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At least 793 records · Page 44

Bromine Incorporation and Suppressed Cation Rotation in Mixed-Halide Perovskites

Engineering the composition of perovskite active layers has been critical in increasing the efficiency of perovskite solar cells (PSCs) to more than 25% in the latest reports. Partial substitutions of the monovalent cation and the halogen have been adopted in the highest-performing devices, but the precise role of bromine incorporation remains incompletely explained. Here we use quasi-elastic neutron scattering (QENS) to study, as a function of the degree of bromine incorporation, the dynamics of organic cations in triple-cation lead mixed-halide perovskites. We find that the inclusion of bromine suppresses low-energy rotations of formamidinium (FA), and we find that inhibiting FA rotation correlates with a longer-lived carrier lifetime. When the fraction of bromine approaches 0.15 on the halogen site—a composition used extensively in the PSC literature—the fraction of actively rotating FA molecules is minimized: indeed, the fraction of rotating FA is suppressed by more than 25% compared to the bromine-free perovskite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anisotropic magnetic and transport properties of orthorhombic o-Pr 2 Co 3 Ge 5

Abstract The crystal structure, electron energy-loss spectroscopy (EELS), heat capacity, and anisotropic magnetic and resistivity measurements are reported for Sn flux grown single crystals of orthorhombic Pr 2 Co 3 Ge 5 (U 2 Co 3 Si 5 -type, Ibam ). Our findings show that o -Pr 2 Co 3 Ge 5 hosts nearly trivalent Pr ions, as evidenced by EELS and fits to temperature dependent magnetic susceptibility measurements. Complex magnetic ordering with a partially spin-polarized state emerges near T sp = 32 K, with a spin reconfiguration transition near T M = 15 K. Heat capacity measurements show that the phase transitions appear as broad peaks in the vicinity of T sp and T M . The magnetic entropy further reveals that crystal electric field splitting lifts the Hund’s rule degeneracy at low temperatures. Taken together, these measurements show that Pr 2 Co 3 Ge 5 is an environment for complex f state magnetism with potential strongly correlated electron states.

36 MATERIALS SCIENCE↗

Rhizosphere microbiomes diverge among Populus trichocarpa plant-host genotypes and chemotypes, but it depends on soil origin

Abstract Background Plants have developed defense strategies for phytopathogen and herbivore protection via coordinated metabolic mechanisms. Low-molecular weight metabolites produced within plant tissues, such as salicylic acid, represent one such mechanism which likely mediates plant – microbe interactions above and below ground. Salicylic acid is a ubiquitous phytohormone at low levels in most plants, yet are concentrated defense compounds in Populus , likely acting as a selective filter for rhizosphere microbiomes. We propagated twelve Populus trichocarpa genotypes which varied an order of magnitude in salicylic acid (SA)-related secondary metabolites, in contrasting soils from two different origins. After four months of growth, plant properties (leaf growth, chlorophyll content, and net photosynthetic rate) and plant root metabolomics specifically targeting SA metabolites were measured via GC-MS. In addition, rhizosphere microbiome composition was measured via Illumina MiSeq sequencing of 16S and ITS2 rRNA-genes. Results Soil origin was the primary filter causing divergence in bacterial/archaeal and fungal communities with plant genotype secondarily influential. Both bacterial/archaeal and fungal evenness varied between soil origins and bacterial/archaeal diversity and evenness correlated with at least one SA metabolite (diversity: populin; evenness: total phenolics). The production of individual salicylic acid derivatives that varied by host genotype resulted in compositional differences for bacteria /archaea (tremuloidin) and fungi (salicylic acid) within one soil origin (Clatskanie) whereas soils from Corvallis did not illicit microbial compositional changes due to salicylic acid derivatives. Several dominant bacterial (e.g., Betaproteobacteria, Acidobacteria, Verrucomicrobia, Chloroflexi, Gemmatimonadete, Firmicutes ) and one fungal phyla ( Mortierellomycota ) also correlated with specific SA secondary metabolites; bacterial phyla exhibited more negative interactions (declining abundance with increasing metabolite concentration) than positive interactions. Conclusions These results indicate microbial communities diverge most among soil origin. However, within a soil origin, bacterial/archaeal communities are responsive to plant SA production within greenhouse-based rhizosphere microbiomes. Fungal microbiomes are impacted by root SA-metabolites, but overall to a lesser degree within this experimental context. These results suggest plant defense strategies, such as SA and its secondary metabolites, may partially drive patterns of both bacterial/archaeal and fungal taxa-specific colonization and assembly.

