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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Stability of chromium (III) sulfate in atmospheres containing oxygen and sulfur

The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).

Jacob, K. T.↗
DOE OSTI2014

Recognizing molecular patterns by machine learning: An agnostic structural definition of the hydrogen bond

The concept of chemical bonding can ultimately be seen as a rationalization of the recurring structural patterns observed in molecules and solids. Chemical intuition is nothing but the ability to recognize and predict such patterns, and how they transform into one another. Here, we discuss how to use a computer to identify atomic patterns automatically, so as to provide an algorithmic definition of a bond based solely on structural information. We concentrate in particular on hydrogen bonding – a central concept to our understanding of the physical chemistry of water, biological systems, and many technologically important materials. Since the hydrogen bond is a somewhat fuzzy entity that covers a broad range of energies and distances, many different criteria have been proposed and used over the years, based either on sophisticate electronic structure calculations followed by an energy decomposition analysis, or on somewhat arbitrary choices of a range of structural parameters that is deemed to correspond to a hydrogen-bonded configuration. We introduce here a definition that is univocal, unbiased, and adaptive, based on our machine-learning analysis of an atomistic simulation. The strategy we propose could be easily adapted to similar scenarios, where one has to recognize or classify structural patterns in a material or chemical compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Inviscid criterion for decomposing scales

The proper scale decomposition in flows with significant density variations is not as straightforward as in incompressible flows, with many possible ways to define a “length scale.” A choice can be made according to the so-called inviscid criterion [Aluie, Physica D 24, 54 (2013)]. It is a kinematic requirement that a scale decomposition yield negligible viscous effects at large enough length scales. It has been proved [Aluie, Physica D 24, 54 (2013)] recently that a Favre decomposition satisfies the inviscid criterion, which is necessary to unravel inertial-range dynamics and the cascade. We present numerical demonstrations of those results. We also show that two other commonly used decompositions can violate the inviscid criterion and, therefore, are not suitable to study inertial-range dynamics in variable-density and compressible turbulence. Our results have practical modeling implication in showing that viscous terms in Large Eddy Simulations do not need to be modeled and can be neglected.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Pyrolysis Pathways of the Furanic Ether 2-Methoxyfuran

Substituted furans, including furanic ethers, derived from nonedible biomass have been proposed as second-generation biofuels. In order to use these molecules as fuels, it is important to understand how they break apart thermally. In this work, a series of experiments were conducted to study the unimolecular and low-pressure bimolecular decomposition mechanisms of the smallest furanic ether, 2-methoxyfuran. Electronic structure (CBS-QB3) calculations indicate this substituted furan has an unusually weak O - CH 3 bond, approximately 190 kJ mol -1 (45 kcal mol -1 ); thus, the primary decomposition pathway is through bond scission resulting in CH 3 and 2-furanyloxy (O - C 4 H 3 O) radicals. Final products from the ring opening of the furanyloxy radical include 2 CO, HC$\equiv$CH, and H. The decomposition of methoxyfuran is studied over a range of concentrations (0.0025-0.1%) in helium or argon in a heated silicon carbide (SiC) microtubular flow reactor (0.66-1 mm i.d., 2.5-3.5 cm long) with reactor wall temperatures from 300 to 1300 K. Inlet pressures to the reactor are 150-1500 Torr, and the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products formed at early pyrolysis times (100 μs) are detected by 118.2 nm (10.487 eV) photoionization mass spectrometry (PIMS), tunable synchrotron VUV PIMS, and matrix infrared absorption spectroscopy. Secondary products resulting from H or CH 3 addition to the parent and reaction with 2-furanyloxy were also observed and include CH 2 =CH-CHO, CH 3 -CH=CH-CHO, CH 3 =CO-CH=CH 2 , and furanones; under the conditions in the reactor, we estimate these reactions contribute to at most 1-3% of total methoxyfuran decomposition. This work also includes observation and characterization of an allylic lactone radical, 2-furanyloxy (O-C 4 H 3 O), with the assignment of several intense vibrational bands in an Ar matrix, an estimate of the ionization threshold, and photoionization efficiency. A pressure-dependent kinetic mechanism is also developed to model the decomposition behavior of methoxyfuran and provide pathways for the minor bimolecular reaction channels that are observed experimentally.

