Material Extrusion Reactive Precursor Additive Manufacturing of Carbides
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Engineering↗
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System and method for engineered ceramic packages for use in fluid treatment technologies
The present disclosure relates to a method for making a ceramic mini-tube configured for use in a fluid modification system. The method involves using an electrospinning system to receive a quantity of precursor solution. The electrospinning system creates an electric field which causes the precursor solution, when emitted, to be stretched into a fiber jet. The fiber jet is deposited on a collector resulting in a fiber mat. The fiber mat is removed from the collector, wherein the fiber mat is formed into a shape. The fiber mat is further processed so that the fiber mat retains a desired shape. A heat treatment operation is then performed to convert the fiber mat into a ceramic structure having the desired shape.
Kelly, James Patrick↗
Diversifying Isoprenoid Platforms via Atypical Carbon Substrates and Non-model Microorganisms
Isoprenoid compounds are biologically ubiquitous, and their characteristic modularity has afforded products ranging from pharmaceuticals to biofuels. Isoprenoid production has been largely successful in Escherichia coli and Saccharomyces cerevisiae with metabolic engineering of the mevalonate (MVA) and methylerythritol phosphate (MEP) pathways coupled with the expression of heterologous terpene synthases. Yet conventional microbial chassis pose several major obstacles to successful commercialization including the affordability of sugar substrates at scale, precursor flux limitations, and intermediate feedback-inhibition. Now, recent studies have challenged typical isoprenoid paradigms by expanding the boundaries of terpene biosynthesis and using non-model organisms including those capable of metabolizing atypical C1 substrates. Conversely, investigations of non-model organisms have historically informed optimization in conventional microbes by tuning heterologous gene expression. Here, we review advances in isoprenoid biosynthesis with specific focus on the synergy between model and non-model organisms that may elevate the commercial viability of isoprenoid platforms by addressing the dichotomy between high titer production and inexpensive substrates.
59 BASIC BIOLOGICAL SCIENCES↗
Geologic Maps for Civil Engineering and Infrastructure Planning
The Artemis Program mandate for sustainable, long-term presence on the Moon requires learning to "Live Off the Land". Geologic maps enable a paradigm shift to model the development and scaling of infrastructure for robotic and human exploration inside a bounded system on the lunar surface. Relying on geologic maps produced from orbital data and robotic precursor missions, in-situ resource utilization (ISRU) will be required to produce infrastructure, building materials and consumables. The ISRU value chain must be mapped to identify linkages of resources, producers, processes and equipment capabilities for transforming excavated regolith into usable feedstocks. Coordination will be required to balance supply and demand across the whole system of lunar infrastructure and operations, at each stage of development.
Geologic Mapping↗
Ceramic Inclusions in Powder Metallurgy Disk Alloys: Characterization and Modeling
Powder metallurgy alloys are increasingly used in gas turbine engines, especially in turbine disk applications. Although powder metallurgy materials have many advantages over conventionally cast and wrought alloys (higher strength, higher temperature capability, etc.), they suffer from the rare occurrence of ceramic defects (inclusions) that are inherent to the powder atomization process. These inclusions can have a potentially large detrimental effect on the durability of individual components. An inclusion in a high stress location can act as a site for premature crack initiation and thereby considerably reduce the fatigue life. Because these inclusions are exceedingly rare, they typically do not reveal themselves in the process of characterizing the material for a particular application (the cumulative volume of the test bars in a fatigue life characterization is typically on the order of a single actual component). Ceramic inclusions have, however, been found to be the root cause of a number of catastrophic engine failures. To investigate the effect of these inclusions in detail, we have undertaken a study where known populations of ceramic particles, whose composition and morphology are designed to mimic the "natural" inclusions, are added to the precursor powder. Surface-connected inclusions have been found to have a particularly large detrimental effect on fatigue life; therefore, the quantity of ceramic "seeds" added is calculated to ensure that a minimum number will intersect the surface of the fatigue test bars. Because the ceramic inclusions are irregularly shaped and have a tendency to break up in the process of extrusion and forging, a method of calculating the probability of occurrence and expected intercepted surface area was needed. We have developed a Monte Carlo simulation to determine the distributions of these parameters and have verified the simulated results with observations of ceramic inclusions found in macroscopic slices from extrusions and forgings. Fatigue specimens have been machined from Udimet 720 (a powder metallurgy superalloy) forgings, to determine the effects of the inclusions on fatigue life. The ultimate goal of this study will be to use probabilistic methods to determine the reliability detriment that can be attributed to these ceramic inclusions. This work has been supported by the Ultra Safe and Ultra- Efficient Engine Technologies programs.
