC. The goal of this final technical project report is to comprehensively summarize the work conducted on project DE-FE0032043. In accordance with the Statement of Project Objectives (SOPO), the University of Kentucky (UK) (Project Prime Recipient) has developed and studied a biomass/plastic fuel with a hydrophobic surface area less than 10 m 2 /m 3 that is suitable for oxygen-blown entrained flow gasification with slurry feed. The project involved the utilization of an existing thermogravimetric analysis (TGA)-mass spectrometer (MS), 1.5” drop tube furnace, 1 ton per day (TPD) coal gasifier, and high-pressure extruder operated at UK. The pilot-scale production of blended material was done at the Polymers Technology Center in Charlotte, North Carolina. Parametric testing and solid fuel blend slurry performance validation was completed using the UK entrained flow gasifier with multiple opposed burners to narrow the major near-term technical gaps that impede gasification of biomass and carbonaceous mixed wastes such as plastics in order to achieve net-negative CO 2 emissions. Project results validated the UK approach to address the major technical challenges on the biomass/plastic pretreatment and gasification. Previously, this has been limited in application to fluidized-type or moving bed-type gasifiers due to the high-water uptake of porous biomass containing hydroxyl groups during the conventional slurry preparation, resulting in a highly viscous, un-pumpable slurry. The biomass pretreatment with plastic developed for this project demonstrates advantages in cost and flexibility, which include: 1) the development of a blended solid fuel slurry with 55-60 wt% solids and comparable heating value to 100% coal-based water slurry; 2) the collection of gasification kinetic data and identification of preliminary operating conditions by performing thermogravimetric analysis, gasification experiments by using a 1.5” drop tube furnace; and finally 3) the demonstrated gasification of the blended solid fuel in the UK entrained flow gasifier with a long-lasting stable solid fuel blend slurry, dataset detailing operating conditions, and characterization of slag phase formation and solidification. The lab-scale data and experience obtained during this project encourages the development of technologies and commercial approaches to enable a hydrogen-based energy economy while achieving net-negative CO 2 emissions through gasification of coal, biomass, and carbonaceous mixed wastes such as plastics.

01 COAL, LIGNITE, AND PEAT↗

Rapidly ramp cryogenic air separation unit without loss of O2 product purity—application for low-carbon fossil-fuel plants

The rapid integration of intermittent renewable sources into the electricity grid is driving the need for low-carbon, fossil-fuel power plant capable of rapid ramping. Therefore, a cryogenic air separation unit (ASU) as part of low-carbon, fossil-fuel power plant should be capable of rapid ramping. However, highly integrated and nonlinear processes of the ASU would significantly restrict this rapid ramping. To overcome this fundamental issue, we study the basic dynamic process of a state-of-the-art double-column ASU. A flow-driven dynamic model was established in Aspen Plus Dynamics, assuming perfect flow controls, to capture the basic dynamics of ramping ASU. We find the vapor-liquid counter-current flow structure in the low-pressure column is critical to the air separation when rapidly ramping the ASU. This flow structure is established based on a complicated heat integration process. It is simplified as an apparent counter-current heat transfer process in this work, which greatly reduces the complexity for studying the dynamics of ASU. For keeping this basic flow structure, the heat integration is maintained as its heat duty follows the ASU load, through several basic feed-forward and feed-back controllers on the critical stream flowrates. Moreover, we find a fundamental issue of mismatched dynamics in the low-pressure column, resulting in a significant loss of O2 product purity when rapidly ramping down the ASU and an obvious fluctuation of O2 product purity. Based on these explorations, we propose a basic control method for rapidly ramping the ASU without loss of O2 product purity. Results show the ASU basic dynamic process successfully ramps at a rate up to 10%/min (40-100% load) while maintaining the O2 product purity within 95.2-95.6 mol%.

Cheng, Mao↗

Arc termination cracks in Inconel 718 and Incoloy 903

The welding of the nickel base, heat resistant alloys that are used extensively for welded Shuttle engine components revealed solidification cracking characteristics at weld termination points. If not detected and removed, these crater cracks may cause costly component failure. To better understand this characteristic, welding termination techniques were studied and methods developed to eliminate crater cracks. It was determined that weld termination solidification cracking can be eliminated by controlled decrease of welding current, welding voltage, wire feed, and travel speed.