09 BIOMASS FUELS↗
DOE OSTI2026

Point-scale organic-matter decomposition in streambeds is weakly associated with reach-scale respiration

Stream and river ecosystems play a central role in the movement and decomposition of particulate organic matter, serving as a conduit between terrestrial hillslopes and coastal environments. Microbial-catalyzed decomposition generates simpler organic molecules that fuel respiration, often in the sediments of these ecosystems. However, the degree of connection between sediment-associated respiration (ER??d) and organic-matter decomposition remains poorly understood. How that relationship compares to decomposition’s relationship with whole ecosystem (ERtot) and water column (ERwc) respiration is also not clear. We examined the link between particulate organic matter decomposition—using cellulose-based cotton strips as a standardized substrate—and all three components of respiration across 48 sites in the environmentally diverse Yakima River Basin (Washington State, USA). We hypothesized that decomposition within sediments would be most strongly related to ERsed, but decomposition rates were more closely associated with ERtot, with little connection to ERsed or ERwc. This suggests that particulate organic matter decomposition within stream/river sediments reflects integrated system respiration rather than processes confined to sediments or the water column alone. Further, across the basin, decomposition rates nearly spanned the previously reported global range for streams and rivers and were best explained by total dissolved nitrogen (TDN), sediment grain size, and aridity of the upstream drainage area. These results highlight the strong influence of land cover and basin-scale biophysical variation on sediment-associated decomposition processes and indicate that mechanistic models of organic matter decomposition in streams/rivers should account for coupled sediment–water–land interactions.

Stegen, James C. (ORCID:0000000191357424)↗
DOE OSTI2018

Alternative mechanisms of thermal decomposition of o-nitrotoluene in the gas phase

The density functional theory methods were used to demonstrate that during the thermal decomposition of o-nitrotoluene, with the formation of 5-methylene-6-aci-nitrocyclohexa- 1,3-diene (aci-form) being the primary event, the rotation of the =N(O)OH group around the CN double bond in the aci-form is of key importance. The activation enthalpy is lower for this step than for the alternative process of H atom transfer between the O atoms in this group. This accounts for the competitive formation of the experimentally observed products of о-nitrotoluene thermal decomposition, namely, the hydroxyl radical and water. The activation barriers of the reactions were estimated over a broad temperature range, which indicated the possible contribution of о-nitrotoluene thermal decomposition and other alternative primary event mechanisms (nitro—nitrite rearrangement, bicyclization) to the efficient rate constant. The results account for the differences between the activation parameters experimentally determined at various temperatures by different authors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Quantitative acetylene measurements in laminar and turbulent flames using 1D Raman/Rayleigh scattering

Our research presents the extension of the established detection of seven major species in 1D Raman/Rayleigh measurements to incorporate acetylene (C 2 H 2 ) as an eighth species. Acetylene is an important soot precursor which is generated in hydrocarbon flames as an intermediate species following decomposition. It occurs over a broad temperature range in flames and has been identified as a potentially detectable species in 1D Raman/Rayleigh measurements. In this paper, we discuss the Raman spectral signature of acetylene, its temperature dependence, calibration procedures, and the interference with other Raman-active species, C 2 and broadband interferences, all of which are essential to quantify for accurate data processing. In this regard, Raman measurements in laminar and turbulent dimethyl ether flames were acquired. The data are spectrally analyzed and low-temperature calibrations of the Raman response are combined with an extrapolation model for high temperatures in order to place the acetylene signals on an absolute scale. Single-shot and conditional-mean values are presented as a function of mixture fraction for a laminar partially-premixed DME/air flame. Measurements from the laminar flame are compared to a 1D laminar flame calculation to assess the accuracy of the calibration and analysis procedures. Furthermore, detection limits, signal-to-noise, and signal-to-interference ratio of the C 2 H 2 measurement are discussed, and single-shot measurements of acetylene in a turbulent DME/air jet flame are demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals

Intermolecular interactions between radicals and closed-shell molecules are ubiquitous in chemical processes, ranging from the benchtop to the atmosphere and extraterrestrial space. While energy decomposition analysis (EDA) schemes for closed-shell molecules can be generalized for studying radical–molecule interactions, they face challenges arising from the unique characteristics of the electronic structure of open-shell species. In this work, we introduce additional steps that are necessary for the proper treatment of radical–molecule interactions to our previously developed unrestricted Absolutely Localized Molecular Orbital (uALMO)-EDA based on density functional theory calculations. A “polarize-then-depolarize” (PtD) scheme is used to remove arbitrariness in the definition of the frozen wavefunction, rendering the ALMO-EDA results independent of the orientation of the unpaired electron obtained from isolated fragment calculations. The contribution of radical rehybridization to polarization energies is evaluated. It is also valuable to monitor the wavefunction stability of each intermediate state, as well as their associated spin density profiles, to ensure the EDA results correspond to a desired electronic state. The examples suggest that this second generation uALMO-EDA is a useful tool for furthering one's understanding of both energetic and property changes associated with radical–molecule interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effect of process temperature on morphology of CNTs grown in a vertically fluidized bed reactor with Fe{sub 2}O{sub 3}/Al{sub 2}O{sub 3} catalyst

