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All sources NASA NTRS DOE OSTI

DOE OSTI2023

Structural elucidation of polydopamine facilitated by ionic liquid solvation

Minimal understanding of the formation mechanism and structure of polydopamine (pDA) and its natural analogue, eumelanin, impedes the practical application of these versatile polymers and limits our knowledge of the origin of melanoma. The lack of conclusive structural evidence stems from the insolubility of these materials, which has spawned significantly diverse suggestions of pDA's structure in the literature. We discovered that pDA is soluble in certain ionic liquids. Using these ionic liquids (ILs) as solvents, we present an experimental methodology to solvate pDA, enabling us to identify pDA's chemical structure. The resolved pDA structure consists of self-assembled supramolecular aggregates that contribute to the increasing complexity of the polymer. The underlying molecular energetics of pDA solvation and a macroscopic picture of the disruption of the aggregates using IL solvents have been investigated, along with studies of the aggregation mechanism in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Automated identification of local contamination in remote atmospheric composition time series

Abstract. Atmospheric observations in remote locations offer a possibility of exploring trace gas and particle concentrations in pristine environments. However, data from remote areas are often contaminated by pollution from local sources. Detecting this contamination is thus a central and frequently encountered issue. Consequently, many different methods exist today to identify local contamination in atmospheric composition measurement time series, but no single method has been widely accepted. In this study, we present a new method to identify primary pollution in remote atmospheric datasets, e.g., from ship campaigns or stations with a low background signal compared to the contaminated signal. The pollution detection algorithm (PDA) identifies and flags periods of polluted data in five steps. The first and most important step identifies polluted periods based on the derivative (time derivative) of a concentration over time. If this derivative exceeds a given threshold, data are flagged as polluted. Further pollution identification steps are a simple concentration threshold filter, a neighboring points filter (optional), a median, and a sparse data filter (optional). The PDA only relies on the target dataset itself and is independent of ancillary datasets such as meteorological variables. All parameters of each step are adjustable so that the PDA can be “tuned” to be more or less stringent (e.g., flag more or fewer data points as contaminated). The PDA was developed and tested with a particle number concentration dataset collected during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in the central Arctic. Using strict settings, we identified 62 % of the data as influenced by local contamination. Using a second independent particle number concentration dataset also collected during MOSAiC, we evaluated the performance of the PDA against the same dataset cleaned by visual inspection. The two methods agreed in 94 % of the cases. Additionally, the PDA was successfully applied to a trace gas dataset (CO2), also collected during MOSAiC, and to another particle number concentration dataset, collected at the high-altitude background station Jungfraujoch, Switzerland. Thus, the PDA proves to be a useful and flexible tool to identify periods affected by local contamination in atmospheric composition datasets without the need for ancillary measurements. It is best applied to data representing primary pollution. The user-friendly and open-access code enables reproducible application to a wide suite of different datasets. It is available at https://doi.org/10.5281/zenodo.5761101 (Beck et al., 2021).

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2016

The Role of Probabilistic Design Analysis Methods in Safety and Affordability

For the last several years, NASA and its contractors have been working together to build space launch systems to commercialize space. Developing commercial affordable and safe launch systems becomes very important and requires a paradigm shift. This paradigm shift enforces the need for an integrated systems engineering environment where cost, safety, reliability, and performance need to be considered to optimize the launch system design. In such an environment, rule based and deterministic engineering design practices alone may not be sufficient to optimize margins and fault tolerance to reduce cost. As a result, introduction of Probabilistic Design Analysis (PDA) methods to support the current deterministic engineering design practices becomes a necessity to reduce cost without compromising reliability and safety. This paper discusses the importance of PDA methods in NASA's new commercial environment, their applications, and the key role they can play in designing reliable, safe, and affordable launch systems. More specifically, this paper discusses: 1) The involvement of NASA in PDA 2) Why PDA is needed 3) A PDA model structure 4) A PDA example application 5) PDA link to safety and affordability.