16S rRNA↗

Activation of propane on Ag–PdO(101) model surfaces

Oxidation of alkanes remains a central challenge in catalysis due to the high activation barriers of C–H bonds and the thermodynamic favorability of complete oxidation. Palladium oxide (PdO), particularly its (101) facet, is known for its high reactivity in alkane oxidation, which is attributed to its coordinatively unsaturated palladium (Pd) and O atoms. In this study, we investigate the effect of silver (Ag) incorporation on the oxidation behavior of propane over PdO(101) using temperature-programmed reaction spectroscopy (TPRS) under controlled conditions. While pristine PdO(101) exhibits complete oxidation of propane with CO₂ and H₂O desorption at high temperatures (approximately 475 K), Ag incorporation induces a new CO₂ desorption peak at significantly lower temperatures (approximately 330 K). This shift is attributed to the formation of new active sites at the Ag–PdO(101) interface. Quantitative analysis reveals that low-temperature activity correlates with Ag coverage, while overall CO₂ production decreases, suggesting a redistribution of reactivity rather than an increase in active surface area. Activation energy estimations using the Redhead method confirm that C–H bond activation becomes more facile at the interface, with a 46 kJ/mol reduction compared to pristine PdO(101). These findings demonstrate that incorporating a less reactive metal such as Ag into PdO surfaces not only modifies the reaction energetics but also enables the design of bimetallic catalysts with improved selectivity for partial oxidation reactions.

Chemistry↗

In-flight and laboratory vacuum-friction test results

Coefficient of friction measurements were made for six unlubricated metal couples exposed to the space environment aboard the OV-1-13 spacecraft and exposed to laboratory vacuum. Materials studied included mutually soluble, partially soluble, and insoluble metal combinations. Two samples of each material couple were tested in space and in the laboratory using the disk and rider technique. Linear velocity was 0.10 cm/s (2.5 in/min) and rider normal load was 4.45 N (1 lb) for the gold versus silver couples and 8.90 N (2lb) for the other combinations. Results showed that friction data obtained in a clean ion-pumped laboratory vacuum of 10 to the minus 10 power materials with low mutual solubility can be correlated to operation in the vicinity of a typical scientific spacecraft that is exposed to an ambient pressure as low as 10 to the minus 12 power torr. The expected increase in coefficient of friction with solubility was shown. Material couples with high mutual solubility present the hazard of unpredictable drastic friction increase in orbit which may not be evident in laboratory testing at levels down to 10 to the minus 10 power torr. It was also shown that gross cold welding of unlubricated metals exposed to a satellite environment does not occur.

Devine, E. J.↗

Sodium D-line emission from Io - Synoptic observations from Table Mountain Observatory

We report the first results of a program initiated at Table Mountain Observatory to study the time variation of the sodium D-line emission around Io. During 1974 July and August, 51 spectra were obtained. These data demonstrate that (1) the sodium emission is highly correlated with Io's orbital position, (2) the gross temporal and amplitude characteristics of the emission are explained if resonance scattering of sunlight is the dominant excitation mechanism, (3) the emission is not directly related to dekametric noise storms from Jupiter, (4) an upper limit of 130 kR is placed on any constant near-surface (auroral) source of emission, (5) a steady-state source of sodium operated during our 7-week observing interval, (6) the sodium cloud is probably distributed in a partial toroid, possibly with more sodium leading than trailing Io, and (7) the D-line emission does not depend strongly on the solar phase angle.