Bayless, E.↗

Molecular-beam sampling study of extinguishment of methane-air flames by dry chemicals

The use of Al2O3, NaHCO3, KHCO3, NH4H2PO4 and KCl powders for the inhibition of a methane/oxygen diffusion flame is studied through measurement of composition and temperature profiles, using a molecular beam mass spectrometer sampling system. In order to obtain significant inhibition without extinguishing the flame, a powder feeding rate of 2 mg/liter of gas was used for KCl and Al2O3, and of 3 mg/liter of gas for the remaining powders. CH4, O2, N2, H2O and CO2 concentrations were measured by the mass spectrometer, while temperature was measured by the time-of-flight technique. For the powder feeding rates used, Al2O3 was the least and KCl and NH2H4PO2 the most effective in reducing temperature; in reaction-inhibition effectiveness, Al2O3 was again lowest while KCl was superior to all others. Because the KCl concentration was only 2/3 that of NH4H2PO4, it is recommended as the most effective temperature reducer and reaction inhibitor.

Knuth, E. L.↗

Discrete-vortex model for the symmetric-vortex flow on cones

A relatively simple but accurate potential flow model was developed for studying the symmetric vortex flow on cones. The model is a modified version of the model first developed by Bryson, in which discrete vortices and straight-line feeding sheets were used to represent the flow field. It differs, however, in the zero-force condition used to position the vortices and determine their circulation strengths. The Bryson model imposed the condition that the net force on the feeding sheets and discrete vortices must be zero. The proposed model satisfies this zero-force condition by having the vortices move as free vortices, at a velocity equal to at the local crossflow velocity at their centers. When the free-vortex assumption is made, a solution is obtained in the form of two nonlinear algebraic equations that relate the vortex center coordinates and vortex strengths to the cone angle and angle of attack. The vortex center locations calculated using the model are in good agreement with experimental values. The cone normal forces as well as center locations are in good agreement with the vortex cloud method of calculating symmetric flow fields.

Gainer, Thomas G.↗

Shock Associated Periodicities

The magnetosphere is often thought of as a cavity resonator, with eigenfrequencies dependent on the size of the magnetospheric cavity and the Alfven speed profile. A commonly invoked mechanism to "ring the bell" is a solar wind shock or dynamic pressure discontinuity. The sudden impulse feeds broadband compressional power into the magnetosphere, feeding energy into the cavity eigenmodes. Although the cavity mode model has strong theoretical and simulation support, there are few observations validating the scenario. We present several case studies indicating that damped oscillations observed in the magnetosphere following a shock are clearly directly driven by oscillations already present in the solar wind. We discuss these new observations in the context of the turbulent solar wind model, and discuss recent observations relating these periodicities to the solar surface. We further report on similar oscillations observed in magnetotail flow bursts, and relate them to the solar wind phenomena. We close with a discussion of the role of modulated magnetic reconnection, a potentially universal physical process.

Kepko, Larry↗

Addressing genome scale design tradeoffs in Pseudomonas putida for bioconversion of an aromatic carbon source

Genome-scale metabolic models (GSMM) are commonly used to identify gene deletion sets that result in growth coupling and pairing product formation with substrate utilization and can improve strain performance beyond levels typically accessible using traditional strain engineering approaches. However, sustainable feedstocks pose a challenge due to incomplete high-resolution metabolic data for non-canonical carbon sources required to curate GSMM and identify implementable designs. Here we address a four-gene deletion design in the Pseudomonas putida KT2440 strain for the lignin-derived non-sugar carbon source, p-coumarate (p-CA), that proved challenging to implement. We examine the performance of the fully implemented design for p-coumarate to glutamine, a useful biomanufacturing intermediate. In this study glutamine is then converted to indigoidine, an alternative sustainable pigment and a model heterologous product that is commonly used to colorimetrically quantify glutamine concentration. Through proteomics, promoter-variation, and growth characterization of a fully implemented gene deletion design, we provide evidence that aromatic catabolism in the completed design is rate-limited by fumarase hydratase (FUM) enzyme activity in the citrate cycle and requires careful optimization of another fumarate hydratase protein (PP_0897) expression to achieve growth and production. A double sensitivity analysis also confirmed a strict requirement for fumarate hydratase activity in the strain where all genes in the growth coupling design have been implemented. Metabolic cross-feeding experiments were used to examine the impact of complete removal of the fumarase hydratase reaction and revealed an unanticipated nutrient requirement, suggesting additional functions for this enzyme. While a complete implementation of the design was achieved, this study highlights the challenge of completely inactivating metabolic reactions encoded by under-characterized proteins, especially in the context of multi-gene edits.