Safie, Fayssal M.↗

DOE OSTI2021

Performance Study of Distance-Weighting Approach with Loopy Sum-Product Algorithm for Multi-Object Tracking in Clutter

In this paper, we explore the performance of the distance-weighting probabilistic data association (DWPDA) approach in conjunction with the loopy sum-product algorithm (LSPA) for tracking multiple objects in clutter. First, we discuss the problem of data association (DA), which is to infer the correspondence between targets and measurements. DA plays an important role when tracking multiple targets using measurements of uncertain origin. Second, we describe three methods of data association: probabilistic data association (PDA), joint probabilistic data association (JPDA), and LSPA. We then apply these three DA methods for tracking multiple crossing targets in cluttered environments, e.g., radar detection with false alarms and missed detections. We are interested in two performance metrics: tracking accuracy and computation time. LSPA is known to be superior to PDA in terms of the former and to dominate JPDA in terms of the latter. Last, we consider an additional DA method that is a modification of PDA by incorporating a weighting scheme based on distances between position estimates and measurements. This distance-weighting approach, when combined with PDA, has been shown to enhance the tracking accuracy of PDA without significant change in the computation burden. Since PDA constitutes a crucial building block of LSPA, we hypothesize that DWPDA, when integrated with LSPA, would perform better under the two performance metrics above. Contrary to expectations, the distance-weighting approach does not enhance the performance of LSPA, whether in terms of tracking accuracy or computation time.

47 OTHER INSTRUMENTATION↗

DOE OSTI2023

Biologically inspired reinforcement using polydopamine of polymer bound composites

Interfacial strength plays a critical role in the mechanical properties of a composite system. In this work, a proven mock high explosive (HE), 5-iodo-2’-deoxyuridine (IDOX) was coated by the adhesive promoting polymer polydopamine (PDA), then formulated with an Estane binder system to form an improved HE mock composite. An extensive comparison study of mechanical properties was performed to determine the effects, if any, of PDA on the composite system. To aid in interpretation of the mechanical test data, neutron reflectometry experiments were performed to determine the thickness and structure of the as deposited PDA films. The mechanical performance of PDA-treated IDOX was then compared to untreated specimens by compression testing in the Brazilian disk geometry. The results strongly suggested that the structure of PDA consists of two layers: one low in density caused by polymer agglomerates attaching to the substrate during polymerization, and the second high in density caused by controlled linear deposition of polydopamine. Finally, the mechanical testing showed that PDA greatly increased the stiffness and yield strength of IDOX based mocks without causing any disruption to the underlying crystal system.

42 ENGINEERING↗

DOE OSTI2026

Mechanistic insights into CO 2 capture and electrochemical conversion in nonaqueous Na–CO 2 batteries

Developing efficient energy storage systems that capture and convert CO 2 is critical for mitigating carbon emissions. Here, we report a Na–CO 2 battery with ruthenium dioxide (RuO 2 ) cathode catalysts and propane-1,3-diamine (PDA) as an electrolyte additive to enhance CO 2 capture and conversion efficiency. The integration of CO 2 adsorption and electrochemical reduction facilitates activation of the inert CO 2 molecule and circumvents gas–solid–liquid ternary-phase reactions at the interface. We employed density functional theory (DFT) calculations to systematically unravel the reaction mechanisms and energetics governing CO 2 reduction, both with and without PDA. Our results reveal an energetically favorable pathway toward the formation of Na 2 CO 3 and C as final discharge products, rather than sodium oxalate (Na 2 C 2 O 4 ). The CO 2 –amine adduct facilitates charge transfer from PDA to CO 2 , which results in activation of CO 2 . The kinetics of CO 2 conversion and regeneration of PDA were found to be significantly enhanced on the RuO 2 surface compared to the bulk electrolyte. More importantly, pre-activation of CO 2 via the amine–CO 2 adduct lowers the total overpotential to 2.44 V, compared to 3.13 V without PDA. This study provides fundamental insights into CO 2 electroreduction in Na–CO 2 batteries and underscores the promise of electrolyte engineering for sustainable CO 2 utilization and high-performance energy storage.

25 ENERGY STORAGE↗

DOE OSTI2023

Probing sub-5 Ångstrom micropores in carbon for precise light olefin/paraffin separation

Olefin/paraffin separation is an important but challenging and energy-intensive process in petrochemical industry. The realization of carbons with size-exclusion capability is highly desirable but rarely reported. Herein, we report polydopamine-derived carbons (PDA-Cx, where x refers to the pyrolysis temperature) with tailorable sub-5 Å micropore orifices together with larger microvoids by one-step pyrolysis. The sub-5 Å micropore orifices centered at 4.1–4.3 Å in PDA-C800 and 3.7–4.0 Å in PDA-C900 allow the entry of olefins while entirely excluding their paraffin counterparts, performing a precise cut-off to discriminate olefin/paraffin with sub-angstrom discrepancy. The larger voids enable high C 2 H 4 and C 3 H 6 capacities of 2.25 and 1.98 mmol g –1 under ambient conditions, respectively. Breakthrough experiments confirm that a one-step adsorption-desorption process can obtain high-purity olefins. Inelastic neutron scattering further reveals the host–guest interaction of adsorbed C 2 H 4 and C 3 H 6 molecules in PDA-Cx. This study opens an avenue to exploit the sub-5 Å micropores in carbon and their desirable size-exclusion effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1976

