Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “chemical homogenization”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Eliminating Yield Anisotropy and Enhancing Ductility in Mg Alloys by Shear Assisted Processing and Extrusion

Solid phase processing techniques such as friction stir welding, Shear assisted processing and extrusion (ShAPE)/ friction extrusion and cold spray have been successfully demonstrated as promising thermomechanical methods to produce metallic materials with enhanced performance. In this study, AZ series with and without silicon, ZK60 Mg alloys in as-received forms (as-cast or as-extruded) were processed using Shear Assisted Processing and Extrusion (ShAPE). Microstructural characterization was performed using EBSD and TEM and revealed that as compared to the feedstock materials/ billets, friction extruded Mg alloys had more uniform microstructure, equiaxed grains, finer and homogeneously distributed precipitates and chemical homogeneity. It was also observed that basal planes were not oriented parallel to extrusion axis. As a result, rod products exhibited significantly reduced (in some cases eliminated) yield asymmetry and achieved enhanced ductility, which were uncommon or difficult to attain using conventional processing techniques. In addition, modified texture likely suppressed deformation twinning under compressive deformation.

Shear Assisted Processing and Extrusion, SHAPE, ma↗

Custom-designed heat treatment simultaneously resolves multiple challenges facing 3D-printed single-crystal superalloys

Single-crystal Ni-based superalloys are currently the material of choice for turbine blade applications, especially with the emerging additive manufacturing (AM) that facilitates the manufacture/repair of these single crystals. This promising AM route, however, comes with a dilemma: in the fusion and heat affected zones after e-beam or laser induced melting, one needs a solutionizing annealing to relieve the residual stresses and homogenize the chemical/microstructure. The super-solvus solutionizing temperature is usually adopted from the protocol for the cast superalloys, which almost always causes recrystallization and stray grain growth, resulting in a polycrystalline microstructure and degrading the high-temperature mechanical performance. Here, in this paper, we demonstrate a custom-designed post-printing heat treatment to replace the conventional super-solvus one. The recovery and relatively low temperature diminish the driving force for recrystallization and the movement of stray grain boundaries, without suffocating the chemical/microstructural homogenization thanks to the narrow dendrite width and short element segregation distance. The optimal duration of the heat treatment is proposed to achieve atomic-diffusion mediated chemical homogenization while limiting γ'-particle coarsening in the interdendritic regions. Our strategy makes it practically feasible to resolve several bottleneck problems with one processing/treatment, removing a seemingly formidable obstacle to effective additive manufacturing of superalloy single crystal products.

36 MATERIALS SCIENCE↗

Origins of GEMS Grains

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

Messenger, S.↗

Textural variations and impact history of the Millbillillie eucrite

We have investigated 10 new specimens of the Millbillillie eucrite to study its textures and mineral compositions by electron probe microanalyser and scanning electron microscope. Although originally described as having fine-grained texture, the new specimens show diversity of texture. The compositions (Mg/Fe ratios) of the host pigeonites and augite lamellae are homogeneous, respectively, in spite of the textural variation. In addition to their chemical homogeneity, pyroxenes in coarse and fine-grained clasts are partly inverted to orthopyroxene. Chemical zoning of plagioclase during crystal growth is preserved. This eucrite includes areas of granulitic breccias and impact melts. Large scale textures show a subparallel layering suggesting incomplete mixing and deposition of impact melt and lithic fragments. An Ar-39-Ar-40 age determination for a coarse-grained clast indicates a strong degassing event at 3.55 +/- 0.02 Ga. We conclude that Millbillillie is among the most equilibriated eucrites produced by thermal annealing after impact brecciation. According to the classificcation of impact breccias, Millbillillie can be classified as a mixture of granulitic breccias and impact melts. The last significant thermal event is characterized by network-like glassy veins that run through clasts and matrices. Consideration of textual observations and requirements for Ar-degassing suggests that the Ar-39-Ar-40 age could in principle date either the earlier brecciation and annealing event or the event which produced the veins.

Yamaguchi, Akira↗

Evolution of Shock Melt Compositions in Lunar Agglutinates

Lunar agglutinates are aggregates of regolith grains fused together in a glassy matrix of shock melt produced during smaller-scale (mostly micrometeorite) impacts. Agglutinate formation is a key space weathering process under which the optically-active component of nanophase metallic Fe (npFe(sup 0)) is added to the lunar regolith. Here we have used energy-dispersive X-ray (EDX) compositional spectrum imaging in the SEM to quantify the chemical homogeneity of agglutinitic glass, correlate its homogeneity to its parent soil maturity, and identify the principle chemical components contributing to the shock melt compositional variations.