Bonacuse, Peter J.↗
Transition-metal doped titanate nanowire photocatalysts boosted by selective ion-exchange induced defect engineering
Defect engineering through elemental doping is an efficient way to boost the performance of semiconductor photocatalysts. For this work, transition-metal (TM) doped titanate nanowires (TNWs) were prepared via ion-exchange over the titanate precursors and demonstrated for the Rhodamine B (RhB) degradation under ultraviolet (UV) light irradiation. The ion-exchange of selective ions (V 5+ , Cr 3+ , Ni 2+ , and Zn 2+ ) with protons from pristine TNWs resulted in the hierarchical meso-porosity of nanowires with large pores of ~5–20 nm by TM doping and small pores of ~3.6–4.5 nm inherited from pristine TNWs, which facilitates the mass transfer while maintaining high surface area and active sites. Meanwhile, the TM intercalation partially reduces the Ti 4+ to Ti 3+ and narrows the optical bandgap, which, together with oxygen vacancies and superoxide radicals from pristine TNWs, enhance the adsorption and photocatalytic degradation performance of RhB. This work helps to elucidate the effects of transition-metal doping and provides a rational strategy towards high performance titanate-based photocatalysts for efficient and sustainable wastewater treatment.
36 MATERIALS SCIENCE↗
In Situ Monitoring the Nucleation and Growth of Nanoscale CaCO 3 at the Oil–Water Interface
Interfaces can actively control the nucleation kinetics, orientations, and polymorphs of calcium carbonate (CaCO 3 ). Prior studies have revealed that CaCO 3 formation can be affected by the interplay between chemical functional moieties on solid–liquid or air–liquid interfaces as well as CaCO 3 ’s precursors and facets. Yet little is known about the roles of a liquid–liquid interface, specifically an oil–liquid interface, in directing CaCO 3 mineralization which are common in natural and engineered systems. Here, in this study, by using in situ X-ray scattering techniques to locate a meniscus formed between water and a representative oil, isooctane, we successfully monitored CaCO 3 formation at the pliable isooctane–water interface and systematically investigated the pivotal roles of the interface in the formation of CaCO 3 (i.e., particle size, its spatial distribution with respect to the interface, and its mineral phase). Different from bulk solution, ∼5 nm CaCO 3 nanoparticles form at the isooctane–water interface. They stably exist for a long time (36 h), which can result from interface-stabilized dehydrated prenucleation clusters of CaCO 3 . There is a clear tendency for enhanced amounts and faster crystallization of CaCO 3 at locations closer to isooctane, which is attributed to a higher pH and an easier dehydration environment created by the interface and oil. Our study provides insights into CaCO 3 nucleation at an oil–water interface, which can deepen our understanding of pliable interfaces interacting with CaCO 3 and benefit mineral scaling control during energy-related subsurface operation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Computational Aerodynamic Analysis in Support of the CRM Tail Cone Thruster Configuration Wind Tunnel Test
NASA’s Advanced Air Transport Technology (AATT) project is breaching the boundaries of aircraft design in pursuit of eco-friendly solutions that are compatible with urban noise comfort levels. Boundary layer ingesting (BLI) propulsion systems promise to reduce fuel burn with additional potential benefits in noise reduction. Type-II BLI systems of the STARC-ABL type are the subject of a test campaign planned for fiscal year 2022 in the National Transonic Facility (NTF), for which a CRM-based model with a retrofitted tail cone thruster (TCT) has been designed. The present work is a precursor to the NTF test, where the 240 cases planned for the experiment were simulated using the Launch, Ascent and Vehicle Aerodynamics (LAVA)computational framework. Solution sensitivity to angle of attack, engine operating conditions, and the presence of the supporting structure (sting) in the wind tunnel test are analyzed in the extensive dataset. The main flow features contributing to the inlet distortion are identified as the vertical tail wake, wing downwash and fuselage upsweep vortices, with the latter two experiencing the greatest sensitivity to angle of attack. Finally, results from an inlet-guide-vane(IGV) design/integration study are presented. The LAVA team and the turbomachinery design team at NASA’s Ames and Glenn Research Centers are collaborating in an effort to reduce flow distortion upstream of the fan by means of integrating an IGV system into the CRM-TCT model. A significant improvement in flow distortion metrics has been achieved since the initial design iteration. Results employing an actuator zone model with realistic radially-varying thrust profiles to simulate first-order fan effects within LAVA are presented.