Bergstralh, J. T.↗

Carbon and oxygen isotope study of carbonates from highly shocked clasts of the polymict breccia of the Haughton Crater (Canada)

It is known that the release of volatiles on impact is an important controlling factor in cratering processes in carbonate terranes and in the mobility of chemical elements. In order to assess the nature and the role of carbon- and oxygen-bearing volatiles during impact-induced metamorphism of sedimentary rocks, the C-13/C-12 and O-18/O-16 ratios and carbonate contents were determined for 30 shocked clasts from the Haughton Crater polymict breccia as well as for some unshocked carbonates from the sedimentary cover adjacent to the crater. Shock-induced CO2 loss during decarbonation of calcite is known to be a function of peak pressure and ambient partial pressure of the volatile species. In our clast samples, shocked from 20 to 60 GPa, we expect about 20 to 100 percent CO2 loss and preferential depletion in C-13 and O-18 in the residual carbonate. Rayleigh model (progressive loss of CO2) and batch model (single-step loss of CO2) curves for this depletion are shown. The magnitudes of the C-13 and O-18 depletions increase with the increase of the CO2 loss. In addition, the isotopic depletions should be correlated with an enrichment in CaO and MgO in the residual solid.

Agrinier, P.↗

Micromechanical simulation of damage progression in carbon phenolic composites

Carbon/phenolic composites are used extensively as ablative insulating materials in the nozzle region of solid rocket motors. The current solid rocket motor (RSRM) on the space shuttle is fabricated from woven rayon cloth which is carbonized and then impregnated with the phenolic resin. These plies are layed up in the desired configuration and cured to form the finished part. During firing, the surface of the carbon/phenolic insulation is exposed to 5000 F gases from the rocket exhaust. The resin pyrolizes and the material chars to a depth which progresses with time. The rate of charring and erosion are generally predictable, and the insulation depth is designed to allow adequate safety margins over the firing time of the motor. However, anomalies in the properties and response of the carbon/phenolic materials can lead to severe material damage which may decrease safety margins to unacceptable levels. Three macro damage modes which were observed in fired nozzles are: ply lift, 'wedge out', and pocketing erosion. Ply lift occurs in materials with plies oriented nearly parallel to the surface. The damage occurs in a region below the charred material where material temperatures are relatively low - about 500 F. Wedge out occurs at the intersection of nozzle components whose plies are oriented at about 45 deg. The corner of the block of material breaks off along a ply interface. Pocketing erosion occurs in material with plies oriented normal to the surface. Thermal expansion is restrained in two directions resulting in large tensile strains and material failure normal to the surface. When a large section of material is removed as a result of damage, the insulation thickness is reduced which may lead to failure of the nozzle due to excessive heating of critical components. If these damage events cannot be prevented with certainty, the designer must increase the thickness of the insulator thus adding to both weight and cost. One of the difficulties in developing a full understanding of these macro damage mechanisms is that the loading environment and the material response to that environment are extremely complex. These types of damage are usually only observed in actual motor firings. Therefore, it is difficult and expensive to evaluate the reliability of new materials. Standard material tests which measure mechanical and thermal properties of test specimens can only provide a partial picture of how the material will respond in the service environment. The development of the ANALOG test procedure which can combine high heating rates and mechanical loads on a specimen will improve the understanding of the interactive effects of the various loads on the system. But a mechanistic model of material response which can account for the heterogeneity of the material, the progression of various micromechanical damage mechanisms, and the interaction of mechanical and thermal stresses on the material is required to accurately correlate material tests with response to service environments. A model based on fundamental damage mechanisms which is calibrated and verified under a variety of loading conditions will provide a general tool for predicting the response of rocket nozzles. The development of a micromechanical simulation technique was initiated and demonstrated to be effective for studying across-ply tensile failure of carbon/phenolic composites.

