Subsolidus reequilibration, grain growth, and compositional changes of native FeNi metal in lunar rocks
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Taylor, L. A.↗
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Ordering of FeNi in clear taenite from meteorites
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Scott, E. R. D.↗
Comparative FeNi and Silicate Chronology in Portales Valley
Re-Os and U-Pb data on Portales Valley suggest an early formation for the metal and silicates. These two chronometers and Rb-Sr and Sm-Nd require a young disturbance. This is inconsistent with the 39 Ar-40 Ar age and in need of clarification.
Chen, J. H.↗
Solvent Influence on the Magnetization and Phase of Fe-Ni Alloy Nanoparticles Generated by Laser Ablation in Liquids
The synthesis of bimetallic iron-nickel nanoparticles with control over the synthesized phases, particle size, surface chemistry, and oxidation level remains a challenge that limits the application of these nanoparticles. Pulsed laser ablation in liquid allows the properties tuning of the generated nanoparticles by changing the ablation solvent. Organic solvents such as acetone can minimize nanoparticle oxidation. Yet, economical laboratory and technical grade solvents that allow cost-effective production of FeNi nanoparticles contain water impurities, which are a potential source of oxidation. Here, we investigated the influence of water impurities in acetone on the properties of FeNi nanoparticles generated by pulsed laser ablation in liquids. To remove water impurities and produce “dried acetone”, cost-effective and reusable molecular sieves (3 Å) are employed. The results show that the Fe50Ni50 nanoparticles’ properties are influenced by the water content of the solvent. The metastable HCP FeNi phase is found in NPs prepared in acetone, while only the FCC phase is observed in NPs formed in water. Mössbauer spectroscopy revealed that the FeNi nanoparticles oxidation in dried acetone is reduced by 8% compared to acetone. The high-field magnetization of Fe50Ni50 nanoparticles in water is the highest, 68 Am2/kg, followed by the nanoparticles obtained after ablation in acetone without water impurities, 59 Am2/kg, and acetone, 52 Am2/kg. The core-shell structures formed in these three liquids are also distinctive, demonstrating that a core-shell structure with an outer oxide layer is formed in water, while carbon external layers are obtained in acetone without water impurity. The results confirm that the size, structure, phase, and oxidation of FeNi nanoparticles produced by pulsed laser ablation in liquids can be modified by changing the solvent or just reducing the water impurities in the organic solvent.
36 MATERIALS SCIENCE↗
Low temperature diffusion coefficients in the Fe-Ni and FeNiP systems: Application to meteorite cooling rates
The interdiffusion coefficient of FeNi in fcc taenite (gamma) of Fe-Ni and Fe-Ni-0.2 P alloys was measured as a function of temperature between 600 and 900 C. This temperature range is directly applicable to the nucleation and growth of the Widmanstatten pattern in iron meteorites and metal regions of stony and stony-iron meteorites. Diffusion couples were made from FeNi or FeNiP alloys which ensured that the couples were in the taenite phase at the diffusion temperature. The presence or absence of grain boundary diffusion was determined by measuring the Ni profile normal to the existing grain boundaries with the AEM. Ignoring any variation of interdiffusion coefficient with composition, the measured data was plotted versus the reciprocal of the diffusion temperature. The FeNi data generally follow the extrapolated Goldstein, et al. (1965) data from high temperatures. The FeNiP data indicates that small additions of P (0.2 wt%) cause a 3 to 10 fold increase in the FeNi interdifussion coefficient increasing with decreasing temperature. This increase is about the same as that predicted by Narayan and Goldstein (1983) at the Widmanstatten growth temperature.
Dean, D. C.↗
Mineralogy of new Antarctic achondrites with affinity to Lodran and a model of their evolution in an asteroid
We studied five new Antartic achondrites, MacAlpine Hills (MAC) 88177, Yamato (Y)74357, Y75274, Y791491 and Elephant Moraine (EET)84302 by mineralogical techniques to gain a better understanding of the mineral assemblages of a group of meteorites with an affinity to Lodran (stony-iron meteorite) and their formation processes. This group is being called lodranites. These meteorites contain major coarse-grained orthopyroxene (Opx) and olivine as in Lodran and variable amounts of FeNi metal and troilite etc. MAC88177 has more augite and less FeNi than Lodran; Y74357 has more olivine and contains minor augite; Y791491 contains in addition plagioclase. EET84302 has an Acapulco-like chondritic mineral assembladge and is enriched in FeNi metal and plagioclase, but one part is enriched in Opx and chromite. The EET84302 and MAC88177 Opx crystals have dusty cores as in Acapulco. EET84302 and Y75274 are more Mg-rich than other members of the lodranite group, and Y74357 is intermediate. Since these meteorites all have coarse-grained textures, similar major mineral assemblages, variable amounts of augite, plagioclase, FeNi metal, chromite and olivine, we suggest that they are related and are linked to a parent body with modified chondritic compositions. The variability of the abundances of these minerals are in line with a proposed model of the surface mineral assemblages of the S asteroids. The mineral assemblages can best be explained by differing degrees of loss or movements of lower temperature partial melts and recrystallization, and reduction. A portion of EET84302 rich in metal and plagioclase may represent a type of component removed from the lodranite group meteorites. Y791058 and Caddo County, which were studied for comparison, are plagioclase-rich silicate inclusions in IAB iron meteorites and may have been derived by similar process but in a different body.