Vance, A. M.↗

Combining Astrometry and Elemental Abundances: The Case of the Candidate Pre-Gaia Halo Moving Groups G03-37, G18-39, and G21-22

While most moving groups are young and nearby, a small number have been identified in the Galactic halo. Understanding the origin and evolution of these groups is an important piece of reconstructing the formation history of the halo. Here we report on our analysis of three putative halo moving groups: G03-37, G18-39, and G21-22. Based on Gaia EDR3 data, the stars associated with each group show some scatter in velocity (e.g., Toomre diagram) and integrals of motion (energy, angular momentum) spaces, counter to expectations of moving-group stars. We choose the best candidate of the three groups, G21-22, for follow-up chemical analysis based on high-resolution spectroscopy of six presumptive members. Using a new Python code that uses a Bayesian method to self-consistently propagate uncertainties from stellar atmosphere solutions in calculating individual abundances and spectral synthesis, we derive the abundances of α- (Mg, Si, Ca, Ti), Fe-peak (Cr, Sc, Mn, Fe, Ni), odd-Z (Na, Al, V), and neutron-capture (Ba, Eu) elements for each star. We find that the G21-22 stars are not chemically homogeneous. Based on the kinematic analysis for all three groups and the chemical analysis for G21-22, we conclude the three are not genuine moving groups. The case for G21-22 demonstrates the benefit of combining kinematic and chemical information in identifying conatal populations when either alone may be insufficient. Comparing the integrals of motion and velocities of the six G21-22 stars with those of known structures in the halo, we tentatively associate them with the Gaia-Enceladus accretion event.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Derivation of the chemical-equilibrium rate coefficient using scattering theory

Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

Mickens, R. E.↗

Dependence of Aerosol-Droplet Partitioning on Turbulence in a Laboratory Cloud

Activation is the first step in aerosol-cloud interactions, which have been identified as one of the principal uncertainties in Earth's climate system. Aerosol particles become cloud droplets, or activate, when the ambient saturation ratio exceeds a threshold, which depends on the particle's size and hygroscopicity. In the traditional formulation of the process, only average, uniform saturation ratios are considered. Furthermore, turbulent environments like clouds intrinsically have fluctuations around mean values in the scalar fields of temperature and water vapor concentration, which determine the saturation ratio. Through laboratory measurements, we show that these fluctuations are an important parameter that needs to be addressed to fully describe activation. Our results show, even for single-sized, chemically homogeneous aerosols, that fluctuations blur the correspondence between activation and a particle's size and chemical composition, that turbulence can increase the fraction of aerosol particles which activate, and that the activated fraction decreases monotonically as the concentration of aerosol increases. Taken together, our data demonstrate that fluctuations can have effects equivalent to the aerosol limited and updraft limited regimes, known from adiabatic parcel theory.

58 GEOSCIENCES↗

The Relationship between Age, Metallicity, and Abundances for Disk Stars in a Simulated Milky Way

Observations of the Milky Way's low-α disk show that several element abundances correlate with age at fixed metallicity, with unique slopes and small scatters around the age–[X/Fe] relations. In this study, we turn to simulations to explore the age–[X/Fe] relations for the elements C, N, O, Mg, Si, S, and Ca that are traced in a FIRE-2 cosmological zoom-in simulation of a Milky Way–like galaxy, m12i, and understand what physical conditions give rise to the observed age–[X/Fe] trends. We first explore the distributions of mono-age populations in their birth and current locations, [Fe/H], and [X/Fe], and find evidence for inside-out radial growth for stars with ages <7 Gyr. We then examine the age–[X/Fe] relations across m12i's disk and find that the direction of the trends agrees with observations, apart from C, O, and Ca, with remarkably small intrinsic scatters, σ int (0.01 - 0.04 dex). This σ int measured in the simulations is also metallicity dependent, with σ int ≈ 0.025 dex at [Fe/H] = -0.25 dex versus σ int ≈ 0.015 dex at [Fe/H] = 0 dex, and a similar metallicity dependence is seen in the GALAH survey for the elements in common. Additionally, we find that σ int is higher in the inner galaxy, where stars are older and formed in less chemically homogeneous environments. The age–[X/Fe] relations and the small scatter around them indicate that simulations capture similar chemical enrichment variance as observed in the Milky Way, arising from stars sharing similar element abundances at a given birth place and time.