Slattery, Kerry T.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCI, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approximately 17-47 km) altitude range and over 10 degree latitude bins from 70 deg S to 70 deg N. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and CIONO2; (2) from the N2O-NOy correlation, (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approximately 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Comparative Magma Oceanography

The question of whether the Earth ever passed through a magma ocean stage is of considerable interest. Geochemical evidence strongly suggests that the Moon had a magma ocean and the evidence is mounting that the same was true for Mars. Analyses of martian (SNC) meteorites have yielded insights into the differentiation history of Mars, and consequently, it is interesting to compare that planet to the Earth. Three primary features of Mars contrast strongly to those of the Earth: (i) the extremely ancient ages of the martian core, mantle, and crust (about 4.55 b.y.); (ii) the highly depleted nature of the martian mantle; and (iii) the extreme ranges of Nd isotopic compositions that arise within the crust and depleted mantle. The easiest way to explain the ages and diverse isotopic compositions of martian basalts is to postulate that Mars had an early magma ocean. Cumulates of this magma ocean were later remelted to form the SNC meteorite suite and some of these melts assimilated crustal materials enriched in incompatible elements. The REE pattern of the crust assimilated by these SNC magmas was LREE enriched. If this pattern is typical of the crust as a whole, the martian crust is probably similar in composition to melts generated by small degrees of partial melting (about 5%) of a primitive source. Higher degrees of partial melting would cause the crustal LREE pattern to be essentially flat. In the context of a magma ocean model, where large degrees of partial melting presumably prevailed, the crust would have to be dominated by late-stage, LREE-enriched residual liquids. Regardless of the exact physical setting, Nd and W isotopic evidence indicates that martian geochemical reservoirs must have formed early and that they have not been efficiently remixed since. The important point is that in both the Moon and Mars we see evidence of a magma ocean phase and that we recognize it as such. Several lines of theoretical inference point to an early Earth that was also hot and, perhaps, mostly molten. The Giant Impact hypothesis for the origin of the Moon offers a tremendous input of thermal energy and the same could be true for core formation. And current solar system models favor the formation of a limited number of large (about 1000 km) planetesimals that, upon accreting to Earth, would cause great heating, being lesser versions of the Giant Impact. Several lines of geochemical evidence do not favor this hot early Earth scenario. (i) Terrestrial man-tle xenoliths are sometimes nearly chondritic in their major element compositions, suggesting that these rocks have never been much molten. Large degrees of partial melting probably promote differentiation rather than homogenization. (ii) Unlike the case of Mars, the continental crust probably did not form as a highly fractionated residual liquid from a magma ocean (about 99% crystallization), but, rather, formed in multiple steps. [The simplest model for the formation of continental crust is complicated: (a) about 10% melting of a primitive mantle, making basalt; (b) hydrothermal alteration of that basalt, converting it to greenstone; and (c) 10% partial melting of that greenstone, producing tonalite.] This model is reinforced by the recent observation from old (about 4.1 b.y.) zircons that the early crust formed from an undepleted mantle having a chondritic Lu/Hf ratio. (iii) If the mantle were once differentiated by a magma ocean, the mantle xenolith suite requires that it subsequently be homogenized. The Os isotopic compositions of fertile spinel lherzolites place constraints on the timing of that homogenization. The Os isotopic composition of spinel lherzolites approaches that of chondrites and correlates with elements such as Lu and Al. As Lu and Al concentrations approach those of the primitive mantle, Os isotopic compositions approach chondritic. The Re and Os in these xenoliths were probably added as a late veneer. Thus, the mantle that received the late veneer must have been nearly chondritic in terms of its major elements (excluding Fe). If the mantle that the veneer was mixed into was not al-ready homogenized, then Os isotopes should not correlate with incompatible elements such as Al. Consequently, either early differentiation of the mantle did not occur or the homogenization of this differentiation must have occurred before the late veneer was added. The timing of the late veneer is itself uncertain but presumably postdated core formation at about 4.45 b.y. and did not postdate the 3.8-3.9 b.y. late bombardment of the Moon. This timing based on siderophile elements is consistent with the Hf isotopic evidence cited above. If the Earth, Moon and Mars had magma oceans, the Earth subsequently rehomogenized whereas the Moon and Mars did not. The simplest solution to this observation is that homogenization of igneous differentiates was never necessary on Earth, either because the hypothetical magma ocean never occurred or because this event did not produce mantle differentiation.

