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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination

Cyclopentadiene (CPD) and cyclopentadienyl radical (CPDyl) reactions are known to provide fast routes to naphthalene and other polycyclic aromatic hydrocarbon (PAH) precursors in many systems. In this work, we combine literature quantum chemical pathways for the CPDyl + CPDyl recombination reaction and provide pressure dependent rate coefficient calculations and analysis. Here we find that the simplified 1-step global reaction leading to naphthalene and two H atoms used in many kinetic models is not an adequate description of this chemistry at conditions of relevance to pyrolysis and steam cracking. The C 10 H 10 species is observed to live long enough to undergo H abstraction reactions to enter the C 10 H 9 potential energy surface (PES). Rate coefficient expressions as functions of T and P are reported in CHEMKIN format for future use in kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca 0.5 Ba 0.5 CO 3 ) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca 1- x Ba x CO 3 ·1.2H 2 O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sites that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Alternative analysis of the MINERVE ZPR oscillation experiments

Delayed neutrons are of fundamental importance in the field of nuclear reactor dynamics and control. However, the precursor yield fraction for a given nuclear reactor are dependent on the properties of the reactor. Thus, in-pile experiments, such as oscillation experiments are conducted in order to measure those values. In this work, an alternative analysis of the piston oscillation experiments that have been conducted in the MINERVE reactor in 2013 is performed. A new method which evolves effective terms that cancel out undesired drifts of the flux during the experiments is presented. The evaluation of the uncertainty on the values of the response function is also presented. Moreover, the effective delayed neutron fraction β{sub eff} is evaluated and is compared to results in previous works. As the analysis has led to an estimation of β{sub eff} with a large uncertainty, it has been deduced that the oscillation experiments that have been conducted in MINERVE are not a reliable method of experimentation to determine the value of β{sub eff} in the reactor and that the noise experiments are better suited for that purpose.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from Ir$_x$Cl$_y$ precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts–IrCl 3 , IrCl 4 , H 2 IrCl 6 , or Na 2 IrCl 6 –colloidal nanoparticles as small as Ir ~55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic ($fcc$) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl 3 or IrCl 4 , metallic iridium nanoparticles form rapidly from Ir$_x$Cl$_y$$^{n–}$ complexes, whereas using H 2 IrCl 6 or Na 2 IrCl 6 , the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H 2 IrCl 6 , the formation of different Ir$_n$ ($n$ = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. In conclusion, the results show that the synthesis of iridium nanoparticles from Ir$_x$Cl$_y$ is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Techno-economic and life cycle analyses of the synthesis of a platinum–strontium titanate catalyst

The heterogeneous platinum/strontium titanate (Pt/SrTiO 3 or Pt/STO) catalyst has garnered significant attention as a promising candidate for the hydrogenolysis of polyolefins to hydrocarbon oils. This study evaluates the cost and environmental impacts of a newly developed scalable Pt/STO catalyst production, which includes the synthesis of the STO support and the deposition of Pt onto the support. This two-step synthesis plays a significant role in assessing the commercial feasibility of the catalyst, while energy consumption during the process plays an important role in its environmental impacts. The CatCost and the Research and Development Greenhouse Gases, Regulated Emissions, and Energy use in Technologies (R&D GREET) models were used, respectively, to perform techno-economic analysis (TEA) and life cycle analysis (LCA) of the newly developed catalyst. The TEA showed that the raw materials, accounting for approximately 76% of the total operation cost, has a profound effect on the estimated catalyst cost, mainly due to the platinum precursor. The LCA findings indicated that the catalyst production generates greenhouse gas (GHG) emissions of 66 kg CO 2 e per kg, primarily due to the use of solvents and electricity in the process. The sensitivity analysis indicated that the total operating costs (OpEX), platinum precursor cost, and spent catalyst value (SCV) significantly impact the cost of the synthesized catalyst. Additionally, adopting solvent recovery strategies and using renewable electricity can reduce the GHG emissions of catalyst production to 29 kg CO 2 e per kg.