79 ASTRONOMY AND ASTROPHYSICS↗

Chandra Grating Spectroscopy of Three Hot White Dwarfs

High-resolution soft X-ray spectroscopic observations of single hot white dwarfs are scarce. With the Chandra Low-Energy Transmission Grating, we have observed two white dwarfs, one is of spectral type DA (LB1919) and the other is a non-DA of spectral type PG1159 (PG1520+525). The spectra of both stars are analyzed, together with an archival Chandra spectrum of another DA white dwarf (GD246). Aims. The soft X-ray spectra of the two DA white dwarfs are investigated in order to study the effect of gravitational settling and radiative levitation of metals in their photospheres. LB1919 is of interest because it has a significantly lower metallicity than DAs with otherwise similar atmospheric parameters. GD246 is the only white dwarf known that shows identifiable individual iron lines in the soft X-ray range. For the PG1159 star, a precise effective temperature determination is performed in order to confine the position of the blue edge of the GW Vir instability region in the HRD. Methods. The Chandra spectra are analyzed with chemically homogeneous as well as stratified NLTE model atmospheres that assume equilibrium between gravitational settling and radiative acceleration of chemical elements. Archival EUV and UV spectra obtained with EUVE, FUSE, and HST are utilized to support the analysis. Results. No metals could be identified in LB1919. All observations are compatible with a pure hydrogen atmosphere. This is in stark contrast to the vast majority of hot DA white dwarfs that exhibit light and heavy metals and to the stratified models that predict significant metal abundances in the atmosphere. For GD246 we find that neither stratified nor homogeneous models can fit the Chandra spectrum. The Chandra spectrum of PG1520+525 constrains the effective temperature to T(sub eff) = 150 000 +/- 10 000 K. Therefore, this nonpulsating star together with the pulsating prototype of the GWVir class (PG1159-035) defines the location of the blue edge of the GWVir instability region. The result is in accordance with predictions from nonadiabatic stellar pulsation models. Such models are therefore reliable tools to investigate the interior structure of GW Vir variables. Conclusions. Our soft X-ray study reveals that the understanding of metal abundances in hot DA white dwarf atmospheres is still incomplete. On the other hand, model atmospheres of hydrogen-deficient PG1159-type stars are reliable and reproduce well the observed spectra from soft X-ray to optical wavelengths.

Adamczak, J.↗

Evolution of Shock Melt Compositions in Lunar Regoliths

Space weathering processes - driven primarily by solar wind ion and micrometeorite bombardment, are constantly changing the surface regoliths of airless bodies, such as the Moon. It is essential to study lunar soils in order to fully under-stand the processes of space weathering, and how they alter the optical reflectance spectral properties of the lunar surface relative to bedrock. Lunar agglutinates are aggregates of regolith grains fused together in a glassy matrix of shock melt produced during micrometeorite impacts into the lunar regolith. The formation of the shock melt component in agglutinates involves reduction of Fe in the target material to generate nm-scale spherules of metallic Fe (nanophase Fe0 or npFe0). The ratio of elemental Fe, in the form of npFe0, to FeO in a given bulk soil indicates its maturity, which increases with length of surface exposure as well as being typically higher in the finer-size fraction of soils. The melting and mixing process in agglutinate formation remain poorly understood. This includes incomplete knowledge regarding how the homogeneity and overall compositional trends of the agglutinate glass portions (agglutinitic glass) evolve with maturity. The aim of this study is to use sub-micrometer scale X-ray compositional mapping and image analysis to quantify the chemical homogeneity of agglutinitic glass, correlate its homogeneity to its parent soil maturity, and identify the principal chemical components contributing to the shock melt composition variations. An additional focus is to see if agglutinitic glass contains anomalously high Fe sub-micron scale compositional domains similar to those recently reported in glassy patina coatings on lunar rocks.

