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DOE OSTI2025

Fiber-optic bolometer with low detection limit fabricated using thermal release tape and precise laser heating

Fiber-optic bolometers (FOBs) based on a fiber-tipped silicon Fabry–Perot (FP) interferometric temperature sensor and a gold disk absorber have been shown to be an attractive alternative to conventional resistive bolometers for plasma radiation measurement in fusion devices. Either a high-finesse FP or a low-finesse FP can be used, each with trade-offs between noise performance and fabrication complexity. In this paper, we present an FOB design that overcomes these limitations by combining a low-finesse long silicon FP cavity with a large gold disk absorber to achieve enhanced sensitivity and noise performance without increasing the fabrication complexity and the time constant. We also demonstrated a fabrication method for the sensor head facilitated by thermal release tape and precise laser heating. Our FOB demonstrates a temperature resolution of 0.08 mK, a cooling time constant of 230 ms, and a noise equivalent power density of 0.015 W m −2 . This represents an eightfold improvement over previous high-finesse FOBs and 26-fold improvement over previous low-finesse FOBs with similar demodulation bandwidths and similar cooling time constants.

Fabry–Perot interferometer↗

NASA NTRS2001

Reaction Kernel Structure of a Slot Jet Diffusion Flame in Microgravity

Diffusion flame stabilization in normal earth gravity (1 g) has long been a fundamental research subject in combustion. Local flame-flow phenomena, including heat and species transport and chemical reactions, around the flame base in the vicinity of condensed surfaces control flame stabilization and fire spreading processes. Therefore, gravity plays an important role in the subject topic because buoyancy induces flow in the flame zone, thus increasing the convective (and diffusive) oxygen transport into the flame zone and, in turn, reaction rates. Recent computations show that a peak reactivity (heat-release or oxygen-consumption rate) spot, or reaction kernel, is formed in the flame base by back-diffusion and reactions of radical species in the incoming oxygen-abundant flow at relatively low temperatures (about 1550 K). Quasi-linear correlations were found between the peak heat-release or oxygen-consumption rate and the velocity at the reaction kernel for cases including both jet and flat-plate diffusion flames in airflow. The reaction kernel provides a stationary ignition source to incoming reactants, sustains combustion, and thus stabilizes the trailing diffusion flame. In a quiescent microgravity environment, no buoyancy-induced flow exits and thus purely diffusive transport controls the reaction rates. Flame stabilization mechanisms in such purely diffusion-controlled regime remain largely unstudied. Therefore, it will be a rigorous test for the reaction kernel correlation if it can be extended toward zero velocity conditions in the purely diffusion-controlled regime. The objectives of this study are to reveal the structure of the flame-stabilizing region of a two-dimensional (2D) laminar jet diffusion flame in microgravity and develop a unified diffusion flame stabilization mechanism. This paper reports the recent progress in the computation and experiment performed in microgravity.

Takahashi, F.↗

NASA NTRS2012

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Archer, Douglas↗

NASA NTRS2001

Thermal Desorption/GCMS Analysis of Astrobiologically Relevant Organic Materials

Several macromolecular organic materials, both biologically-derived (type II kerogen and humic acid) and abiotic in origin (Murchison insoluble organic material, cyanide polymer, and Titan tholin) were subjected to thermal desorption using a Chromatoprobe attachment on a Varian Saturn 2000 GCMS system. Each sample was heated sequentially at 100, 200, and 300 C to release volatile components. The evolved compounds were then separated on a Supelco EC-1 dimethylsilica GC column and detected by the Saturn 2000 ion trap mass spectrometer. The various types of macromolecular organic material subjected to thermal desorption produced distinctly different GCMS chromatograms at each temperature, containing fractions of both low and high chromatographic mobility. The relative amounts of detectable volatiles released at each temperature also differed, with type II kerogen and cyanide polymer containing the highest percentage of low-temperature components. In all the samples, the highest yield of released compounds occurred at 300 C. Only cyanide polymer evolved a homologous hydrocarbon series, suggesting that it is the only material among those examined that contains a truly polymeric structure. Pyrolysis/gas chromatography/mass spectrometry has been used extensively for analysis of terrestrial organic macromolecular materials, and was also part of the instrument package on the Viking landers. Thorough analysis by pyrolysis usually employs temperatures of 500 C or higher, which for in situ analyses can be problematic given spacecraft power and materials constraints. This study demonstrates that heating of organic materials of astrobiological relevance to temperatures as low as 200-300 C for short periods releases volatile components that can be analyzed by gas chromatography and mass spectrometry. Even in the absence of full pyrolysis, useful chemical information on samples can be obtained, and materials from different biological and abiological sources can be distinguished. The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