Takeda, Hiroshi↗
Shock Effects in the Metal-rich Chondrites QUE 94411, Hammadah al Hamra 237 and Bencubbin
We have studied the metal-rich chondrites QUE94411 (QUE), Hammadah al Hamra 237 (HH237) and Bencubbin with an emphasis on the petrographical and mineralogical effects of the shock processing that these meteorite assemblages have undergone. Iron-nickel metal and chondrule silicates are the main components in these meteorites. These high-temperature components are held together by shock melts consisting of droplets of dendritically intergrown FeNi metal/sulfide embedded in ferrous silicate glass. The silicate glass component of the shock melt is substantially more FeO-rich (FeO: 30 to 40 wt%) than the prevailing chondrule silicates (FeO less than 5 wt%). Fine-grained matrix material, which is a major component in most other chondritic assemblages, is extremely scarce in QUE4411 and HH237; it has not been observed in Bencubbin. This material occurs as rare, hydrated, and fine-grained matrix lumps with major and minor element abundances roughly similar to the ferrous silicate shock melts (and CI). We infer that hydrated, fine-grained material, compositionally similar to these matrix lumps, was originally present between the FeNi metal grains and chondrules, but was preferentially heated by the shock wave and melted. Other shock-related features in QUE94411, HH237, and Bencubbin include a distinct alignment and occasionally strong plastic deformation of metal and chondrule fragments. However, the existence of chemically zoned and metastable FeNi metal condensates condensates in direct contact with shock melts indicates that the shock did not substantially increase the average temperature of the aggregate. TEM analyses of the FeNi metal droplets embedded in the shock melts show martensitic crystal structures, indicating rapid cooling, essentially quenching, of the shock melts. These findings indicate that the preshock temperature of the assemblage was low. Because porphyritic olivine-pyroxene chondrules are absent in QUE94411, HH237, and Bencubbin, it is difficult to determine the precise shock stage of these meteorites, but the shock was probably relatively light (S2- S3; 5-20 GPa) consistent with a bulk temperature increase of the assemblages of less than 200 C. The higher pressures within this range (i.e. 15-20 GPa) are consistent with the findings of shock produced diamonds in Bencubbin. The many mineralogical, petrological and isotopic (e.g. O and N) similarities between Bencubbin, Weatherford, Gujba and QUE/HH237 have been used to argue for a common origin of these meteorites on a single asteroidal parent body. The findings of this study, which indicate similar shock processing, lend support to this view.
Meibom, A.↗
Nitrogen-Doped Carbon Flowers with Fe and Ni Dual Metal Centers for Effective Electroreduction of Oxygen
Carbon-based nanocomposites have been attracting extensive attention as high-performance catalysts in alkaline media towards the electrochemical reduction of oxygen. Herein, polyacrylonitrile nanoflowers are synthesized via a free-radical polymerization route and used as a structural scaffold and precursor, whereby controlled pyrolysis leads to the ready preparation of carbon nanocomposites (FeNi-NCF) doped with both metal (Fe and Ni) and nonmetal (N) elements. Transmission electron microscopy studies show that the FeNi-NCF composites retain the flower-like morphology, with the metal species atomically dispersed into the flaky carbon petals. Remarkably, despite a similar structure, elemental composition, and total metal content, the FeNi-NCF sample with a high Fe:Ni ratio exhibits an electrocatalytic performance towards oxygen reduction reaction (ORR) in alkaline media that is similar to that by commercial Pt/C, likely due to the Ni to Fe electron transfer that promotes the adsorption and eventual reduction of oxygen, as evidenced in X-ray photoelectron spectroscopic measurements. Results from this study underline the importance of the electronic properties of metal dopants in the manipulation of the ORR activity of carbon nanocomposites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The origin of the Moon
Bulk density alone shows that the Moon is depleted in metallic FeNi relative to the Earth or to chondritic meteorites. This depletion implies that the Moon formed not from chondrites but from differentiated material. Origin of the Moon by fission from the Earth offers a simple explanation for its depletion in FeNi, but this mechanism seems unlikely because of associated dynamical difficulties. Lunar volatile element depletions were invoked in support of fission, but volatile contents of eucritic meteorites are similarly low and the eucrites did not form by Earth fission. A more plausible origin of the Moon is accretion from the circumterrestrial swarm. The low FeNi content of the Moon is understood if the mean size of interplanetary silicate particles was much smaller than that for metal particles, since this would have led to preferential capture of silicates into Earth orbit, but the question arises whether the mean particle size of the metallic particles was great enough to prevent their capture into the swarm.