Jones, J. H.↗

TPSAS-NF1676L-10874-DND

An unstructured grid flow solver, FUN3D has been used for simulation of unsteady flow on a partially dressed nose landing gear with closed cavities. Results obtained from an hybrid RANS/LES and delayed DES turbulence models are presented. Solutions have been obtained for a series of successively finer grids to quantify the effect of grid refinement. Computed surface pressures and perturbation pressures, and flow quantities in selected planes are compared with the experimental data. The power spectral density at several locations is also compared with the measured data. Overall agreement of FUN3D results with the experimental data is encouraging and the correlation with the measured data generally improves with grid refinement.

Veer N Vatsa↗

TPSAS-NF1676L-10770-DND

An unstructured grid flow solver, FUN3D has been used for simulation of unsteady flow on a partially dressed nose landing gear with closed cavities. Results obtained from an hybrid RANS/LES and delayed DES turbulence models are presented. Solutions have been obtained for a series of successively finer grids to quantify the effect of grid refinement. Computed surface pressures and perturbation pressures, and flow quantities in selected planes are compared with the experimental data. The power spectral density at several locations is also compared with the measured data. Overall agreement of FUN3D results with the experimental data is encouraging and the correlation with the measured data generally improves with grid refinement.

Veer N Vatsa↗

Application of Interparticle Spacing Model to Maximize Filler Content in Cementitious Pastes

One of the most impactful ways to reduce embodied carbon of concrete in the near term is by partially replacing Portland cement with supplementary cementitious materials and/or fillers. This article describes an approach to reduce cement content in concrete through the development of high filler, low water (HFLW) cementitious pastes. Pastes with cement content as low as 50% (% weight of fines) were designed by applying models that maximize the packing density of the granular system and that consider the characteristics of the materials to calculate interparticle spacing (IPS), thereby allowing to obtain pastes with higher solids concentration and lower water demand. Strong correlations were found between IPS, the consistency index of the Herschel-Bulkley rheological model, and cement hydration kinetic parameters of binary and ternary pastes containing a Portland limestone cement and up to two different types of ground limestone. The approach showed to be feasible for the design of HFLW concrete paste fraction.

Antunes da Silva, Denise↗

Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (Cu x Mo 6 S 8 , x = 1-3)

Herein this work presents a systematic investigation of the electrochemical intercalation of aqueous copper cations into the Chevrel phase (CP) Mo 6 S 8 and its effect on the host's electronic and structural characteristics as a function of stoichiometry. The electrochemical potentials at which copper intercalates into the CP Mo 6 S 8 host in 1 M CuSO 4 were identified for Cu x Mo 6 S 8 (x = 1–3) as 0.23 V, 0.11 V, and 0.055 V (vs. Cu/Cu 2+ ) for Cu 1 Mo 6 S 8 , Cu 2 Mo 6 S 8 , and Cu 3 Mo 6 S 8 , respectively, and correlated via ex situ PXRD to stoichiometric content. Potentials were also identified that yield non-stoichiometric phases with traceable Cu content-dependent structural changes. Ab initio DFT calculations were performed to probe thermodynamic stability of Cu x Mo 6 S 8 CP compositions and the metal-to-semiconductor transitions as a function of copper content. Lastly, we demonstrate that the SK-pre-edge intensity is a successful probe for intercalant content: as copper equivalents increase, so does charge transfer to the partially occupied S 3p orbitals, resulting in a decrease in the pre-edge intensity corresponding to the excitation of a S 1s-to-3p/Mo 4d hybridized orbital.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scaled equation of state parameters for gases in the critical region

In the light of recent theoretical developments, the paper presents an accurate characterization of anomalous thermodynamic behavior of xenon, helium 4, helium 3, carbon dioxide, steam and oxygen in the critical region. This behavior is associated with long range fluctuations in the system and the physical properties depend primarily on a single variable, namely, the correlation length. A description of the thermodynamic behavior of fluids in terms of scaling laws is formulated, and the two successfully used scaled equations of state (NBS equation and Linear Model parametric equation) are compared. Methods for fitting both equations to experimental equation of state data are developed and formulated, and the optimum fit for each of the two scaled equations of the above gases are presented and the results are compared. By extending the experimental data for the above one-component fluids to partially miscible binary liquids, superfluid liquid helium, ferromagnets and solids exhibiting order-disorder transitions, the principle of universality is concluded. Finally by using this principle, the critical regions for nine additional fluids are described.