Carbon nanotubes (CNTs) are one of the most researched materials due to their exceptional mechanical and electrical properties. Among the various techniques, catalytic chemical vapor deposition in a fluidized bed reactor is the most promising technique for bulk production of CNTs. To meet the demand of good quality along with the bulk production of CNTs, the effect of reaction temperature on the micro structures, morphology, diameter, quality and quantity of CNTs was investigated in these studies. CNTs were synthesized at process temperature ranging from 700-850°C by catalytic decomposition of C{sub 2}H{sub 4} on Fe{sub 2}O{sub 3}/Al{sub 2}O{sub 3} catalyst a vertical fluidized bed reactor. The microstructures of the grown CNTs at different reaction temperatures were investigated by using scanning electron microscope. The results of this study depicted a positive correlation between the average diameter of CNTs and reaction temperature. Narrow diameters (35∼40 nm) of CNTs with fewer defects were found at the low and mild temperatures, in particular 800°C. At this temperature, a dynamic equilibrium between the rate of C{sub 2}H{sub 4} decomposition and CNTs quantity was found due to maximum carbon diffusion over catalyst. The CNTs produced with Fe{sub 2}O{sub 3}/Al{sub 2}O{sub 3} catalyst wer e also exhibiting high quality with relatively small mean outer diameter and fewer surface defects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

High-pressure and temperature neural network reactive force field for energetic materials

Reactive force fields for molecular dynamics have enabled a wide range of studies in numerous material classes. These force fields are computationally inexpensive compared with electronic structure calculations and allow for simulations of millions of atoms. However, the accuracy of traditional force fields is limited by their functional forms, preventing continual refinement and improvement. Therefore, we develop a neural network-based reactive interatomic potential for the prediction of the mechanical, thermal, and chemical responses of energetic materials at extreme conditions. The training set is expanded in an automatic iterative approach and consists of various CHNO materials and their reactions under ambient and shock-loading conditions. Further, this new potential shows improved accuracy over the current state-of-the-art force fields for a wide range of properties such as detonation performance, decomposition product formation, and vibrational spectra under ambient and shock-loading conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

TU-CD-207-02: Quantification of Breast Lesion Compositions Using Low-Dose Spectral Mammography: A Feasibility Study

Purpose: To investigate the feasibility of measuring breast lesion composition with spectral mammography using physical phantoms and bovine tissue. Methods: Phantom images were acquired with a spectral mammography system with a silicon-strip based photon-counting detector. Plastic water and adipose-equivalent phantoms were used to calibrate the system for dual-energy material decomposition. The calibration phantom was constructed in range of 2–8 cm thickness and water densities in the range of 0% to 100%. A non-linear rational fitting function was used to calibrate the imaging system. The phantom studies were performed with uniform background phantom and non-uniform background phantom. The breast lesion phantoms (2 cm in diameter and 0.5 cm in thickness) were made with water densities ranging from 0 to 100%. The lesion phantoms were placed in different positions and depths on the phantoms to investigate the accuracy of the measurement under various conditions. The plastic water content of the lesion was measured by subtracting the total decomposed plastic water signal from a surrounding 2.5 mm thick border outside the lesion. In addition, bovine tissue samples composed of 80 % lean were imaged as background for the simulated lesion phantoms. Results: The thickness of measured and known water contents was compared. The rootmean-square (RMS) errors in water thickness measurements were 0.01 cm for the uniform background phantom, 0.04 cm for non-uniform background phantom, and 0.03 cm for 80% lean bovine tissue background. Conclusion: The results indicate that the proposed technique using spectral mammography can be used to accurately characterize breast lesion compositions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Optical Properties of Multilayered Sol–Gel Zinc-Oxide Films