AATT↗
Development of a VRC01-class germline targeting immunogen derived from anti-idiotypic antibodies
An effective HIV-1 vaccine will likely need to elicit broadly neutralizing antibodies (bNAbs). Broad and potent VRC01-class bNAbs have been isolated from multiple infected individuals, suggesting that they could be reproducibly elicited by vaccination. Several HIV-1 envelope-derived germline-targeting immunogens have been designed to engage naive VRC01-class precursor B cells. However, they also present off-target epitopes that could hinder development of VRC01-class bNAbs. We characterize a panel of anti-idiotypic monoclonal antibodies (ai-mAbs) raised against inferred-germline (iGL) VRC01-class antibodies. By leveraging binding, structural, and B cell sorting data, we engineered a bispecific molecule derived from two aimAbs; one specific for VRC01-class heavy chains and one specific for VRC01-class light chains. The bispecific molecule preferentially activates iGL-VRC01 B cells in vitro and induces specific antibody responses in a murine adoptive transfer model with a diverse polyclonal B cell repertoire. This molecule represents an alternative non-envelope-derived germline-targeting immunogen that can selectively activate VRC01-class precursors in vivo.
59 BASIC BIOLOGICAL SCIENCES↗
A Summary of Normal Incidence Tube Tests of NASA'S Bio-inspired Broadband Acoustic Absorber
Motivated by the need to reduce noise pollution from aircraft engines, NASA has continued to design, manufacture and test recently patented structures that mimic the geometry and the broadband and low frequency acoustic absorption of assemblies of natural reeds. This report documents a screening test, which is a precursor to more controlled modelling experiments. The purpose of this experiment was to identify variables and prototype design features that might play a dominant role in the acoustic performance of these structures. To date, twenty-four prototypes, each with an overall shape of a cube (nominally 50 mm x 50 mm x 50 mm), were designed and additively manufactured from thermoplastics using a Fused Filament Fabrication technique. The prototypes were tested in the NASA Glenn and Langley Normal Incidence Tubes to experimentally determine the acoustic absorption as a function of frequency from 400 Hz to 3000 Hz. Results indicate that a variety of structures exhibit substantial acoustic absorption in that frequency range, with an average absorption coefficient greater than 0.6, especially in the frequency range of 400 Hz to 1000 Hz. Six basic prototype designs were chosen to inform future modeling research. Results of these experiments can be used to evaluate existing physics-based models of the interaction of sound waves with these structures or to develop new models. Validated physics-based models of these structures can help engineers optimize the designs for different commercial noise control applications.
Acoustics↗
Recent Advances in Synthesis and Application of Lignin Nanoparticles
The ability to engineer material at its nanoscale has shown great potentials in overcoming significant obstacles in numerous fields. Because of its abundance, biodegradability, renewability, and eco-friendliness nature, lignin has become an ideal precursor for producing nanoscale materials from both research and industrial communities. Nanolignin, also known as colloidal lignin particle (CLP) or lignin nanoparticle (LNP), has received significant interest in recent years and its production and application in numerous fields represent an important aspect of lignin valorization. LNPs could be produced via several techniques including sonication, solvent exchange, and precipitation, which could be divided into wet and dry methods. Applications of LNPs in UV protection, cosmetics, food package, coatings, and drug delivery have been reported in the literature. Despite being extensively studied, LNPs as well as their derived materials with controlled shape and architecture are still largely underexploited. This book chapter mainly covers recent advances in the preparation of LNPs and their use in the novel and advanced applications in different areas.