Wasson, J. T.↗
New Nickel Vapor Pressure Measurements: Possible Implications for Nebular Condensates
Temperatures high enough to vaporize even refractory solids existed in the midplane of the solar nebula during its earliest evolutionary stages and played an important role in the processing of materials that went into the formation of the inner planets and asteroids. A variety of such high-T materials have been identified in primitive chondritic meteorites. These include chemically zoned FeNi metal grains that are generally believed to have formed directly by gas-solid condensation from a gas of approximately solar composition. These FeNi particles provide important information about the times scales of formation and physical transport mechanisms in the nebula, as well as formation temperature, pressure and gas chemistry. Currently, however, the interpretation of the chemical signatures in these FeNi particles rests on less than perfect information about the condensation sequence of siderophile elements. For example much, if not all, of the thermodynamic data for the vapor pressures of moderately refractory metals , such as Fe, Ni and Co, do not cover the desired temperature range. As a result, quite large extrapolations are needed. These extrapolations can be complex and uncertain due to factors such as oxygen fugacity or the presence of hydrogen gas.
Johnson, N. M.↗
Coupling computational thermodynamics with density-function-theory based calculations to design L12 precipitates in Fe Ni based alloys
Achieving a high-volume fraction of thermodynamically stable L12-type precipitates that are resistant to coarsening is of great importance for the development of low-cost FeNi based austenitic steels. With the aid of computational thermodynamics, this work designed two model alloys: Fe-37.4Ni-6.1Al-2.9Ti (FNAT) and Fe-45.2Ni-5.9Al-8.5Si (FNAS). Both alloys were designed to contain a similar amount of L1 2 precipitate in Fe-Ni matrix without forming other precipitates. Density-Function-Theory (DFT) calculation was coupled with computational thermodynamics to predict the critical radius at which the precipitates change shape from spherical to cuboidal. The calculation results suggest that critical radius for the FNAT alloy is about two orders of magnitude larger than that for the FeNiAlSi alloy. Phase stability and morphology of the L1 2 precipitates in these two alloys were experimentally investigated through X-ray diffraction, atom probe tomography, and scanning and transmission electron microscopy. The L1 2 precipitates in the FeNiAlSi system were found to be cuboidal and rod shaped, with much larger size than the spherical ones in the FeNiAlTi system, agreeing with the calculation results. This work suggested that coupling computational thermodynamics with DFT calculations can be reliably used to design L1 2 precipitates in FeNi based alloys.
36 MATERIALS SCIENCE↗
Rust in the Apollo 16 rocks
Apollo 16 samples of all four rock types and from all stations contain evidence for hydration and oxidation - i.e., the presence of hydrated iron oxide, probably goethite. Rock 66095 contains native FeNi grains with a characteristic intergrowth of schreibersite and, to lesser extents, of cohenite. Troilite also contains sphalerite. The goethite contains 1.5-4.6 wt.% chlorine and occurs mainly on the edges of FeNi metal, causing a rust color in the cracks and space around the native metal grains, which also contain abundant chlorine. This observation suggests the presence of lawrencite (FeCl2), a phase that deliquesces and oxidizes very rapidly upon exposure to water or to a moist atmosphere.
Taylor, L. A.↗
Fractional crystallization of iron meteorites, an experimental study
Measurements of the distribution coefficients of various elements (Ni, Co, P, Pt, Ir, Ge, Cr, and Au) between solid and liquid phases were made for FeNi alloys. A high thermal gradient crystal growing furnace was employed in order to promote plane front solidification, rapid mixing in the liquid and a minimum of diffusion in the solid. Eight measurements of the nickel distribution coefficient gave an average value of 0.91 plus or minus 0.03 and this value was independent of the Ni concentration in the range 5.5 to 8.75 wt. % Ni. Equilibrium distribution coefficients were also calculated by correcting for the diffusion boundary layer present in the liquid. These values are within 20% of the measured distribution coefficient values. Except for Co and Ni, all the measured distribution coefficient values are closer to 1.0 than those calculated by Scott (1972) for the IIIAB irons. Using the experimental values and the calculated equilibrium values for ternary additions to FeNi melts, it appears that fractional crystallization processes will not explain the observed chemical variations in the major iron meteorite groups. Alternative explanations are suggested which also recognize the fact that cooling rates vary widely in several chemical groups.
