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At least 145 records · Page 8

Cr-Rich and Al-Rich Oxide Grains With 16O-Rich Compositions in Ryugu Samples

Samples returned from asteroid Ryugu by JAXA’s Hayabusa2 mission are CI-like, with abundant hydrated and secondary phases [1]. Rare anhydrous minerals occur in the matrix of the major lithology and in chemically distinct clasts. Oxygen isotopic analysis of coarse (> 10 µm) anhydrous Mg-rich silicates revealed a bimodal distribution, with some grains having compositions similar to amoeboid olivine aggregates (AOAs) and others having compositions similar to chondrule phenocrysts [2, 3]. We previously analyzed < 2 µm-sized Mg-rich silicates within a clast that also showed a range of O isotopic compositions (δ18O from -38 to +5 ‰) [4]. In this study, we conducted coordinated isotopic and mineralogical analysis of anhydrous oxide grains found in the matrix of Ryugu samples

A. N. Nguyen↗

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this “Imperfect OA” process remain the subject of debate. In this paper, molecular dynamics and in situ TEM were used to probe the crystallographic evolution of up to 30 gold and copper nanoparticles during aggregation. It was found that Imperfect OA occurs because (1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and (2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing 9 initially misoriented, agglomerated particles with evidence of dislocation slip and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyelectrolyte Complex Coacervate Assembly with Cellulose Nanofibers

Polyelectrolytes are used in paper manufacturing to increase flocculation and water drainage and improve mechanical properties. In this study, we examine the interaction between charged cellulosic nanomaterials and polyelectrolyte complex coacervates of weak polyelectrolytes, polyacrylic acid salt, and polyallylamine hydrochloride. We observe that by changing the order of addition of the polyelectrolytes to cellulose nanofibers (CNFs), we can tune the interactions between the materials, which in turn changes the degree of association of the coacervates to the CNFs and the rate at which they aggregate. Importantly for the papermaking process, when adding the polyelectrolytes sequentially to the CNFs, we found faster aggregation to the fibers and lower water retention values compared to those when preformed coacervates or CNFs by themselves were used. Coarse-grain molecular dynamic simulations further support the fundamental mechanism of aggregation by taking into consideration the interaction between cellulose and the complexes at the molecular level. The simulations corroborate the experimental observations by showing the importance of strong electrostatic interactions in aggregate formation.

36 MATERIALS SCIENCE↗

Structure and origin of cometary nuclei

There is strong evidence that a comet nucleus consists of a single object whose basic structure is Whipple's icy conglomerate. A number of cometary phenomena indicate that the nucleus is a low density, fragile object with a large degree of radial uniformity in structure and composition. Details of the ice-dust pattern are more uncertain. A working model is proposed which is based on theories of accumulation of larger objects from grains. This nucleus is a distorted spherical aggregate of a hierarchy of ice-dust cometesimals. These cometesimals retain some separate identity which lead to comet fragmentation when larger components break off. The outer layers of new comets were modified by cosmic ray irradiation in the Oort Cloud. The evidence for meteorite-comet association is steill controversial. Current dynamical studies do not seem to require a cometary source of meteorites.

Donn, B.↗

Metastable Eutectic Equilibrium in Natural Environments: Recent Development and Research Opportunities

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica compositions of circumstellar dust presolar and solar nebula grains in the matrix of the collected aggregate IDPs (Interplanetary Dust Particles). Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra) fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous, and typically nano-to micrometer-sized, metastable eutectic materials.

Rietmeijer, Frans J. M.↗

Metastable Eutectic Equilibrium in Natural Environments: Recent Developments and Research Opportunities

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica, compositions of circumstellar dust, presolar and solar nebula grains in the matrix of the collected aggregate IDPs. Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra)fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous and typically nano- to micrometer-sized, metastable eutectic materials.

Rietmeijer, Fans J. M.↗

X-radiography of slices of the Allende Meteorite

A 2.2 kg fragment of the Allende Meteorite was derinded and sliced by bandsawing. Several X-radiographs were made of all slices. The following features are resolved: grains of blocky troilite (bright spots), troilite rimmed chondrules (bright halos), chondrules with central vugs (dim halos), white aggregates (dark patches), and dark inclusions (medium dark patches). The number of FeS grains larger than about 0.5 mm is one per 6 + or - 1 gram of this fragment. Their concentration appears to be uniform at the 1 kg weight level, but is not uniform at the 100 g level. The number of FeS rimmed chondrules is one per 10 g. Their concentration is also nonuniform at the 100 g weight level. The number of white aggregates is roughly one per 20 g. These disc shaped objects show a distinct preferred orientation of the axis orthogonal to the plane of the disc. Chondrules with central vugs are numerous. Linear and curved arrays of chondrules, up to a few cm long, were observed. An interpretation of the observed features is given.