McDonald, Gene D.↗

NASA NTRS1987

Pressure scaling effects in a scramjet combustion chamber

The test results obtained for a model scramjet over a range of pressure levels corresponding to different flight altitudes involve enthalpies that vary from the ignition limit, at the low temperature end, to temperatures where the dissociation of combustion products severely limits heat release. The minimum temperature is noted to be highly pressure-sensitive; above the ignition limit, the amount of heat release increased markedly with pressure and with combustion chamber length. A FEM computer code has been used to model the mixing and combustion processes.

Morgan, R. G.↗

DOE OSTI2021

New insights into fuel blending effects: Intermolecular chemical kinetic interactions affecting autoignition times and intermediate-temperature heat release

Fuel blending effects on chemically-dominated fuel properties, such as gasoline anti-knock quality, are influenced by fundamental chemical kinetic interactions between the blending agent and the base fuel. Historically, quantification of such interactions has focused on changes to the radical pool, including $\dot{O}$H and HO 2 , while intermolecular interactions pertaining to carbonated, non-fuel-specific intermediates are typically overlooked. In this regard, this work aims to derive new insight into intermolecular chemical kinetic interactions that are intrinsic to fuel blending effects via a case study on blends of 0–30% ethanol (by volume) into FGF-LLNL (a multi-component gasoline surrogate for FACE-F research gasoline) using a rapid compression machine at a diluted/stoichiometric fuel loading, compressed pressure of 40 bar and low- to intermediate-temperature regimes that are representative of boosted SI engine operation. Ethanol blending effects on the intermediate temperature heat release (ITHR) of FGF-LLNL are characterized using experimental measurements, where ethanol is found to promote the extent of ITHR and suppress the transition from ITHR to main ignition. Chemical kinetic modeling is undertaken using a recently updated gasoline surrogate model. Sensitivity analyses on ITHR characteristics further corroborate the ethanol blending effects, and highlight the significant dependence of ITHR on both fuel-specific and non-fuel-specific reactions. An approach allowing comprehensive characterization of the complex intermolecular chemical kinetic interactions between constitutes in a fuel blend is then proposed. Application of the approach to FGF-LLNL/E0–E30 reveals that ethanol perturbs the heat release and autoignition characteristics of FGF-LLNL not only by directly changing the $\dot{O}$H and HO 2 radical pools via fuel-specific reactions, but also through intermolecular interactions where participating intermediates can be produced and consumed by various sub-chemistries. Disabling the intermolecular interactions in carbonated species between ethanol and FGF-LLNL sub-chemistries leads to somewhat slower ITHR evolution and lower ignition reactivity. The role of the individual intermolecular interaction is also characterized using the proposed approach. Lastly, implications of intermolecular interactions for future studies that aim to improve model performance are highlighted, where it is found that further investigations on the core C0-C4 chemistry are needed for developing highly accurate chemistry models for complex fuel blends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1970