Study of structural, optical and photocatalytic properties of multilayered (1–8 layers) zinc oxide films deposited on glass substrates by sol-gel method showed, that after thermal treatment at 500°C they consist of random oriented hexagonal crystalline grains with size of 34–40 nm, forming larger particles with sizes of 100–150 nm, which do not depend on number of layers. With an increase in the number of layers, the intensity of exciton photoluminescence decreases by a factor of 10, the absorption of light in the visible and near IR ranges increases, and the efficiency of photocatalytic decomposition of the test organic dye rhodamine B increases by 10–12%. The observed changes are related to the increase in the total area of grain boundaries and to the change in the integral amount of oxygen vacancies and interstitial atoms as the number of layers increases, which makes it possible to control the properties of zinc oxide films for applications in optoelectronics, photovoltaics and photocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A New Multiphase Equation of State for SiO 2

SiO 2 is found as α-quartz at ambient conditions. Under shock compression, it transforms into a much higher density stishovite-like phase around 20 GPa, then into a liquid phase above 100 GPa. The SESAME library contains older equations of state for α-quartz, polycrystalline quartz, and fused quartz. These equations of state model the material as a single phase; i.e., there is no high pressure phase transition. Somewhat more recently (in 1992), Jon Boettger published equations of state for α-quartz, coesite, and stishovite, along with a phase transition model to mix them. However, we do not have a multiphase EOS that captures the phase transitions in this material. Others are working on a high-accuracy model for very high pressure SiO 2 , since liquid quartz is used as an impedance matching standard above 100 GPa; however, we are focused on the 10-50 GPa range. This intermediate pressure range is most relevant for modeling the decomposition products of silicone polymers such as Sylgard 184 and SX358.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Using Additives to Control the Decomposition Temperature of Sodium Borohydride

Hydrogen (H 2 ) shows great promise as zero-carbon emission fuel, but there are several challenges to overcome in regards to storage and transportation to make it a more universal energy solution. Gaseous hydrogen requires high pressures and large volume tanks while storage of liquid hydrogen requires cryogenic temperatures; neither option is ideal due to cost and the hazards involved. Storage in the solid state presents an attractive alternative, and can meet the U.S. Department of Energy (DOE) constraints to find materials containing > 7 % H 2 (gravimetric weight) with a maximum H 2 release under 125 °C. While there are many candidate hydrogen storage materials, the vast majority are metal hydrides. Of the hydrides, this review focuses solely on sodium borohydride (NaBH 4 ), which is often not covered in other hydride reviews. However, as it contains 10.6% (by weight) H 2 that can release at 133 ± 3 JK -1 mol -1 , this inexpensive material has received renewed attention. NaBH 4 should decompose to H 2 (g), Na(s), and B(s), and could be recycled into its original form. Unfortunately, metal to ligand charge transfer in NaBH 4 induces high thermodynamic stability, creating a high decomposition temperature of 530 °C. In an effort make H 2 more accessible at lower temperatures, researchers have incorporated additives to destabilize the structure. This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH 4 , with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed, chemical pathways taken, and the challenges of boron derivative formation on H 2 cycling. Though no trends can be found across all additives, it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH 4 a more viable H 2 fuel source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

Here, the high pressure properties of the novel tetrel-free clathrate, Ba 8 Cu 13.1 Zn 3.3 P 29.6 , were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba 8 Cu 13.1 Zn 3.3 P 29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A 8 Ga 16 Ge 30 (A = Sr, Ba) and Sn 19.3 Cu 4.7 P 22 I 8 , but lower than those for the transition metal-containing silicon-based clathrates, Ba 8 T x Si46–x, T = Ni, Cu; 3 ≤ x ≤ 5.

36 MATERIALS SCIENCE↗
NASA NTRS1929

Effect of oxygen on the ignition of liquid fuels

The ignition temperature, ignition lag, and ignition strength of simple and homogeneous fuels in combustion air of small oxygen content differ from what they are in air of greater oxygen content. In the case of small oxygen content, these fuels behave as if mixed unevenly. In the case of air with a definite oxygen content, the simple fuels have two ignition points, between which ignition takes place within a certain temperature range. The phenomena are explained by pyrogenous decomposition, comparison of the individual heat quantities, and the effect of the walls.

IGNITION - EFFECT OF OXYGEN↗
NASA NTRS2009

New insights into the origin of magnetite crystals in ALH84001 carbonate disks

Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks which are believed to have precipitated approximately 3.9 Ga ago at beginning of the Noachian epoch. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these Fe3O4 are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of Fe3O4 and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. We have sought to resolve between these hypotheses through the detailed characterized of the compositional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded. We focus this discussion on the composition of ALH84001 magnetites and then compare these observations with those from experimental thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios.

Thomas-Keprta, K. L.↗