Heterogeneous Platinum/strontium titanate Catalyst↗
DOE OSTI2018

An Intraseasonal Mode of Atmospheric Variability Relevant to the U.S. Hydroclimate in Boreal Summer: Dynamic Origin and East Asia Connection

In this work intraseasonal modes of atmospheric variability over the Northern Hemisphere (NH) midlatitudes in boreal summer are identified via an empirical orthogonal function (EOF) analysis of the daily 10–90-day bandpass-filtered 250-hPa streamfunction for the period of 1950–2016. The first two EOF modes are characterized, respectively, by (i) a single-signed streamfunction anomaly that extends across the NH and (ii) a regional dipole structure with centers over the Aleutian Islands and northeastern Pacific. The third EOF mode (EOF-3) is a quasi-stationary wave train over the Pacific–North American sector with an equivalent barotropic structure in the vertical. EOF-3 is associated with a northwest–southeast oriented anomalous precipitation dipole over the United States. A nonmodal instability analysis of the boreal summer climatological flow in terms of the 250-hPa streamfunction reveals that one of the top “optimal mode” disturbances mimicking the EOF-3 structure grows from an initial precursor disturbance over East Asia through extracting kinetic energy from background flow and attains its maximum amplitude in around nine days. An additional lag regression analysis illustrates that anomalous latent heating associated with cloud and precipitation formation over East Asia is responsible for generating the precursor disturbance for the EOF-3-like optimal mode. This result suggests the existence of an important connection between the hydrological cycles of East Asia and North America, which is dynamically intrinsic to the boreal summer upper-tropospheric flow. Knowledge of such a connection will help us better understand and model hydroclimate variability over these two continents.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes

Atomic layer deposition (ALD) is a powerful strategy to engineer hybrid organic-inorganic membranes with emergent functionalities. The combination of atomic-level thickness control, a wide materials palette, and unprecedented conformality allows the physiochemical properties (e.g., hydrophilicity) of mesoporous polymer membranes to be precisely tuned. The nucleation of ALD material growth on polymer surfaces relies on Lewis acid-base interactions and remains an overlooked motif with tremendous potential to accelerate ALD nucleation and growth. Strategies to enhance these interactions could enable desirable properties such as antifouling behavior to be imparted on inert polymer surfaces that lack the necessary functional groups for ALD nucleation. Here, in this study, we demonstrate that the reactivity of polyacrylonitrile (PAN) membranes toward ALD metal oxide (MO) precursors with Lewis acid characteristics is enhanced by introducing strong Lewis base functional groups (amidoxime: Am) on the PAN backbone (Am-PAN). The resulting Lewis acid-base interactions accelerate the MO nucleation in Am-PAN and reduce the number of deposition cycles required to achieve hydrophilicity compared with the untreated PAN membrane. Unveiling the reaction mechanism, in situ Fourier transform infrared (FTIR) spectroscopy measurements established enhanced interaction dynamics between the ALD MO precursors and the Am-PAN membrane, unlike the PAN membrane. Spectroscopic ellipsometry and thermogravimetric analysis measurements revealed higher MO loadings in Am-PAN membranes compared to PAN membranes for the same number of ALD cycles. We found that strong Lewis acid-base interactions accelerated the ALD for a range of materials including Al 2 O 3 , TiO 2 , SnO 2 , and ZnO. More broadly, our work demonstrates that tailoring metal-precursor-polymer interactions is a powerful strategy to accelerate and modulate the ALD. We used this design strategy to fabricate Al 2 O 3 -Am-PAN hybrid membranes that showed 2-fold higher antifouling capability compared to pristine PAN membranes prepared with an equivalent number of Al 2 O 3 ALD cycles. Our approach expands the scope of design options for fouling-resistant porous hybrid inorganic-organic membranes and may ultimately reduce the operational costs of water treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In situ characterization of phase transformations in petroleum pitch by high temperature X-ray diffraction

The phase transformation from isotropic to mesophase of a petroleum-derived pitch was monitored by in situ X-ray diffraction at 410 °C. The kinetics of the transformation were characterized by monitoring the growth of a broad peak at 2θ~24° and could be described by Avrami’s equation. The volatilization of low molecular weight components originally present in the pitch, or produced during the condensation reaction, was assessed by thermal gravimetry analysis, following the same thermal history. Ex situ characterizations of the pitch precursor before and after thermal treatment provided insight into the evolution of the molecular structure associated with mesophase generation (optical polarized microscopy, molecular weight distribution by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, X-ray photoelectron spectroscopy, Auger spectroscopy, and thermal stability). Here, this investigation demonstrates the value of using complementary in situ and ex situ experimental techniques to characterize complex mechanisms during the processing of organic materials.