Intumescent Coatings as Fire Retardants

The development of fire-retardant coatings to protect surfaces which may be exposed to fire or extreme heat is a subject of intense interest to many industries. A fire-retardant paint has been developed which represents a new chemical approach for preparing intumescent coatings, and potentially, is very important to fire-prevention authorities. The requirements for a superior coating include ease of application, suitability to a wide variety of surfaces and finishes, and stability over an extended period of time within a broad range of ambient temperature and humidity conditions. These innovative coatings, when activated by the heat of a fire, react to form a thick, low-density, polymeric coating or char layer. Water vapor and sulphur dioxide are released during the intumescent reaction. Two fire-protection mechanisms thus become available: (1) the char layer retards the flow of heat, due to the extremely low thermal conductivity; and (2) water vapor and sulfur dioxide are released, providing fire quenching properties. Still another mechanism functions in cases where the char, by virtue of its high oxidation resistance and low thermal conductivity, reaches a sufficiently high temperature to re-radiate much of the incident heat load. The coatings consist of dispersions of selective salts of a nitro-amino-arornatic compound. Specifically, para-nitroaniline bisulfate and the ammonium salt of para-nitroaniline-ortho sulphuric acid (2-amino-5-nitrobenzenesulphuric acid) are used. Suitable vehicles are cellulose nitrate of lacquer grade, a nitrite-phenolic modified rubber, or epoxy-polysulfide copolymer. Three separate formulations have been developed. A solvent is usually employed, such as methylethyl ketone, butyl acetate, or toluene, which renders the coatings suitably thin and which evaporates after the coatings are applied. Generally, the intumescent material is treated as insoluble in the vehicle, and is ground and dispersed in the vehicle and solvent like an ordinary coating pigment. The char found on intumescence is better in terms of yield and physical properties than chars obtained from many previously known intumescent materials. Prior to intumescence, the coating has a density of 85 pounds per cubic foot. After intumescence, the density is approximately 0.3 pounds per cubic loot. The linear expansion of the coatings ranges from 70 to 200 times the applied coating thickness.

Parker, J. A.↗

NASA NTRS1980

Fission xenon in troctolite 76535

Xenon released in stepwise heating of troctolite 76535 shows remarkable similarity to that from the gas-rich breccias. The low temperature fractions are highly enriched in fissiogenic xenon from Pu-244. Although the quantity of fission xenon is not inconsistent with reported age data, release patterns demonstrate that this component is not due to in situ decay. However, in contrast with the gas-rich breccias, the parentless radionuclear component in 76535 is not accompanied by solar wind xenon. Mechanisms for the emplacement of this component in 76535 cannot, therefore, involve exposure on the lunar surface but most likely involve adsorption along intergranular boundaries or thermally driven redistribution. The fact that xenon released from a gas-poor igneous cumulate can mimic that from gas-rich breccias, except for the presence of solar wind xenon in the latter, suggests that direct exposure to space is not required for the incorporation of these weakly bound, surface-correlated, parentless radionuclear components in lunar samples.

Hohenberg, C. M.↗

NASA NTRS1992

Results of an Icing test on a NACA 0012 airfoil in the NASA Lewis Icing Research Tunnel

Tests were conducted in the Icing Research Tunnel (IRT) at the NASA Lewis Research Center to document the current capability of the IRT, focused mainly on the repeatability of the ice shape over a range of icing conditions. Measurements of drag increase due to the ice accretion were also made to document the repeatability of drag. Surface temperatures of the model were obtained to show the effects of latent-heat release by the freezing droplets and heat transfer through the ice layer. The repeatability of the ice shape was very good at low temperatures, but only fair at near freezing temperatures. In general, drag data shows good repeatability.