Vance, A. M.↗

Sr-Nd-Pb isotope systematics of Australasian tektites: Implications for the nature and composition of target materials and possible volatile loss of Pb

The Australasian tektite (AAT) strewn field is the largest strewn field on the Earth with about ~10–30% coverage, both land and ocean, but a clearly identified source impact crater is absent despite the young age of AAT of ca. 790 ka. A genetic link between the Australasian tektites and their unequivocal parental materials is therefore largely impossible to establish. Nevertheless, the nature of the parental materials and the extent of volatilization can be constrained using the splash form tektites, carrying the chemical signatures of high-temperature processes, and the layered (so-called Muong Nong-type) tektites, which are less chemically homogenized and exceptionally abundant in the AAT field. New high-precision Sr, Nd and Pb isotopic measurements were obtained for a chemically and petrographically well-characterized suite of AAT, which included the Muong Nong-type (MN-AAT) with precisely known field locations in Laos and splash forms (SF-AAT) from different parts of the strewn field. Additionally, optically dark and light zones of the MN-AAT were also separately analyzed. Homogeneous ε Nd values from -11.8 to -11.2, combined with a narrow range of two-stage Nd model ages from 1.67 to 1.72 Ga for the entire AAT suite, point to a well-mixed source, in terms of REE, of the crustal segment from which the sedimentary material for tektites was ultimately derived. The Sr isotopic data largely overlap for SF-AAT and MN-AAT ( 87 Sr/ 86 Sr = 0.71636–0.72021) and indicate Paleozoic to Mesozoic sedimentary parentage. However, late Neogene to early Quaternary re-deposition and formation of a thick silt-sized sedimentary section with vertical stratification is required to comply with 10Be data. Lead isotope systematics documents at least three different components which can perhaps be represented by different mineral phases, such as feldspar, zircon, organic matter adsorbed on young sediments etc., sorted during fluvial transport and final deposition. In addition, the SF-AAT have systematically lower Pb contents than the MN-AAT, and generally show isotopically heavier Pb isotopic ratios. This is theoretically consistent with a preferential volatilization of lighter Pb isotopes during evaporation and considerably larger Pb loss from SF-AAT when compared to MN-AAT. Nevertheless, further experimental work would be necessary to unambiguously distinguish kinetic fractionation from source mixing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upper limit to the mass of pulsationally stable stars with uniform chemical composition

Nuclear-energized pulsational instability is a well-known feature of models of chemically homogeneous stars above a critical mass. With the Rogers-Iglesias opacities, the instability occurs above 120-150 solar mass for normal Galactic Population I chemical compositions, and above approximately 90 solar mass for stars in metal-poor environments like the outer Galaxy and the Small Magellanic Cloud. Models of homogeneous helium-burning stars are unstable above masses of 19 and 14 solar mass, respectively. These significant increases of the critical masses, in the normal metallicity cases, over the values derived previously with the Los Alamos opacities can explain the stability of the brightest observed O-type stars, but they do not exclude the possibility that the most luminous hydrogen-deficient Wolf-Rayet stars are experiencing this type of instability.

Stothers, Richard B.↗

Effects of Nonequilibrium Chemistry and Darcy-Forchheimer Pyrolysis Flow for Charring Ablator

The fully implicit ablation and thermal response code simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid.This work describes new modeling capabilities that are added to a special version of code. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Two groups of parametric studies of the phenolic impregnated carbon ablator are performed. In the first group, an Orion flight environment for a proposed lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results indicate that the presence of chemical nonequilibrium pyrolysis gas flow does not significantly alter the in-depth thermal response performance predicted using the chemical equilibrium gas model.

Chen, Yih-Kanq↗

Fine-Grained Rims in the Allan Hills 81002 and Lewis Cliff 90500 CM2 Meteorites: Their Origin and Modification

Antarctic CM meteorites Allan Hills (ALH) 8 1002 and Lewis Cliff (LEW) 90500 contain abundant fine-grained rims (FGRs) that surround a variety of coarse-grained objects. FGRs from both meteorites have similar compositions and petrographic features, independent of their enclosed objects. The FGRs are chemically homogeneous at the 10 m scale for major and minor elements and at the 25 m scale for trace elements. They display accretionary features and contain large amounts of volatiles, presumably water. They are depleted in Ca, Mn, and S but enriched in P. All FGRs show a slightly fractionated rare earth element (REE) pattern, with enrichments of Gd and Yb and depletion of Er. Gd is twice as abundant as Er. Our results indicate that those FGRs are not genetically related to their enclosed cores. They were sampled from a reservoir of homogeneously mixed dust, prior to accretion to their parent body. The rim materials subsequently experienced aqueous alteration under identical conditions. Based on their mineral, textural, and especially chemical similarities, we conclude that ALH 8 1002 and LEW 90500 likely have a similar or identical source.