59 BASIC BIOLOGICAL SCIENCES↗

In planta single-molecule imaging and holographic force spectroscopy to study real-time, multimodal turnover dynamics of polysaccharides and associated carbohydrate metabolites

Cellular production of polysaccharides from simple sugar molecules serves critical roles in a variety of metabolic processes essential to the survival of every living organism. In the context of photosynthetically fixed carbon, cell wall polysaccharides synthesis is particularly of interest for increased biomass accumulation for human food, animal feed, and bioenergy related applications. Despite a long history of research in plant cell biology, our understanding of in planta cell wall biosynthesis and its regulation is far from complete due to lack of a comprehensive microscopy toolkit that encompass the multiple spatial and temporal scales in which cell wall polysaccharides fibrils are synthesized and assembled into intricate cell wall networks. In this project, a multidisciplinary team of scientists from Rutgers University, Vanderbilt University, and Oak Ridge National Laboratory carried out innovative multimodal, multiscale microscopy studies of cell wall synthesis using single-molecule force-spectroscopy, super-resolution fluorescence microscopy, and in vivo live cell imaging. Our novel multimodal and holistic imaging approach revealed plant cell wall polysaccharides synthesis processes in unprecedented detail across multiple spatiotemporal scales, from a single-molecule to a single-cell. Besides, the team has made technical and scientific innovations across multiple research fields—microscopy, bioengineering, single-molecule biophysics, and plant biology, etc.—to accomplish the goals. The results from this project will greatly advance the mechanistic and holistic understanding of in planta cell wall synthesis, which will accelerate the development of better transgenic crops for bioenergy applications. Moreover, the new toolbox, combining powerful advanced microscopy assays with cell/protein engineering, will have broader impacts on molecular and cellular biology fields by paving the way for studying cellular processes occurring across multiple physical scales with multimodal microscopy methodologies.

59 BASIC BIOLOGICAL SCIENCES↗

Mucilage produced by aerial roots hosts diazotrophs that provide nitrogen in Sorghum bicolor

Sorghum ( Sorghum bicolor ) is an important food, feed, and fodder crop worldwide and is gaining popularity as an energy crop due to its high potential for biomass production. Some sorghum accessions develop many aerial roots and produce an abundant carbohydrate-rich mucilage after rain. This aerial root mucilage is similar to that observed in landraces of maize ( Zea mays ) from southern Mexico, which have been previously shown to host diazotrophs. In this study, we characterized the aerial root development of several sorghum accessions and the impact of humidity on this trait. We conducted a microbiome study of the aerial root mucilage of maize and sorghum and isolated numerous diazotrophs from field sorghum mucilage. We observed that the prevailing phyla in the mucilage were Pseudomonadota, Bacteroidota, and Bacillota. However, bacterial abundances varied based on the genotype and the location. Using acetylene reduction, 15 N 2 gas feeding, and 15 N isotope dilution assays, we confirmed that these sorghum accessions can acquire about 40% of their nitrogen from the atmosphere through these associations on aerial roots. Nitrogen fixation in sorghum aerial root mucilage offers a promising avenue to reduce reliance on synthetic fertilizers and promote sustainable agricultural practices for food, feed, fodder, and bioenergy production.

Venado, Rafael E.↗

Contributions to the study of ultrasonic machining

Problems in the industrial application of ultrasounds are discussed. Starting from the industrial characteristics of ultrasonic working, especially of hard and fragile materials that are difficult to work by means of conventional methods, the characteristics of the feed system, the circulation system of the abrasive suspension, and the ultra-acoustic unit of machines for ultrasonic working are described. Experiments on the behavior of different types of ultra-acoustic unit design and on the optimal operating conditions connected with the manner of execution, fixation, and excitation conditions are analyzed.