02 PETROLEUM↗
DOE OSTI2022

Putting Humpty Dumpty Back Together Again: What Does Protein Quantification Mean in Bottom-Up Proteomics?

Bottom-up proteomics provides peptide measurements and has been invaluable for moving proteomics into large-scale analyses. Commonly, a single quantitative value is reported for each protein-coding gene by aggregating peptide quantities into protein groups following protein inference or parsimony. However, given the complexity of both RNA splicing and post-translational protein modification, it is overly simplistic to assume that all peptides that map to a singular protein-coding gene will demonstrate the same quantitative response. Here, by assuming that all peptides from a protein-coding sequence are representative of the same protein, we may miss the discovery of important biological differences. To capture the contributions of existing proteoforms, we need to reconsider the practice of aggregating protein values to a single quantity per protein-coding gene.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Percolative nature of the direct-current paraconductivity in cuprate superconductors

Abstract Despite extraordinary scientific efforts over the past three decades, the cuprate high-temperature superconductors continue to pose formidable challenges. A pivotal problem, essential for understanding both the normal and superconducting states, is to clarify the nature of the superconducting pre-pairing above the bulk transition temperature T c . Different experimental probes have given conflicting results, in part due to difficulties in discerning the superconducting response from the complex normal-state behavior. Moreover, it has proven challenging to separate common properties of the cuprates from compound-specific idiosyncrasies. Here we investigate the paraconductivity—the superconducting contribution to the direct-current (dc) conductivity—of the simple-tetragonal model cuprate material HgBa 2 CuO 4+ δ . We are able to separate the superconducting and normal-state responses by taking advantage of the Fermi-liquid nature of the normal state in underdoped HgBa 2 CuO 4+ δ ; the robust and simple quadratic temperature-dependence of the normal-state resistivity enables us to extract the paraconductivity above the macroscopic T c with great accuracy. We find that the paraconductivity exhibits unusual exponential temperature dependence, and that it can be quantitatively explained by a simple superconducting percolation model. Consequently, the emergence of superconductivity in this model system is dominated by the underlying intrinsic gap inhomogeneity. Motivated by these insights, we reanalyze published results for two other cuprates and find exponential behavior as well, with nearly the same characteristic temperature scale. The universal intrinsic gap inhomogeneity is not only essential for understanding the supercoducting precursor, but will also have to be taken into account in the analysis of other bulk measurements of the cuprates.

Popčević, Petar↗
DOE OSTI2019

Genetic and structural insights into broad neutralization of hepatitis C virus by human V H 1-69 antibodies

An effective vaccine to the antigenically diverse hepatitis C virus (HCV) must target conserved immune epitopes. Here, we investigate cross-neutralization of HCV genotypes by broadly neutralizing antibodies (bNAbs) encoded by the relatively abundant human gene family V H 1-69. We have deciphered the molecular requirements for cross-neutralization by this unique class of human antibodies from crystal structures of HCV E2 in complex with bNAbs. An unusually high binding affinity is found for germ line–reverted versions of V H 1-69 precursor antibodies, and neutralization breadth is acquired during affinity maturation. Deep sequencing analysis of an HCV-immune B cell repertoire further demonstrates the importance of the V H 1-69 gene family in the generation of HCV bNAbs. This study therefore provides critical insights into immune recognition of HCV with important implications for rational vaccine design.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1974