Sengers, J. M. H. L.↗

Characterizing Non-Uniformity of Performance of Thin-Film Solar Cells

Thin-film Solar Cells are being actively studied for terrestrial and space applications because of their potential to provide low-cost, lightweight, and flexible electric power system. Currently, thin-film solar cell performance is limited partially by the nonuniformity of performance that they typically exhibit. This nonuniformity of performance necessitates more detailed characterization techniques than the well-known macroscopic measurements such as current-voltage and efficiency. This project seeks to explore methods of characterization that take into account the spatial nonuniformity of thin-film solar cells. In this presentation we show results of electroluminescence images, short-circuit maps, and Kelvin Probe maps. All these mapping characterization and analysis tools show that the non-uniformities can correlated with device performance and efficiency.

Clark, Eric B.↗

Investigation of electrolyte measurement in diluted whole blood using spectroscopic and chemometric methods

The feasibility of using near-infrared (NIR) spectroscopy in combination with partial least-squares (PLS) regression was explored to measure electrolyte concentration in whole blood samples. Spectra were collected from diluted blood samples containing randomized, clinically relevant concentrations of Na+, K+, and Ca2+. Sodium was also studied in lysed blood. Reference measurements were made from the same samples using a standard clinical chemistry instrument. Partial least squares (PLS) was used to develop calibration models for each ion with acceptable results (Na+, R2 = 0.86, CVSEP = 9.5 mmol/L; K+, R2 = 0.54, CVSEP = 1.4 mmol/L; Ca2+, R2 = 0.56, CVSEP = 0.18 mmol/L). Slightly improved results were obtained using a narrower wavelength region (470-925 nm) where hemoglobin, but not water, absorbed indicating that ionic interaction with hemoglobin is as effective as water in causing measurable spectral variation. Good models were also achieved for sodium in lysed blood, illustrating that cell swelling, which is correlated with sodium concentration, is not required for calibration model development.

Non-NASA Center↗

Uncertainty Determination for Aeroheating in Uranus and Saturn Probe Entries by the Monte Carlo Method

The 2013-2022 Decaedal survey for planetary exploration has identified probe missions to Uranus and Saturn as high priorities. This work endeavors to examine the uncertainty for determining aeroheating in such entry environments. Representative entry trajectories are constructed using the TRAJ software. Flowfields at selected points on the trajectories are then computed using the Data Parallel Line Relaxation (DPLR) Computational Fluid Dynamics Code. A Monte Carlo study is performed on the DPLR input parameters to determine the uncertainty in the predicted aeroheating, and correlation coefficients are examined to identify which input parameters show the most influence on the uncertainty. A review of the present best practices for input parameters (e.g. transport coefficient and vibrational relaxation time) is also conducted. It is found that the 2(sigma) - uncertainty for heating on Uranus entry is no more than 2.1%, assuming an equilibrium catalytic wall, with the uncertainty being determined primarily by diffusion and H(sub 2) recombination rate within the boundary layer. However, if the wall is assumed to be partially or non-catalytic, this uncertainty may increase to as large as 18%. The catalytic wall model can contribute over 3x change in heat flux and a 20% variation in film coefficient. Therefore, coupled material response/fluid dynamic models are recommended for this problem. It was also found that much of this variability is artificially suppressed when a constant Schmidt number approach is implemented. Because the boundary layer is reacting, it is necessary to employ self-consistent effective binary diffusion to obtain a correct thermal transport solution. For Saturn entries, the 2(sigma) - uncertainty for convective heating was less than 3.7%. The major uncertainty driver was dependent on shock temperature/velocity, changing from boundary layer thermal conductivity to diffusivity and then to shock layer ionization rate as velocity increases. While radiative heating for Uranus entry was negligible, the nominal solution for Saturn computed up to 20% radiative heating at the highest velocity examined. The radiative heating followed a non-normal distribution, with up to a 3x variation in magnitude. This uncertainty is driven by the H(sub 2) dissociation rate, as H(sub 2) that persists in the hot non-equilibrium zone contributes significantly to radiation.

Palmer, Grant↗