Shin, Jaiwon↗

NASA NTRS1992

Results of an icing test on a NACA 0012 airfoil in the NASA Lewis Icing Research Tunnel

Shin, Jaiwon↗

DOE OSTI2021

Ignition delay times of NH 3 /DME blends at high pressure and low DME fraction: RCM experiments and simulations

Here, autoignition delay times of ammonia/dimethyl ether (NH 3 /DME) mixtures were measured in a rapid compression machine with DME fractions of 0, 2 and 5 and 100% in the fuel. The measurements were performed at equivalence ratios $\varphi$= 0.5, 1.0 and 2.0 and pressures in the range 10–70 bar; depending on the fuel composition, the temperatures after compression varied from 610 K to 1180 K. Admixture of DME is seen to have a dramatic effect on the ignition delay time, effectively shifting the curves of ignition delay vs. temperature to lower temperatures, up to ~250 K compared to pure ammonia. Two-stage ignition is observed at $\varphi$= 1.0 and 2.0 with 2% and 5% DME in the fuel, despite the pressure being higher than that at which pure DME shows two-stage ignition. At $\varphi$= 0.5, a reproducible pre-ignition pressure rise is observed for both DME fractions, which is not observed in the pure fuel components. A novel NH 3 /DME mechanism was developed, including modifications in the NH 3 subset and addition of the NH 2 + CH 3 OCH 3 reaction, with rate coefficients calculated from ab initio theory. Simulations faithfully reproduce the observed pre- ignition pressure rise. While the mechanism also exhibits two-stage ignition for NH 3 /DME mixtures, both qualitative and quantitative improvement is recommended. The overall ignition delay times for ammonia/DME mixtures are predicted well, generally being within 50% of the experimental values, although reduced performance is observed for pure ammonia at $\varphi$= 2.0. Simulating the ignition process, we observe that the DME is oxidized much more rapidly than ammonia. Analysis of the mechanism indicates that this ‘early DME oxidation’ generates reactive species that initiate the oxidation of ammonia, which in turn begins heat release that raises the temperature and accelerates the oxidation process towards ignition. The reaction path analysis shows that the low-temperature chain-branching reactions of DME are important in the early oxidation of the fuel, while the sensitivity analysis indicates that several reactions in the oxidation of DME, including cross reactions between DME and NH 3 species presented here, are critical to ignition, even at fractions of 2% DME in the fuel.

10 SYNTHETIC FUELS↗

NASA NTRS1976

A simple approach to metal hydride alloy optimization

Certain metals and related alloys can combine with hydrogen in a reversible fashion, so that on being heated, they release a portion of the gas. Such materials may find application in the large scale storage of hydrogen. Metal and alloys which show high dissociation pressure at low temperatures, and low endothermic heat of dissociation, and are therefore desirable for hydrogen storage, give values of the Hildebrand-Scott solubility parameter that lie between 100-118 Hildebrands, (Ref. 1), close to that of dissociated hydrogen. All of the less practical storage systems give much lower values of the solubility parameter. By using the Hildebrand solubility parameter as a criterion, and applying the mixing rule to combinations of known alloys and solid solutions, correlations are made to optimize alloy compositions and maximize hydrogen storage capacity.

Lawson, D. D.↗

DOE OSTI2023

Sensitivity of Arctic Surface Temperature to Including a Comprehensive Ocean Interior Reflectance to the Ocean Surface Albedo Within the Fully Coupled CESM2

Abstract Almost all current climate models simplify the ocean surface albedo (OSA) by assuming the reflected solar energy without the ocean interior contribution. In this study, an improved ocean surface albedo scheme is incorporated into the Community Earth System Model version 2 (CESM2) to assess the sensitivity of Arctic surface temperature to including ocean interior reflectance to the OSA. Fully coupled CESM2 simulations with and without ocean interior reflectance are subsequently performed, we focus on the analysis of Arctic surface temperature responses. Incorporating ocean interior reflectance increases absorbed solar radiation and warms the ocean, enhancing seasonal heat storage and release across the Arctic Ocean, and increasing sea ice reduction and positive climate feedbacks that elevates Arctic surface temperature. Seasonal variations in air‐surface temperature differences induce changes in turbulent heat flux patterns, concurrently modifying dynamic advection and moisture processes that affect boundary layer humidity and low clouds, especially in winter. Based on partitioning physical processes in the thermodynamic energy equation, surface air warming is induced primarily through positive heating anomalies of vertical advection, latent heat release, and longwave radiative forcing. Through an examination of the surface energy budget, skin temperature warming is driven predominantly by increased downward longwave radiation, positive surface albedo feedback in summer, and increased conductive heat transport from the ocean particularly in winter. Significant effects of ocean interior reflectance on the Arctic Ocean, including sea surface warming and sea ice reduction, justify the importance of ocean interior reflectance in climate models for better understanding of ongoing Arctic climate changes.