Smith, M. J.↗

Heterogeneity of Bulk Oxygen Isotopic Compositions in Anhydrous Interplanetary Dust Particles

Introduction: Anhydrous interplanetary dust particles are one of the least altered ancient solar systemmaterials. Their bulk chemical compositions match those of CI chondrites within a factor of 2-3, except for carbonwhich is enriched in both anhydrous and hydrated IDPs by ~4x CI [1]. Hydrous IDPs often show 16O-poor isotopiccompositions, likely due to the interaction with isotopically heavy H2O [2]. Anhydrous IDPs are interpreted tooriginate from comets from the outer solar system [3]. Oxygen isotopic data for these materials is scarce, but resultspoint to a wider range of compositions [4]. This heterogeneity might be a result of mixing between a 16O-rich and a16O-poor reservoir formed via self-shielding and photodissociation of CO [5]. Here, we report bulk oxygen isotopiccompositions of three anhydrous IDPs in context of their mineralogical composition and discuss possible origins ofisotopic heterogeneity. Experimental: Bulk chemical composition and mineralogy of 70 nm thin ultramicrotomed sections of threeanhydrous IDPs (L2099A7, L2099A8, and L2071AB1) were analyzed using a Thermo Scientific Titan Themis G360-300 TEM equipped with a four-quadrant energy-dispersive X-ray detector (Super-X G2) at University ofMünster. Bulk oxygen isotopic compositions were measured using a NanoSIMS 50 at the Max-Planck-Institut fürChemie in Mainz. A focused Cs+ ion beam (~1 pA, ~100 nm) was rastered over a field of view varying from 5 x 5 to6 x 6 μm2, depending on particle size for 15 layers. Negative secondary ions of 16O, 17O, 18O, 12C14N, and 28Si werecollected on electron multipliers. The 16OH contribution to the 17O peak was 1-2 ‰. As a standard, a matrix regionof meteorite CR2 Queen Alexandra Range (QUE) 99177 was used, whose oxygen isotopic composition wasmeasured by [6]. Results and Discussion: Particles A7 and A8 are both fine-grained, consisting mostly of small, 100 nm-sizedequilibrated aggregates (EA). Both particles exhibit discontinuous magnetite rims with thicknesses up to 50 nm inA7 and 100 nm in A8 on the outsides. In Particle AB1, the upper part of the particle consists of a few EAs, while thelower part contains lots of small GEMS grains with 100-200 nm diameter clustered together. Magnetite rims arenearly absent, the rare rims reaching maximum 20 nm thickness, indicating that AB1 is of more primitive naturethan the other two IDPs [1]. Furthermore, it contains several diffuse GEMS-like areas, identified by an amorphoussilicate groundmass with small nano-inclusions of Fe,Ni-metal and Fe-sulfides. All three particles are subsolar forall major element/Si ratios. Mean S/Si of particles A7 and A8 is 0.046 and 0.048, respectively, while it is an order ofmagnitude higher in AB1 (0.184). This reflects the higher degree of thermal alteration in A7 and A8, resulting in theloss of volatile S and oxidation of Fe-sulfides and FeNi-metal to magnetite as present in particle rims. A8 is rather16O-poor with δ17OSMOW = 7.8 ± 3.4 ‰ and δ18OSMOW = 9.5 ± 3.1 ‰ (1σ), followed by A7 with δ17OSMOW = − 0.8 ±4.6 ‰ and δ18OSMOW = −2.2 ± 3.4 ‰. In contrast to that, AB1 has the most 16O-rich bulk composition with δ17OSMOW= −24.2 ± 5.4 ‰ and δ18OSMOW = −25.3 ± 3.6 ‰. All investigated IDPs plot slightly above the CCAM line aspreviously reported for other anhydrous IDPs [4], maybe due to a contribution from circumstellar dust from AGBstars enriched in 17O [7]. The 16O-rich composition of AB1 is similar to the most 16O-rich anhydrous IDP U2015D21measured by [8] which is dominated by GEMS [9] and the GEMS-rich IDP GM4-2 reported by [10]. Nevertheless,it is unlikely that GEMS are the carrier for the 16O-rich composition of AB1 because most GEMS have O isotopiccompositions indistinguishable from terrestrial values, although errors on these analyses are large [11]. The isotopicheterogeneity is best explained by contribution of grains from different regions in the protoplanetary disk, samplingdifferent O isotope reservoirs, created by self-shielding and photodissociation of CO. This process resulted in 16O-rich CO gas and 16O-poor H2O that froze as ice-mantles onto dust grains [12]. Alternatively, the higher degree ofheating in A7 and A8 could have influenced isotopic fractionation, because higher δ17,18O values are reported fromthe regions of the atmosphere where small particles are heated and oxidized, as observed for the thermal alteration ofcosmic spherules [13]. Acknowledgements: We would like to thank NASA Astromaterials Acquisition & Curation Office for providing IDPsamples and DFG for funding this project (VO1816/5-1)