Savii, G.↗

Extreme Tele-Echocardiography: Methodology for Remote Guidance of In-Flight Echocardiography Aboard the International Space Station

Methods: In the year before launch of an ISS mission, potential astronaut echocardiographic operators participate in 5 sessions to train for echo acquisitions that occur roughly monthly during the mission, including one exercise echocardiogram. The focus of training is familiarity with the study protocol and remote guidance procedures. On-orbit, real-time guidance of in-flight acquisitions is provided by a sonographer in the Telescience Center of Mission Control. Physician investigators with remote access are able to relay comments on image quality to the sonographer. Live video feed is relayed from the ISS to the ground via the Tracking and Data Relay Satellite System with a 2- second transmission delay. The expert sonographer uses these images, along with twoway audio, to provide instructions and feedback. Images are stored in non-compressed DICOM format for asynchronous relay to the ground for subsequent off-line analysis. Results: Since June, 2009, a total of 27 resting echocardiograms and 5 exercise studies have been performed during flight. Average acquisition time has been 45 minutes, reflecting 26,000 km of ISS travel per study. Image quality has been adequate in all studies, and remote guidance has proven imperative for fine-tuning imaging and prioritizing views when communication outages limit the study duration. Typical resting studies have included 27 video loops and 30 still-frame images requiring 750 MB of storage. Conclusions: Despite limited crew training, remote guidance allows research-quality echocardiography to be performed by non-experts aboard the ISS. Analysis is underway and additional subjects are being recruited to define the impact of microgravity on cardiac structure and systolic and diastolic function.

Martin, David S.↗

Material extrusion with integrated compression molding of NdFeB/SmFeN nylon bonded magnets using small- and large-scale pellet-based 3D-printers

High-density bonded rare-earth magnets are manufactured using pellet-fed additive manufacturing (AM)/material extrusion and an integrated additive manufacturing-compression molding (AM-CM) process. Neodymium iron boron – samarium iron nitride in polyamide 12 (NdFeB-SmFeN/PA12) of 93 % weight fraction (65 % volume fraction) are used for the study. The mechanical properties (tensile strength and modulus), magnetic properties (maximum energy density, coercivity, remanence) are reported. Manufacturing parameters such as layer height, barrel temperatures, screw speed and gantry feed rate are optimized to obtain the highest possible density of the magnets using a small-scale desktop material extrusion printer. Large scale integrated additive manufacturing-compression molding (AM-CM) is then utilized to increase the density of the magnets by reducing porosity defects common in the material extrusion process. The density of as-printed magnets was 5.2 g/cm 3 with a BH max value of 124.14 kJ/m 3 , tensile strength of 20 MPa and a modulus of 2 GPa. AM-CM increased the density of the compound by 5.5 % (5.49 g/cm 3 ). The reduction in porosity was confirmed using X-ray tomography (XCT). Improvement in mechanical strength of the material was also observed, with an increase in tensile strength of 25 % (25.09 MPa) and increase in tensile modulus of 275 % (5.49 GPa). Scanning electron microscopy showed increased particle-matrix adhesion with the integrated AM-CM process.

36 MATERIALS SCIENCE↗

Performance characterization of nanofiltration, reverse osmosis, and ion exchange technologies for acetic acid separation

A major obstacle to widespread implementation of bio-based fuels and chemicals is the lack of efficient and costeffective separation methods. To purify acetic acid produced by biochemical conversion of biomass via anaerobic digestion, this work employs two commonly used separation technologies: (1) ion-exchange (IX) resin and (2) pressure-driven membranes. This study tested five commercially available strong- and weak-base anion-exchange resins and five commercially available nanofiltration (NF) and reverse osmosis (RO) membranes. The pH of the feed solution significantly affected adsorption capacity. At pH 6.3, a strong-base IX resin (IRN-78) performed best (95.1% acetate removal). With strong-base IX resins, the Langmuir isotherm model fit well, whereas for weak-base IX resins, the Freundlich isotherm provided a better fit. A pseudo-second-order kinetic model fit well for both IRN-78 and IRA-67. Regarding membrane separation, RO (BW30XFR membrane) achieved the highest rejection (98.6% acetate rejection), whereas an NF membrane (NF*) achieved the best combination of permeate flux (105 L/(h∙m 2 )) and rejection (83.1% acetate rejection). For membrane performance, the experimental data were fit using the solution diffusion model. Increased pH in the feed solution lowered permeate flux but increased acetic acid rejection. Finally, then the acetic acid concentration in the feed solution increased, both permeate flux and acetic acid rejection decreased for membrane NF*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Approaches to investigate crop responses to ozone pollution: from O 3 -FACE to satellite-enabled modeling