Goldstein, J. I.↗
Mossbauer spectroscopy and X-ray diffraction of samples from the Santa Catharina iron meteorite
Conversion electron Mossbauer spectroscopy (CEMS) of samples from the Santa Catharina iron meteorite shows the presence of the ordered iron-nickel phase with 50% Ni, tetrataenite, and of the paramagnetic iron-nickel phase with 25% Ni. The FeNi phase with 50% Ni amounts to 70% of the iron-nickel alloys. Futhermore, the CEM spectra show the presence of small peaks from one or more spinel compounds. These small peaks are more pronounced when regions near the rim of the samples are analyzed. The X-ray diffraction of different areas of the samples, both optically dark and optically light areas, shows the presence of a diffraction pattern from a single f.c.c. lattice with a lattice parameter of a=3.58A This means that the two different Fe-Ni phases seen in the CEMS analysis occupy the same lattice. The X-ray photographs also show the presence of super-structure reflections from the ordered FeNi phase, and that the orientation of the f.c.c. lattice is the same within the whole sample.
Roy-Poulsen, H.↗
Low temperature phase transformations in the metallic phases of iron and stony-iron meteorites
The nickel content and the structure of kamacite and decomposed taenite (clear taenite 1, CT-1; the cloudy zone, CZ; and clear taenite 2, CT-2) in the metallic phases of meteorites were determined using X-ray microanalysis techniques in the AEM. The kamacite near the CT-1 interface was found to contain about 4 wt pct Ni. The CT-1 structure contains 51.4-45.6 wt pct Ni; it is ordered FeNi with the L1(0) superstructure. The CZ structure consists of two phases: a globular phase (ordered FeNi containing 50.9 wt pct Ni) and a surrounding honeycomb martensitic phase containing 11.7 wt pct Ni. The CT-2 was found in all of the iron meteorite groups studied and in the pallasites, but not in the mesosiderites. Based on the preliminary evidence, this region is believed to be ordered Fe3Ni. Possible mechanisms for the decomposition of taenite are discussed.
Reuter, K. B.↗
A new class of natural magnetic materials - The ordering alloys
It is shown that tetrataenite (approximately FeNi), found in many meteorites, and Josephinite (approximately FeNi3), found in many serpentinized peridotites and possibly in Allende, are atomically ordered alloys. Data are presented, showing magnetic hysteresis loops, coercivity-temperature behavior at cryogenic temperatures, and thermomagnetic curves, that show that these ordered magnetic materials have unique magnetic properties and do not fit the conventional rock magnetism paradigms represented by Fe3O4 serpentinites. The ordered state is characterized by induced magnetic anisotropy, reaching the extreme for the tetragonal truly uniaxial anisotropy in FeNi. It is suggested that these ordered magnetic alloys should be considered a new class of natural magnetic materials.
Wasilewski, Peter↗
The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies
Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.
Righter, K.↗
Metal-silicate Partitioning of Re, Ru, Pt, Os, Ti, Nb, and Ta in Reduced Differentiated Planetary Bodies
Siderophile (iron-loving) elements are strongly fractionated during differentiation of planetary bodies into core and mantle [1]. Because the fractionation is controlled by the pressure, temperature, redox conditions, and composition, this group of elements can provide important constraints on the conditions of accretion and core formation in early solar system bodies (planetesimals) and planets (Earth, Mercury, Venus)[2]. At the reducing conditions thought to prevail in the early solar system, Si is known to alloy with FeNi metallic liquids (e.g., [3]) affecting the activity coefficients of siderophile elements in FeNi liquids and thus ultimately their detailed partitioning between metal and silicate melt. The effect of Si can be significant for some siderophile elements, as demonstrated previously by (e.g., [4]: Ni, Co; [5,6]: Ge, As, Sb, Pd, Pt, Au). The effect of Si has not yet been determined for several key groups of siderophile elements including the highly siderophile Re, Ru and Os, and the weakly siderophile Ta, Nb, and Ti. Here, we report new experiments designed to quantify the effect of Si on the partitioning of Re, Pt, Os, Ru, Ti, Ta and Nb between metal and silicate melts. The results will be used to evaluate metal/silicate equilibrium for Nb, Ta, Ti and Nb/Ta ratios in planetary mantles, mantle concentrations of Ru, Re, Pt, Os during accretion, the evolution of Re/Os, Pt/Os ratios in magma oceans, and the role of late veneer in establishing Re and Ru abundances in the terrestrial mantle.
core formation↗