Meng, Xianzhi↗
Biologically Diverse Genetic Engineering Platform
This project focused on methods to genetically edit arbitrary prokaryotes to convert non-agricultural biomass to industrially relevant chemicals at scale and at a price point that would be competitive with petroleum. Our target chemical for this demonstration was succinic acid, a polymer precursor that could theoretically be produced at scale from biomass. We demonstrated genetic control over a selected bacterial type strain: we can make permanent and directed changes to its genome. After thoroughly characterizing its behavior, and the circumstances under which it produced the most succinic acid, the researchers found a wild-type isolate that produces at least eight times more succinic acid than the type strain.
09 BIOMASS FUELS↗
High‐Performance and Stable Semi‐Transparent Perovskite Solar Cells through Composition Engineering
Abstract Semi‐transparent perovskite solar cells (ST‐PeSCs) have tremendous potential as solar windows owing to their higher efficiency and visible transmittance. However, studies toward this application are still nascent, particularly in unraveling the interplay between how the perovskite composition impacts the achievable device performance and stability. Here, the role of A‐ and X‐site modification in APbX 3 perovskites is studied to understand their influence on these factors. Through detailed experimental and simulation work, it is found that a perovskite composition consisting of cesium (Cs) and formamidinium (FA) at the A‐site delivers the best device performance over a range of band gaps, which are tuned by changes to the X‐site anion. Using this optimized perovskite composition, power conversion efficiencies of 15.5% and 4.1% are achieved for ST‐PeSCs with average visible transmittance values between 20.7% and 52.4%, respectively. Furthermore, the CsFA‐based ST‐PeSCs show excellent long‐term stability under continuous illumination and heating. The stability of the precursor solutions across each of the studied compositions has also been considered, showing dramatic differences in the structural properties of the perovskites and their device performance for all mixed A‐site compositions possessing the archetypal methyl ammonium species, while also confirming the superior stability of the CsFA precursor solutions.
14 SOLAR ENERGY↗
Vapor-phase pillarization of MXenes for engineering hierarchical interlayer porosity
MXenes, a family of two-dimensional (2D) multilamellar materials, possess excellent thermal and electronic properties for a range of applications. Their use in heterogeneous catalysis, however, is limited by the low surface area resulting from stacked layers. Pillarization with inorganic oxides can create more open, mesoporous MXene structures, improving accessibility for guest species to diffuse, reside or react in the space between 2D layers. A previous liquid-phase pillarization method, however, involves excessive use of solvent-based precursors and multiple processing steps. Here, we report a vapor-phase pillarization (VPP) strategy to introduce pillars, exemplified by silica pillars, with high pillar precursor usage efficiency and a simplified processing workflow. The resulting silica-pillared mesoporous MXene exhibits significantly increased surface area and porosity. These textural properties can be easily tuned by the VPP synthesis conditions. When applied as a ruthenium (Ru) catalyst support for the hydrogenolysis of low-density polyethylene (LDPE), the silica-pillared MXene enabled high Ru dispersion and catalytic activity. This study highlights the potential of the VPP method for engineering mesoporous, 2D MXene materials and demonstrates the effectiveness of mesoporous MXene as a catalyst support in overcoming mass transport and active-site accessibility challenges in heterogeneous catalysis involving bulky substances, such as plastics upcycling.
Luo, Song [University of Delaware, Newark, DE (Uni↗
Design of multihundredwatt DIPS for robotic space missions
Design of a dynamic isotope power system (DIPS) general purpose heat source (GPHS) and small free piston Stirling engine (FPSE) is being pursued as a potential lower cost alternative to radioisotope thermoelectric generators (RTG's). The design is targeted at the power needs of future unmanned deep space and planetary surface exploration missions ranging from scientific probes to SEI precursor missions. These are multihundredwatt missions. The incentive for any dynamic system is that it can save fuel which reduces cost and radiological hazard. However, unlike a conventional DIPS based on turbomachinery converions, the small Stirling DIPS can be advantageously scaled to multihundred watt unit size while preserving size and weight competitiveness with RTG's. Stirling conversion extends the range where dynamic systems are competitive to hundreds of watts (a power range not previously considered for dynamic systems). The challenge of course is to demonstrate reliability similar to RTG experience. Since the competative potential of FPSE as an isotope converter was first identified, work has focused on the feasibility of directly integrating GPHS with the Stirling heater head. Extensive thermal modeling of various radiatively coupled heat source/heater head geometries were performed using data furnished by the developers of FPSE and GPHS. The analysis indicates that, for the 1050 K heater head configurations considered, GPHS fuel clad temperatures remain within safe operating limits under all conditions including shutdown of one engine. Based on these results, preliminary characterizations of multihundred watt units were established.