Meteorology & Atmospheric Sciences↗

DOE OSTI2020

Effects of isoalcohol blending with gasoline on autoignition behavior in a rapid compression machine: Isopropanol and isobutanol

Alcohols, and particularly isoalcohols, are potentially advantageous blendstocks towards achieving efficient, low-carbon intensity internal combustion engines. Their use in advanced configurations, such as boosted spark-ignition or spark-assisted compression ignition, requires a comprehensive understanding of their blending effects on the low- and intermediate-temperature autoignition behavior of petroleum-derived gasoline. This work reports an experimental and modeling study of such autoignition characteristics quantified in a twin-piston rapid compression machine. Isopropanol and isobutanol are blended into a research-grade gasoline (FACE-F) at oxygenate blend levels of 0 to 30% vol/vol, with tests conducted at pressures of 20 and 40 bar, temperatures from 700 to 1000 K, and dilute stoichiometric fuel loadings. Changes to overall reactivity, including first-stage and main ignition times, and preliminary exothermicity are established, with comparisons made to previous measurements with ethanol-blended FACE-F gasoline. Furthermore, it is found that at low-temperature/NTC conditions (700–860 K) the isoalcohols suppress first-stage reactivity and associated heat release while main ignition times are extended. At NTC/intermediate-temperature (860–1000 K) conditions changes to fuel reactivity are less significant with isopropanol slightly suppressing reactivity and isobutanol promoting ignition. Detailed chemical kinetic modeling is used to interpret the experimental measurements. Overall trends of suppression or promotion in the blending behavior are reasonably captured by the model. Sensitivity and rate of production analyses indicate that at lower temperatures H-atom abstraction reactions from the surrogate fuel molecules (e.g., cyclopentane, isooctane) and the isoalcohols via OH are important leading to TC 3 H 6 OH and IC 4 H 8 OH–C radicals, for isopropanol and isobutanol respectively, which act as scavengers in the system. At higher temperatures, similar chemistries are dominant, but there is an increasing importance of abstraction by HO 2 . The kinetic modeling also indicates that the promoting effect of isobutanol at higher temperatures is due to the increased abstractions at the γ-sites, while at lower temperatures abstraction at the α-site leads to greater reactivity suppression.

36 MATERIALS SCIENCE↗

NASA NTRS2011

Common Warm Dust Temperatures Around Main Sequence Stars

We compare the properties of warm dust emission from a sample of main-sequence A-type stars (B8-A7) to those of dust around solar-type stars (F5-KO) with similar Spitzer Space Telescope Infrared Spectrograph/MIPS data and similar ages. Both samples include stars with sources with infrared spectral energy distributions that show evidence of multiple components. Over the range of stellar types considered, we obtain nearly the same characteristic dust temperatures (∼ 190 K and ∼60 K for the inner and outer dust components, respectively)-slightly above the ice evaporation temperature for the inner belts. The warm inner dust temperature is readily explained if populations of small grains are being released by sublimation of ice from icy planetesimals. Evaporation of low-eccentricity icy bodies at ∼ 150 K can deposit particles into an inner/warm belt, where the small grains are heated to dust Temperatures of -190 K. Alternatively, enhanced collisional processing of an asteroid belt-like system of parent planetesimals just interior to the snow line may account for the observed uniformity in dust temperature. The similarity in temperature of the warmer dust across our B8-KO stellar sample strongly suggests that dust-producing planetesimals are not found at similar radial locations around all stars, but that dust production is favored at a characteristic temperature horizon.