B Schulz↗

Mineralogy and petrology of chondrules and inclusions in the Mokoia CV3 chondrite

The inclusions and chondrules of the Mokoia CV3 chondrite are studied systematically and compared with those in the Allende meteorite. Five polished thin sections of Mokoia were examined by optical microscopy, backscattered scanning electron microscopy, and electronprobe microanalysis, and objects greater than about 100 microns in apparent diameter were measured and classified petrographically. Three major types of olivine chondrules are distinguished: igneous chondrules, which evidently crystallized from droplets of silicate melt; recrystallized chondrules, apparently metamorphosed at relatively high temperatures; and accretional aggregates, which are probably fragments of igneous chondrules. Refractory inclusions in Mokoia are generally similar to those found in Allende, although Mokoia inclusions include phyllosilicates rather than feldspathoids and melilite-rich Ca, Al-rich inclusions (CAIs) are more abundant in Allende. The small, fine-grained CAIs, which are more abundant than coarse-grained CAIs in both meteorites, are observed to represent aggregates of three distinct constituents: concentric objects, chaotic material and inclusion matrix. It is concluded that most of the CAIs probably formed during metamorphism, partial melting, and incomplete distillation of primitive dust aggregates heated in the solar nebula.

Cohen, R. E.↗

Quantifying Single-Ion Transport in Percolated Ionic Aggregates of Polymer Melts

Single-ion conducting polymers such as ionomers are promising battery electrolyte materials, but it is critical to understand how rates and mechanisms of free cation transport depend on the nanoscale aggregation of cations and polymer-bound anions. We perform coarse-grained molecular dynamics simulations of ionomer melts to understand cation mobility as a function of polymer architecture, background relative permittivity, and corresponding ionic aggregate morphology. In systems exhibiting percolated ionic aggregates, cations diffuse via stepping motions along the ionic aggregates. These diffusivities can be quantitatively predicted by calculating the lifetimes of continuous association between oppositely charged ions, which equal the time scales of the stepping (diffusive) motions. In contrast, predicting cation diffusivity for systems with isolated ionic aggregates requires another time scale. Finally, our results suggest that to improve conductivity the Coulombic interaction strength should be strong enough to favor percolated aggregates but weak enough to facilitate ion dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure-sensitive mechanical behavior of an additively manufactured psuedoelastic shape memory alloy

The additive manufacturing of shape memory alloys into complex geometries enables fabrication of advanced functional systems across a variety of fields and domains. This work presents results focused on the mechanical behavior of additively manufactured shape memory pseudoelastic NiTi. The deformation induced solid state phase transformation from austenite to martensite allows this system to accommodate large recoverable strains. This deformation behavior is fundamentally driven by crystal-scale transformation physics. Laser powder bed fusion processing reveals that the resulting microstructure, both grain morphology and crystallographic texture, is strongly dependent on the manufacturing processing history. Exhaustive mechanical testing demonstrates that these microstructural factors strongly impact both tensile and cyclic stress–strain behavior. Cyclic dissipative behavior, however, is similar across all tested microstructures following an initial transient period. Remarkably, analysis of spatial strain fields during tensile loading reveals two distinctly different localization “modes”. The first is initiation of localized deformation bands which continuously propagate through the tensile bar during loading. In the second mode localization is observed but lacks propagation; instead additional localization cites nucleate during subsequent loading. The latter phenomena is suspected to be driven by grain-scale deformation physics as the localized band morphologies coincide with grain morphologies. These phenomena strongly impact the resulting aggregate stress–strain behavior. Hence, manufacturers and designers of psuedoelastic functional components must at the very least consider the potential variability in properties when considering additive manufacturing processing. More ideally the process–structure–property relations can be used to further tailor and optimize final functional performance.