Bents, D. J.↗
Direct synthesis of ordered mesoporous materials from thermoplastic elastomers
Abstract The ability to manufacture ordered mesoporous materials using low-cost precursors and scalable processes is essential for unlocking their enormous potential to enable advancement in nanotechnology. While templating-based methods play a central role in the development of mesoporous materials, several limitations exist in conventional system design, including cost, volatile solvent consumption, and attainable pore sizes from commercial templating agents. This work pioneers a new manufacturing platform for producing ordered mesoporous materials through direct pyrolysis of crosslinked thermoplastic elastomer-based block copolymers. Specifically, olefinic majority phases are selectively crosslinked through sulfonation reactions and subsequently converted to carbon, while the minority block can be decomposed to form ordered mesopores. We demonstrate that this process can be extended to different polymer precursors for synthesizing mesoporous polymer, carbon, and silica. Furthermore, the obtained carbons possess large mesopores, sulfur-doped carbon framework, with tailorable pore textures upon varying the precursor identities.
36 MATERIALS SCIENCE↗
Expression of dehydroshikimate dehydratase in poplar induces transcriptional and metabolic changes in the phenylpropanoid pathway
Abstract Modification of lignin in feedstocks via genetic engineering aims to reduce biomass recalcitrance to facilitate efficient conversion processes. These improvements can be achieved by expressing exogenous enzymes that interfere with native biosynthetic pathways responsible for the production of the lignin precursors. In planta expression of a bacterial 3-dehydroshikimate dehydratase in poplar trees reduced lignin content and altered the monomer composition, which enabled higher yields of sugars after cell wall polysaccharide hydrolysis. Understanding how plants respond to such genetic modifications at the transcriptional and metabolic levels is needed to facilitate further improvement and field deployment. In this work, we acquired fundamental knowledge on lignin-modified poplar expressing 3-dehydroshikimate dehydratase using RNA-seq and metabolomics. The data clearly demonstrate that changes in gene expression and metabolite abundance can occur in a strict spatiotemporal fashion, revealing tissue-specific responses in the xylem, phloem, or periderm. In the poplar line that exhibited the strongest reduction in lignin, we found that 3% of the transcripts had altered expression levels and ~19% of the detected metabolites had differential abundance in the xylem from older stems. The changes affected predominantly the shikimate and phenylpropanoid pathways as well as secondary cell wall metabolism, and resulted in significant accumulation of hydroxybenzoates derived from protocatechuate and salicylate.
59 BASIC BIOLOGICAL SCIENCES↗
Summary of Liquid Propulsion System Needs in Support of the Constellation Program
In January 2004, the President of the United States established the Vision for Space Exploration (VSE) to complete the International Space Station, retire the Space Shuttle and develop its replacement, and expand the human presence on the Moon as a stepping stone to human exploration of Mars and worlds beyond. In response, NASA developed the Constellation Program, consisting of the components shown in Figure 1. This paper will summarize the manned spaceflight liquid propulsion system needs in support of the Constellation Program over the next 10 years. It will address all liquid engine needs to support human exploration from low Earth orbit (LEO) to the lunar surface, including an overview of engines currently under contract, those baselined but not yet under contract, and those propulsion needs that have yet to be initiated. There may be additional engine needs for early demonstrators, but those will not be addressed as part of this paper. Also, other portions of the VSE architecture, including the planned Orion abort test boosters and the Lunar Precursor Robotic Program, are not addressed here as they either use solid motors or are focused on unmanned elements of returning humans to the Moon.
Lorier, Terry↗