Morales, Farisa↗

DOE OSTI2025

Magnetic Properties and Large Second-Harmonic Generation Response of a Chiral Ternary Chalcogenide: Eu 2 SiSe 4

Eu(II)-containing chalcogenides are an emerging class of materials that are of great interest due to their high optical activity and intriguing magnetism. Here, we synthesized Eu 2 SiSe 4 as red-colored single crystals and characterized its structure with single-crystal X-ray diffraction, confirming the reported chiral monoclinic P2 1 symmetry at room temperature. The crystal structure of Eu 2 SiSe 4 comprises distorted SiSe 4 tetrahedral units and charge-balancing Eu(II) cations. Here, we develop a two-step solid-state synthesis method for Eu 2 SiSe 4 and compare it to the known boron chalcogenide method. We find the second-harmonic generation (SHG) activity of polycrystalline Eu 2 SiSe 4 to be ∼7 × AgGaS 2 , placing it among the highest-known SHG-active chalcogenides. No symmetry lowering is observed down to 100 K in single-crystal X-ray diffraction, although an anomalous expansion in the b-axis lattice parameter occurs and may be correlated to lattice modes of the SiSe 4 tetrahedra. We investigate the physical properties of Eu 2 SiSe 4 using magnetometry and heat capacity measurements and find a transition to an antiferromagnetic ground state at T N ≈ 5.5 K. The low-temperature transition releases less entropy than expected, which may be due to the complex crystal electric field effects of Eu(II).

36 MATERIALS SCIENCE↗

NASA NTRS1978

A neon-E rich phase in Orgueil - Results of stepwise heating experiments

A Ne-E rich phase was separated from the Orgeuil carbonaceous chondrite. He and Ne were analyzed in this phase and in an Orgueil residual bulk silicate sample using the stepwise heating technique. Ne-E was found to be released from the Ne-E rich phase at temperatures as low as 500 C; however, gas richest in Ne-E is observed at the highest temperatures (1230 C). The following limits for the isotopic composition of Ne-E were obtained: Ne-20/Ne-22 less than 1.52; Ne-21/Ne-22 less than 0.0244.

Eberhardt, P.↗

NASA NTRS1994

Noble gases in presolar diamonds II: Component abundances reflect thermal processing

Using the isotopic compositions derived in Huss and Lewis, 1994a, abundances of the P3, HL, and P6 noble-gas components were determined for 15 diamonds separates from primitive chondrites of 8 chondrite classes. Within a meteorite class, the relative abundances of these components correlate with the petrologic subtype of the host meteorite, indicating that metamorphism is primarily responsible for the variations. Relative abundances of P3, HL, and P6 among diamond samples can be understood in terms of thermal processing of a single mixture of diamonds like those now found in CI and CM2 chondrites. With relatively gentle heating, primitive diamonds first lose their low-temperature P3 gases and a 'labile' fraction of the HL component. Mass loss associated with release of these components produces an increase in the HL and P6 content of the remaining diamond relative to unprocessed diamond. Higher temperatures initiate destruction of the main HL carrier, while the HL content of the surviving diamonds remains essentially constant. At the same time, the P6 carrier begins to preferentially lose light noble gases. Meteorites that have experienced metamorphic temperatures greater than or = 650 C have lost essentially all of their presolar diamond through chemical reactions with surrounding minerals. The P3 abundance seems to be a function only of the maximum temperature experienced by the diamonds and thus is independent of the nature of the surrounding environment. If all classes inherited the same mixture of primitive diamonds, then P3 abundances would tie together the metamorphic scales in different meteorite classes. However, if the P3 abundance indicates a higher temperature than do other thermometers applicable to the host meteorite, then the P3 abundance may contain information about heating prior to accretion. Diamonds in the least metamorphosed EH, CV, and CO chondrites seem to carry a record of pre-accretionary thermal processing.

Huss, Gary R.↗