Viscous, radiating hypersonic flow about a blunt body

The viscous, radiating hypersonic flow past an axisymmetric blunt body is analyzed based on the Navier-Stokes equations, plus a radiative equation of transfer derived from the Milne-Eddington differential approximation. The fluid is assumed to be a perfect gas with constant specific heats, a constant Prandtl number of order unity, a viscosity coefficient varying as a power of the temperature, and an absorption coefficient varying as the first power of the density and as a power of the temperature. The gray gas assumption is invoked, thereby making the absorption coefficient independent of the spectral frequency. Limiting forms of the solutions are studied as the freestream Mach number freestream Reynolds number and the temperature ratio across the shock wave, go to infinity, and as the Bouguer number and the density ratio across the shock wave go to zero. The method of matched asymptotic expansions is used in the analysis, and it is shown that there is a far-field precursor, composed of two regions, in which the fluid mechanics can be neglected for all practical purposes but included for completeness.

Passamaneck, R. S.↗
NASA NTRS1974

Post-earthquake dilatancy recovery

Geodetic measurements of the 1964 Niigata, Japan earthquake and of three other examples are briefly examined. They show exponentially decaying subsidence for a year after the quakes. The observations confirm the dilatancy-fluid diffusion model of earthquake precursors and clarify the extent and properties of the dilatant zone. An analysis using one-dimensional consolidation theory is included which agrees well with this interpretation.

Scholz, C. H.↗
NASA NTRS1976

Quinoxaline polymers and copolymers derived from 1,4-bis(1'-naphthalenyloxalyl)benzene and their graphite composites

Experimental studies were performed with new polyquinoxalines and their graphite composites. Four polymers were synthesized, and then were characterized with respect to their inherent viscosity, elemental chemical analysis, mechanical, and thermodynamic properties. Structural formulas of the polymers and their precursors are given; methods of synthesis are described; and specifically examined was the preparation of polymers from 3,3' diamino-benzidine from 1,4- and 1,3- bis ((1'-napthalenyl) oxalyl) benzene respectively. Also considered was the preparation of polyquinoxalines from poly (p-benzil), and 1,2- aryldiamines.

Port, W. S.↗
NASA NTRS1992

Effects of spaceflight on hypothalamic peptide systems controlling pituitary growth hormone dynamics

Possible effects of reduced gravity on central hypophysiotropic systems controlling growth hormone (GH) secretion were investigated in rats flown on Cosmos 1887 and 2044 biosatellites. Immunohistochemical (IHC)staining for the growth hormone-releasing factor (GRF), somatostatin (SS), and other hypothalamic hormones was performed on hypothalami obtained from rats. IHC analysis was complemented by quantitative in situ assessments of mRNAs encoding the precursors for these hormones. Data obtained suggest that exposure to microgravity causes a preferential reduction in GRF peptide and mRNA levels in hypophysiotropic neurons, which may contribute to impared GH secretion in animals subjected to spaceflight. Effects of weightlessness are not mimicked by hindlimb suspension in this system.

Sawchenko, P. E.↗
NASA NTRS2002

Viscoelastic and Mechanical Properties of Thermoset PMR-type Polyimide-Clay Nanocomposites

High temperature thermoset polyimide-clay nanocomposites were prepared by blending 2.5 and 5 wt% of an unmodified Na(+-) montmorillonite (PGV) and two organically modified FGV (PGVCl0COOH, PGVC12) with a methanol solution of PMR-15 precursor. The methanol facilitated the dispersal of the unmodified clay. Dynamic mechanical analysis results showed a significant increase in the thermomechanical properties (E' and E") of 2.5 wt% clay loaded nanocomposites in comparison with the neat polyimide. Higher glass transition temperatures were observed for 2.5 wt% nanocomposites compared to the neat polyimide. Flexural properties measurements for the 2.5 wt% nanocomposites showed a significant improvement in the modulus and strength, with no loss in elongation. This trend was not observed for the 5 wt% nanocomposites. An improvement in the CTE was observed for the PGV/PMR-15 nanocomposites, while a decrease was observed for the organically modified samples. This was attributed to potential variations in the interface caused by modifier degradation.

Abdalla, Mohamed O.↗