Additive manufacturing↗

Microchondrule-bearing clast in the Piancaldoli LL3 meteorite - A new kind of type 3 chondrite and its relevance to the history of chondrules

Electron microprobe, scanning electron microscope, and petrographic analyses of the microchondritic clast of the Piancaldoli LL3 chondrite are reported and compared with other type three chondrites. The clast, like other type three chondrites, has a fine-grained Fe-rich opaque silicate matrix, sharply defined chondrules, abundant low-Ca clinopyroxene and minor troilite and Si and Cr-bearing metallic Fe, Ni. However, the very high model matrix abundance, unique characteristics of the chondrules, and absence of microscopically observable olivine indicate that the clast is a new type of type three chondrite. It is concluded that the microchondrules were formed by the same process that formed normal-sized chondrules in type three chondrites: melting of preexisting dustballs. It is suggested that dust grains were mineralogically sorted in the nebula before aggregating into dustballs.

Rubin, A. E.↗

Laboratory dust experiments - Tracing the composition of cometary dust

The structure and composition of the comet nucleus are investigated theoretically on the basis of aggregation models and laboratory simulations of interstellar-grain evolution. The results are presented in graphs, diagrams, and drawings and discussed in detail. The nucleus is described as a loose tangle of rodlike grains containing about 28 percent H2O, 10 percent CO2 and CO, and 33 percent nonvolatile submicron-size grit particles (silicates, complex organics, and carbon). Evidence from meteorites suggests that the C-12/C-13 ratio of the volatile components is greater than 100.

Greenberg, J. M.↗

Lunar and Planetary Science XXXV: Carbonaceous Chondrites

The titles in this section include: 1) A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites; 2) An Infrared Study of the Matrices of CI1 and CM2 Chondrites; 3) A Study of the Morphology, Composition and Mineral Associations of Fe-Ni Sulphides in CM Carbonaceous Chondrites; 4) Aqueous Alteration Mineralogy in CM Carbonaceous Chondrites; 5) In Situ Location and Characterization of Carbon-bearing Phases in Carbonaceous; 6) Chondrites: Insights from Yamato 791198, a Weakly-altered CM2 Chondrite; 7) Unique Texture in EET 83389: Clues to Formation of Fine Grained Rims in CM Chondrites; 8) Amoeboid Olivine Aggregates in the NWA 760 CV3 Chondrite; 9) Petrologic Type of CV3 Chondrites as Revealed by Raman Spectroscopy of Organic Matter; 10) A First Look at Acfer 324: Evidence for Another CR 3 Chondrite? 11) Hydrogen Isotopic Composition of the Bencubbin Meteorite; 12) The Fountain Hills Meteorite: A New CBa Chondrite from Arizona; 13) Shock Effects in the Metal-rich Chondrites QUE 94411, Hammadah al Hamra 237 and Bencubbin; 14) Mineralogy and Petrology of Al-rich Objects in the CH Carbonaceous Chondrite North West Africa 739.

Source record↗

Constraints on Mechanisms of Chondrule Formation from Chondrule Precursors and Chronology of Transient Heating Events in the Protoplanetary Disk