Ozone (O 3 ) is a damaging air pollutant to crops. As one of the most reactive oxidants known, O 3 rapidly forms other reactive oxygen species (ROS) once it enters leaves through stomata. Those ROS in turn can cause oxidative stress, reduce photosynthesis, accelerate senescence, and decrease crop yield. To improve and adapt our feed, fuel, and food supply to rising O 3 pollution, a number of Free Air Concentration Enrichment (O 3 -FACE) facilities have been developed around the world and have studied key staple crops. In this review, we provide an overview of the FACE facilities and highlight some of the lessons learned from the last two decades of research. We discuss the differences between C 3 and C 4 crop responses to elevated O 3 , the possible trade-off between productivity and protection, genetic variation in O 3 response within and across species, and how we might leverage this observed variation for crop improvement. We also highlight the need to improve understanding of the interaction between rising O 3 pollution and other aspects of climate change, notably drought. Finally, we propose the use of globally modeled O 3 data that are available at increasing spatial and temporal resolutions to expand upon the research conducted at the limited number of global O 3 -FACE facilities.

54 ENVIRONMENTAL SCIENCES↗

Method for X-ray study under extreme temperature and pressure conditions

Vacuum chamber environmental simulator and X ray camera are used to study the stability of various minerals in extreme environmental conditions. An ion pump creates the desired vacuum. Exact sample positioning is obtained with a bellows sealed linear motion feed-through. Temperature control is by means of fluid conductive heat transfer.

Paus, L. L.↗

Global L-band Observatory for Water Cycle Studies (GLOWS)

L-band observations have proven useful for estimating soil moisture and ocean salinity variables to study the land surface and ocean. The European Space Agency (ESA) Soil Moisture and Ocean Salinity (SMOS) mission was the first (2009-present) spaceborne L-band radiometer. This was followed by two L-band missions flown by the National Aeronautics and Space Administration (NASA) to measure sea surface salinity (Aquarius 2011-2015) and soil moisture (SMAP 2015-present). It is critical to continue the time series of L-band observations that these missions have begun. To address this need we propose a new low-cost instrument concept known as the Global L-band active/passive Observatory for Water cycle Studies (GLOWS) that will include an L-band radiometer and radar to provide data continuity. The new mission concept includes a deployable reflectarray lens antenna with a compact feed that can be flown on an Earth Venture class satellite in a EELV Secondary Payload Adapter (ESPA) Grande-class mission. GLOWS will continue the science observations of SMAP and SMOS at the same resolution and accuracy at substantially lower cost, size, and weight.

David Long↗

System-Theoretic Analysis of Unsafe Collaborative Control in Teaming Systems

The interactions that occur in human-teaming are inspiring novel aerospace designs aimed at improving how humans and machines, or multiple machines, work together. Unfortunately, current Systems Engineering processes are ill-equipped to handle these complex relationships and are unable to design and assure the safety for these systems. To close part of this gap, this paper introduces a novel system-theoretic analytical process to identify unsafe collaborative control actions. It is part of a broader set of techniques that extend the state-of-the-art in hazard analysis, System Theoretic Process Analysis (STPA), to systematically address collaboration. The method rigorously expresses the different ways multiple commands may be unsafe together. Using Systems Theory, it employs abstraction to manage the combinatorial complexity in enumerating control contributions from multiple collaborating components. An algorithm integrates these concepts into an end-to-end process and is supported by automation to enumerate, refine, prune, and prioritize unsafe combinations of control actions. The output of the method feeds the specification of system requirements to implement safety-guided design starting early in concept development. The process is demonstrated on a manned-unmanned aircraft teaming case study and finds new causal factors that were not previously found in a past hazard analysis of the same system.

System Safety↗