Fabrication of PDA/HTS prototype components

A process was developed for autoclave molding structural poly-(Diels-Alder) polyimide (PDA) resin/HTS graphite composites for short-term 600 F service. The autoclave molding process used to fabricate these composites required a maximum cure temperature of 427 K (400 F) and a maximum molding pressure of 0.7 MN/sq m (100 psig). This process then was adapted to the fabrication of co-cured polyimide sandwich panels consisting of PDA/HTS skins, PDA syntactic foam and polyimide/glass honeycomb core. Fabrication ease was demonstrated by manufacturing five three-quarter scale YF-12 wing panels using the PDA resin. It was concluded from successful evaluation of these prototype units that the PDA resin is suitable for fabrication of components using commercial equipment.

Sheppard, C. H.↗

NASA NTRS1998

Photonic and Opto-Electronic Applications of Polydiacetylene Films Photodeposited from Solution and Polydiacetylene Copolymer Networks

Polydiacetylenes (PDAS) are attractive materials for both electronic and photonic applications because of their highly conjugated electronic structures. They have been investigated for applications as both one-dimensional (linear chain) conductors and nonlinear optical (NLO) materials. One of the chief limitations to the use of PDAs has been the inability to readily process them into useful forms such as films and fibers. In our laboratory we have developed a novel process for obtaining amorphous films of a PDA derived from 2-methyl4-nitroaniline using photodeposition with Ultraviolet (UV) light from monomer solutions onto transparent substrates. Photodeposition from solution provides a simple technique for obtaining PDA films in any desired pattern with good optical quality. This technique has been used to produce PDA films that show potential for optical applications such as holographic memory storage and optical limiting, as well as third-order NLO applications such as all-optical refractive index modulation, phase modulation and switching. Additionally, copolymerization of diacetylenes with other monomers such as methacrylates provides a means to obtain materials with good processibility. Such copolymers can be spin cast to form films, or drawn by either melt or solution extrusion into fibers. These films or fibers can then be irradiated with UV to photopolymerize the diacetylene units to form a highly stable cross-linked PDA-copolymer network. If such films are electrically poled while being irradiated, they can achieve the asymmetry necessary for second-order NLO applications such as electro-optic switching. On Earth, formation of PDAs by the above mentioned techniques suffers from defects and inhomogeneities caused by convective flows that can arise during processing. By studying the formation of these materials in the reduced-convection, diffusion-controlled environment of space we hope to better understand the factors that affect their processing, and thereby, their nature and properties. Ultimately it may even be feasible to conduct space processing of PDAs for technological applications.

Paley, Mark S.↗

NASA NTRS2009

Performance Support Tools for Space Medical Operations

The early Constellation space missions are expected to have medical capabilities very similar to those currently on the Space Shuttle and International Space Station (ISS). For Crew Exploration Vehicle (CEV) missions to ISS, medical equipment will be located on ISS, and carried into CEV in the event of an emergency. Flight Surgeons (FS) on the ground in Mission Control will be expected to direct the Crew Medical Officer (CMO) during medical situations. If there is a loss of signal and the crew is unable to communicate with the ground, a CMO would be expected to carry out medical procedures without the aid of a FS. In these situations, performance support tools can be used to reduce errors and time to perform emergency medical tasks. Human factors personnel at Johnson Space Center have recently investigated medical performance support tools for CMOs on-orbit, and FSs on the ground. This area of research involved the feasibility of Just-in-time (JIT) training techniques and concepts for real-time medical procedures. In Phase 1, preliminary feasibility data was gathered for two types of prototype display technologies: a hand-held PDA, and a Head Mounted Display (HMD). The PDA and HMD were compared while performing a simulated medical procedure using ISS flight-like medical equipment. Based on the outcome of Phase 1, including data on user preferences, further testing was completed using the PDA only. Phase 2 explored a wrist-mounted PDA, and compared it to a paper cue card. For each phase, time to complete procedures, errors, and user satisfaction were captured. Information needed by the FS during ISS mission support, especially for an emergency situation (e.g. fire onboard ISS), may be located in many different places around the FS s console. A performance support tool prototype is being developed to address this issue by bringing all of the relevant information together in one place. The tool is designed to include procedures and other information needed by a FS during an emergency, as well as procedures and information to be used after the emergency is resolved. Several walkthroughs of the prototype with FSs have been completed within a mockup of an ISS FS console. Feedback on the current tool design as well as recommendations for existing ISS FS displays were captured.