Hua, X.↗

The R -Process Alliance: Exploring the cosmic scatter among ten r -process sites with stellar abundances

Context. The astrophysical origin of the rapid neutron-capture process (r-process), responsible for producing roughly half of the elements heavier than iron, remains uncertain. Detailed chemical signatures from the oldest, most metal-poor stars, which act as fossil records of the earliest nucleosynthesis events, can be used to identify the dominant r-process sites. Aims. We present a homogeneous chemical abundance analysis of ten r-process element-enhanced stars. These old and metal-poor stars are strongly enriched in r-process elements with minimal contamination from other nucleosynthetic sources. By focusing on this chemically pure sample, we aim to investigate intrinsic variations in the r-process abundance patterns and explore their implications for the nature and potential diversity of r-process sites. Methods. We performed a detailed chemical abundance analysis of high-resolution, high-signal-to-noise spectra. For each star, we inspected over 1400 individual absorption lines using a combination of equivalent width measurements and spectral synthesis. The analysis was conducted under the assumption of 1D local thermodynamic equilibrium and employing the MOOG radiative transfer code. Results. We derived abundances for 54 chemical species, including 29 neutron-capture (n-capture) elements, covering the full mass range of the r-process abundance pattern. A kinematic analysis reveals that stars likely originated from ten kinematically distinct systems. Based on this assumption, we used the sample to probe the maximum variation expected from ten independent r-process nucleosynthesis events and computed the intrinsic dispersion of each element relative to Zr and Eu for the light and heavy r-process elements, respectively. This exercise resulted in a remarkably low cosmic scatter across the ten r-process sites enriching these stars; for the rare earth and third peak elements, for example, we find σ [La/Eu] = 0.08 and σ [Os/Eu] = 0.11 dex, while the scatter between light and heavy elements, σ [Zr/Eu] , is slightly higher at 0.18 dex. Conclusions. The elemental abundance patterns across the ten independent r-process sites show remarkably small cosmic dispersions. This minimal dispersion suggests a high degree of uniformity in r-process yields across diverse astrophysical environments.

Astronomy and AstroPhysics↗

Future aircraft and potential effects on stratospheric ozone and climate

Initial studies with LLNL models of global atmospheric chemical, radiative, and transport processes have indicated that substantial decreases in stratospheric ozone concentrations could result from emissions of NO(x) from aircraft flying in the stratosphere, depending on fleet size and magnitude of the engine emissions. These studies used homogeneous chemical reaction rates (e.g., gas-phase chemistry). Recent evidence indicates that reactions on particles in the stratosphere may be important. Heterogeneous chemical reactions convert NO(x) (NO and NO2) molecules to HNO3. This decreases the odd oxygen loss from the NO(x) catalytic cycle and increases the odd oxygen loss from the Cl(x) catalytic cycle. By including these heterogeneous reactions in the LLNL model, the relative partitioning of odd oxygen loss between these two families changes, with the result that emissions of NO(x) from proposed aircraft fleets flying in the stratosphere now increase ozone. Having these heterogeneous processes present also increases ozone concentration in the troposphere relative to gas-phase only chemistry calculations for emissions of NO(x) from subsonic aircraft.

Kinnison, Douglas E.↗

Chemo‐Mechanical Coupling in Hydrogels: Dynamics in the Diffusion‐Limited Regime

Hydrogels are characterized by substantial volume changes in response to external stimuli, making them promising candidates for developing smart materials with enhanced adaptability and responsiveness. By integrating chemical reactions, hydrogels acquire dynamic and tunable responsiveness to external stimuli through chemo‐mechanical coupling, expanding their potential in emerging applications. However, capturing their transient behavior remains challenging due to the complex interplay of chemical reactions, solvent transport, and polymer network deformation. Classical theories capture equilibrium swelling but fail to describe time‐dependent phenomena. To address this, a time‐dependent continuum model is developed that explicitly couples these processes. Volume phase transition in hydrogels with homogeneous chemical reactions is investigated, then the effects of reaction kinetics on these transitions are analyzed. The coupling of these mechanisms is further explored through a study of transient mechanical instabilities. To illustrate the impact of distinct reaction and diffusion timescales, a photo‐active gripper is studied for robotic applications. Finally, a photo‐active microswimmer that exhibits non‐reciprocal motion is proposed to highlight the solvent diffusion for locomotion at the micro‐ and nano‐ scales. The work establishes that transient dynamics of chemo‐mechanical hydrogels generate functions not accessible by steady state models and provides a predictive platform for designing adaptive materials in emerging applications.

chemo-mechanical coupling↗