The mineralogy, petrography, and oxygen-isotope compositions of porphyritic chondrules—dominant chondrule type in most chondrite groups—suggest formation by incomplete melting of isotopically diverse precursors during localized transient heating events in dust-rich regions of the protoplanetary disk characterized by 16O-poor compositions (D17Odust+gas~ –7‰ to +4‰) relative to the inferred Sun’s value (D17O ~ –28 ± 2‰). The chondrule precursors included Ca,Al-rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), chondrules of earlier generations, fine-grained matrix-like material, and possibly fragments of pre-existing planetesimals. Like porphyritic chondrules, igneous CAIs formed by melting of isotopically diverse precursors during transient heating events, but in an isotopically distinct, solar-like reservoir of the protoplanetary disk (D17O dust + gas ~ –24‰), probably near the proto Sun. Based on a narrow range of the initial 26Al/27Alratios inferred from the internal Al-Mg isochrons in igneous CAIs, their melting started at the very beginning of Solar System formation (t0), defined by the CV CAIs with U-corrected Pb-Pb age of 4567.3 ± 0.16 Ma and the canonical 26Al/27Al ratio of (5.25 ± 0.02) ¥ 10–5, and lasted at least 0.3 Ma. The U-corrected Pb-Pb absolute and 26Al-26Mg relative ages of porphyritic chondrules from type 3 ordinary, CO, CV, and CR carbonaceous chondrites (assuming uniform distribution of 26Al in the disk at the canonical level) suggest chondrule formation started at t0 and lasted for about 4 Ma. These observations may preclude formation of the majority of porphyritic chondrules by splashing of differentiated planetesimals and by collisions between planetesimals; instead, they are consistent with melting of dust balls by bow shocks or magnetized turbulence in the disk. Some porphyritic chondrules in equilibrated (petrologic type 4–6) ordinary chondrites contain relict fragments of coarse-grained chromite, ilmenite, phosphates, and albitic plagioclase. The similar mineral assemblage is commonly observed in type 4–6 ordinary chondrites, but is absent in type 3 chondrites, suggesting these chondrules formed by incomplete melting of thermally metamorphosed ordinary chondrite material, possibly by impacts. The CB metal-rich carbonaceous chondrites contain exclusively magnesian non-porphyritic chondrules crystallized from complete melts. These chondrules formed in a gas-melt plume generated by a hypervelocity (≥20 km/s) collision between planetesimals ~4.8 Ma after t0 in a transition or a debris disk. One of the colliding bodies was probably differentiated. The CH metal-rich carbonaceous chondrites contain chondrules formed by different mechanisms. The magnesian non-porphyritic chondrules formed in the CB impact plume ~4.8 Ma after t0. The chemically diverse (magnesian, ferroan, and Al-rich) porphyritic chondrules formed by incomplete melting of isotopically diverse precursors in the protoplanetary disk, most likely prior the CB impact plume event. We conclude that there are multiple mechanisms of chondrule formation that operated over the entire life-time of the disk.

Chondrules↗

Helium Reservoirs in Iron Nanoparticles on the Lunar Surface

The Moon’s surface is directly exposed to the space environment and subject to alteration by space weathering. One agent of space weathering, the solar wind, enriches the lunar surface with helium. Although we understand how helium is delivered to the Moon, certain aspects of helium concentration processes on the surface remain unknown, such as why impact-generated glass aggregates contain more helium than equally sized soil grains of other types. Here we have analyzed the contents of vesicular iron nanoparticles in lunar impact glasses using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy and show that the nanoparticles contain high concentrations of helium (10-24 atoms/nm3). The widespread occurrence of vesicular iron nanoparticles among lunar samples suggests that they may be an important helium reservoir. These results also suggest that space weathering of iron-rich minerals plays a role in helium sequestration on the Moon and potentially on other airless bodies.

Brittany A. Cymes↗

Friction Stir Welding – an Advanced Approach to Repair Nuclear Power Plant Components

Solid phase joining technique friction stir welding (FSW) has been shown to mitigate helium-related issues in fusion welding of irradiated steels. Here, we present detailed characterization results of the first friction stir weld of an irradiated 304L stainless steel (SS) coupon contained 5.2 atomic parts per million (appm) helium. Scanning electron microscopy (SEM) was used to characterize a cross section specimen removed from the friction stir weld. No macro helium induced crack was observed at the analyzed cross-section, and only 1 – 1.5 µm size pores were found in the stir zone (SZ) and the thermal-mechanical affected zone (TMAZ). Moreover, some minor helium aggregations (Maximum ~20 µm in length) appeared along grain boundaries inside the TMAZ. Thereafter, miniature tensile specimens were extracted from the SZ, TMAZ and heat affected zone (HAZ), and base metal (BM) and tested. All welded specimens showed high total elongations (> 60%) and strengths (> 75% BM strengths). Overall, the weld made by FSW showed much better results comparing with traditional fusion welding on irradiated SS.

Tang, Wei↗

Layer silicates in a chondritic porous interplanetary dust particle

Analytical electron microscopy on individual grains from a portion of a chondritic porous interplanetary dust particle (aggregate W7029C1 from the NASA Johnson Space Center Cosmic Dust Collection) shows that layer silicates compose 50 percent of the silicate fraction examined. These layer silicates can be classified into two distinct crystallochemical groups: (1) fine-grained, polycrystalline smectite minerals; and (2) well-ordered, single crystals of kaolinite and Mg-poor talc. The layer silicates in this portion of sample W7029(asterisk)A are dissimilar to those described in other chondritic porous aggregates. The predominant layer silicate assemblage in W7029(asterisk)A indicates that heating of the aggregate during atmospheric entry was brief and probably to a temperature less than 300 C. Comparison with terrestrial phyllosilicate occurrences suggests that some layer silicates in aggregate W7029(asterisk)A may have been formed by alteratiton from preexisting silicate minerals at low temperatures (less than 25 C) after aggregate formation.

Rietmeijer, F. J. M.↗