Byrne, Vicky E.↗

NASA NTRS2009

Human Factors in Training - Space Medicine Proficiency Training

The early Constellation space missions are expected to have medical capabilities very similar to those currently on the Space Shuttle and International Space Station (ISS). For Crew Exploration Vehicle (CEV) missions to ISS, medical equipment will be located on ISS, and carried into CEV in the event of an emergency. Flight Surgeons (FS) on the ground in Mission Control will be expected to direct the Crew Medical Officer (CMO) during medical situations. If there is a loss of signal and the crew is unable to communicate with the ground, a CMO would be expected to carry out medical procedures without the aid of a FS. In these situations, performance support tools can be used to reduce errors and time to perform emergency medical tasks. Work on medical training has been conducted in collaboration with the Medical Training Group at the Space Life Sciences Directorate and with Wyle Lab which provides medical training to crew members, Biomedical Engineers (BMEs), and to flight surgeons under the JSC Space Life Sciences Directorate s Bioastronautics contract. The space medical training work is part of the Human Factors in Training Directed Research Project (DRP) of the Space Human Factors Engineering (SHFE) Project under the Space Human Factors and Habitability (SHFH) Element of the Human Research Program (HRP). Human factors researchers at Johnson Space Center have recently investigated medical performance support tools for CMOs on-orbit, and FSs on the ground, and researchers at the Ames Research Center performed a literature review on medical errors. The work proposed for FY10 continues to build on this strong collaboration with the Space Medical Training Group and previous research. This abstract focuses on two areas of work involving Performance Support Tools for Space Medical Operations. One area of research building on activities from FY08, involved the feasibility of just-in-time (JIT) training techniques and concepts for real-time medical procedures. In Phase 1, preliminary feasibility data was gathered for two types of prototype display technologies: a hand-held PDA, and a Head Mounted Display (HMD). The PDA and HMD were compared while performing a simulated medical procedure using ISS flight-like medical equipment. Based on the outcome of Phase 1, including data on user preferences, further testing was completed using the PDA only. Phase 2 explored a wrist-mounted PDA, and compared it to a paper cue card. For each phase, time to complete procedures, errors, and user satisfaction ratings were captured.

Connell, Erin↗

NASA NTRS2018

NASA ACC High Energy Dynamic Impact Methodology and Outcomes

High fidelity analysis methods known as Progressive Damage Analysis (PDA) methods, capable of reliably predicting the onset and progression of damage in composite materials, are being developed for HEDI event simulation. Four state-of-the-art PDA methods are being investigated: LS-DYNA MAT162, LS-DYNA MAT261, Smooth-Particle Galerkin (SPG), and EMU Peridynamics. Validation of these PDA models aims to follow a building block approach, starting with coupon- and component-level development. As part of the overall effort, material characterization testing was performed to bridge gaps between existing experimental data and the material property inputs required to predict ballistic impact behavior at the component-level. The material models were updated with the results of the coupon-level testing and were then used to predict panel behavior and damage in ballistic impact events. To assess the accuracy of the PDA methods, these pre-test predictions were compared to the results of ballistic impact testing.

Hunziker, Kenneth J.↗

NASA NTRSDate not supplied

Critical Progressive Damage Analysis Model Features for Low-Velocity Impact on Thermoset and Thermoplastic Panels

A previous verification and validation framework evaluated the ability of various progressive damage analysis (PDA) tools to predict the mechanical response and damage state in post-buckled stiffened aerospace structures composed of fiber-reinforced thermoset composite materials. Herein, the ability of PDA tools to predict damage in thermoplastic composite materials subject to low-velocity impact (LVI) loading has been assessed. LVI tests and analyses have been conducted for similar panels, comprising thermoset or thermoplastic composite materials. Preliminary test/analysis correlations revealed that using the same combination of PDA model features and finite element model-building guidelines for the thermoset and thermoplastic LVI specimens resulted in underprediction of matrix crack lengths and delaminated area in the thermoplastic analyses despite yielding good correlations for the thermoset specimens. In this paper, the quality of the test/analysis correlations for analyses of thermoplastic LVI specimens performed with different combinations of PDA model features using the NASA CompDam material model are presented. Model features that were assessed in terms of effect on the quality of the test/analysis correlation include the representation of damageable interfaces, residual thermal stresses, and fiber damage.

Frank Leone↗

NASA NTRSDate not supplied

Critical Progressive Damage Analysis Model Features for Low-Velocity Impact on Thermoset and Thermoplastic Panels

Frank Leone↗

DOE OSTI2025

Scalable thin graphene oxide membranes enabled by polydopamine gutter layer

Two-dimensional (2D) nanosheets have been widely used to fabricate thin-film composite membranes for dye desalination. However, they often need to be thick to mitigate the defects resulting from their random stacking and rough support surface. Herein, bio-adhesive polydopamine (PDA) is used as a gutter layer to prepare graphene oxide (GO)-based membranes by improving the adhesion between the GO and porous support and providing a smooth surface to form thin, highly selective layers. For example, the PDA priming reduces the GO layer thickness by 57 %, from 447 to 190 nm, while achieving similar dye desalination properties. The effect of the dopamine concentration, exposure time, and GO layer thickness on the membrane structure and desalination performance are thoroughly investigated using various techniques, such as scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). The PDA gutter layer is also applied for hollow fiber membranes, achieving water permeance of 79 L m -2 h −1 bar−1 and rejection of ∼99 % for Direct red 80. The membranes were challenged by simulated dye/salt mixtures to elucidate the complicated effect of the compositions on the desalination performance. Furthermore, this study unveils a new avenue to improve separation performance and large-scale manufacturability of 2D material-based membranes.

Dye desalination↗

DOE OSTI2022

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. Here, the molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derived compounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ~23–64% of the total light absorption measured by the PDA detector in the wavelength range of 300–370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/ lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet–visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Large Ensemble Particle Filter for Spatial Climate Reconstructions Using a Linear Inverse Model

Proxy records that document the last 2000 years of climate provide evidence for the wide range of the natural climate variability from inter-annual to secular timescales not captured by the short window of recent direct observations. Assessing climate models ability to reproduce such natural variations is crucial to understand climate sensitivity and impacts of future climate change. Paleoclimate data assimilation (PDA) offers a powerful way to extend the short instrumental period by optimally combining the physics described by General Circulation Climate Models (GCMs) with information from available proxy records while taking into account their uncertainties. Here we present a new PDA approach based on a sequential importance resampling (SIR) Particle filter (PF) that uses Linear Inverse Modeling (LIM) as an emulator of several CMIP-class GCMs. We examine in a perfect-model framework the skill of the various LIMs to forecast the dynamics of the surface temperatures and provide spatial field reconstructions over the last millennium in a SIR PF. Our results show that the LIMs allow for skillful ensemble forecasts at 1-year lead-time based on GCMs dynamical knowledge with best prediction in the tropics and the North Atlantic. The PDA further provides a set of physically consistent spatial fields allowing robust uncertainty quantification related to climate models biases and proxy spatial sampling. Our results indicate that the LIM yields dynamical memory improving climate variability reconstructions and support the use of the LIM as a GCM-emulator in real reconstruction to propagate large ensembles of particles at low cost in SIR PF.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1989

Structure/permeability relationships of silicon-containing polyimides

The permeability to H2, O2, N2, CO2 and CH4 of three silicone-polyimide random copolymers and two polyimides containing silicon atoms in their backbone chains, was determined at 35.0 C and at pressures up to about 120 psig (approximately 8.2 atm). The copolymers contained different amounts of BPADA-m-PDA and amine-terminated poly (dimethyl siloxane) and also had different numbers of siloxane linkages in their silicone component. The polyimides containing silicon atoms (silicon-modified polyimides) were SiDA-4,4'-ODA and SiDA-p-PDA. The gas permeability and selectivity of the copolymers are more similar to those of their silicone component than of the polyimide component. By contrast, the permeability and selectivity of the silicon-modified polyimides are more similar to those of their parent polyimides, PMDA-4,4'-ODA and SiDA-p-PDA. The substitution of SiDA for the PMDA moiety in a polyimide appears to result in a significant increase in gas permeability, without a correspondingly large decrease in selectivity. The potential usefulness of the above polymers and copolymers as gas separation membranes is discussed.

Stern, S. A.↗