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All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

Miniature Cryogenic Valves for a Titan Lake Sampling System

The Cassini mission has revealed Titan to be one of the most Earthlike worlds in the Solar System complete with many of the same surface features including lakes, river channels, basins, and dunes. But unlike Earth, the materials and fluids on Titan are composed of cryogenic organic compounds with lakes of liquid methane and ethane. One of the potential mission concepts to explore Titan is to land a floating platform on one of the Titan Lakes and determine the local lake chemistry. In order to accomplish this within the expected mass volume and power budgets there is a need to pursue the development for a low power lightweight cryogenic valves which can be used along with vacuum lines to sample lake liquid and to distribute to various instruments aboard the Lander. To meet this need we have initiated the development of low power cryogenic valves and actuators based on a single crystal piezoelectric flextensional stacks produced by TRS Ceramics Inc. Since the origin of such high electromechanical properties of Relaxor-PT single crystals is due to the polarization rotation effect, (i.e., intrinsic contributions), the strain per volt decrease at cryogenic temperatures is much lower than in standard Lead Zirconate Titanate (PZT) ceramics. This makes them promising candidates for cryogenic actuators with regards to the stroke for a given voltage. This paper will present our Titan Lake Sampling and Sample Handling system design and the development of small cryogenic piezoelectric valves developed to meet the system specifications.

Piezoelectric Devices↗
NASA NTRS2016

A Piezoelectric Shear Stress Sensor

In this paper, a piezoelectric sensor with a floating element was developed for shear stress measurement. The piezoelectric sensor was designed to detect the pure shear stress suppressing effects of normal stress generated from the vortex lift-up by applying opposite poling vectors to the: piezoelectric elements. The sensor was first calibrated in the lab by applying shear forces and it showed high sensitivity to shear stress (=91.3 +/- 2.1 pC/Pa) due to the high piezoelectric coefficients of PMN-33%PT (d31=-1330 pC/N). The sensor also showed almost no sensitivity to normal stress (less than 1.2 pC/Pa) because of the electromechanical symmetry of the device. The usable frequency range of the sensor is 0-800 Hz. Keywords: Piezoelectric sensor, shear stress, floating element, electromechanical symmetry

Kim, Taeyang↗
NASA NTRS2016

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approx.576-867 C. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Metallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120deg triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3+, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Srinivasan, P.↗
NASA NTRS2015

The Safety Course Design and Operations of Composite Overwrapped Pressure Vessels (COPV)

Following a Commercial Launch Vehicle On-Pad COPV (Composite Overwrapped Pressure Vessels) failure, a request was received by the NESC (NASA Engineering and Safety Center) June 14, 2014. An assessment was approved July 10, 2014, to develop and assess the capability of scanning eddy current (EC) nondestructive evaluation (NDE) methods for mapping thickness and inspection for flaws. Current methods could not identify thickness reduction from necking and critical flaw detection was not possible with conventional dye penetrant (PT) methods, so sensitive EC scanning techniques were needed. Developmental methods existed, but had not been fully developed, nor had the requisite capability assessment (i.e., a POD (Probability of Detection) study) been performed.

Saulsberry, Regor↗
NASA NTRS2016

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Srinivasan, P.↗
NASA NTRS2016

Experimental Comparison of Piezoelectric and Magnetostrictive Shunt Dampers

A novel mechanism called the vibration ring is being developed to enable energy conversion elements to be incorporated into the driveline of a helicopter or other rotating machines. Unwanted vibration is transduced into electrical energy, which provides a damping effect on the driveline. The generated electrical energy may also be used to power other devices (e.g., health monitoring sensors). PZT (piezoceramic) and PMN-30%PT (single crystal) stacks, as well as a Tb_0.3 Dy_0.7 Fe_1.92 (Terfenol-D) rod with a bias magnet array and a pickup coil, were tested as alternative energy conversion elements to use within the vibration ring. They were tuned for broadband damping using shunt resistors, and dynamic compression testing was conducted in a high-speed load frame. Energy conversion was experimentally optimized at 750Hz by tuning the applied bias stress and resistance values. Dynamic testing was conducted up to 1000Hz to determine the effective compressive modulus, shunt loss factor, internal loss factor, and total loss factor. Some of the trends of modulus and internal loss factor versus frequency were unexplained. The single crystal device exhibited the greatest shunt loss factor whereas the Terfenol-D device had the highest internal and total loss factors. Simulations revealed that internal losses in the Terfenol-D device were elevated by eddy current effects, and an improved magnetic circuit could enhance its shunt damping capabilities. Alternatively, the Terfenol-D device may be simplified to utilize only the eddy current dissipation mechanism (no pickup coil or shunt) to create broadband damping.

piezoelectric↗
NASA NTRS2017

Metallized Nanotube Polymer Composite (MNPC) and Methods for Making Same

A novel method to develop highly conductive functional materials which can effectively shield various electromagnetic effects (EMEs) and harmful radiations. Metallized nanotube polymer composites (MNPC) are composed of a lightweight polymer matrix, superstrong nanotubes (NT), and functional nanoparticle inclusions. MNPC is prepared by supercritical fluid infusion of various metal precursors (Au, Pt, Fe, and Ni salts), incorporated simultaneously or sequentially, into a solid NT-polymer composite followed by thermal reduction. The infused metal precursor tends to diffuse toward the nanotube surface preferentially as well as the surfaces of the NT-polymer matrix, and is reduced to form nanometer-scale metal particles or metal coatings. The conductivity of the MNPC increases with the metallization, which provides better shielding capabilities against various EMEs and radiations by reflecting and absorbing EM waves more efficiently. Furthermore, the supercritical fluid infusion process aids to improve the toughness of the composite films significantly regardless of the existence of metal.

Park, Cheol↗
NASA NTRS2017

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Sarafian, Adam R.↗
NASA NTRS2017

Chorus Whistler Wave Source Scales As Determined From Multipoint Van Allen Probe Measurements

Whistler mode chorus waves are particularly important in outer radiation belt dynamics due to their key role in controlling the acceleration and scattering of electrons over a very wide energy range. The key parameters for both nonlinear and quasi-linear treatment of wave-particle interactions are the temporal and spatial scales of the wave source region and coherence of the wave field perturbations. Neither the source scale nor the coherence scale is well established experimentally, mostly because of a lack of multipoint VLF waveform measurements. We present an unprecedentedly long interval of coordinated VLF waveform measurements (sampled at 16384 s(exp -1)) aboard the two Van Allen Probes spacecraft-9 h (0800-1200 UT and 1700-2200 UT) during two consecutive apogees on 15 July 2014. The spacecraft separations varied from about 100 to 5000 km (mostly radially); measurements covered an L shell range from 3 to 6; magnetic local time 0430-0900, and magnetic latitudes were approximately 15 and approximately 5 deg during the two orbits. Using time-domain correlation techniques, the single chorus source spatial extent transverse to the background magnetic field has been determined to be about 550-650 km for upper band chorus waves with amplitudes less than 100 pT and up to 800 km for larger amplitude, lower band chorus waves. The ratio between wave amplitudes measured on the two spacecraft is also examined to reveal that the wave amplitude distribution within a single chorus element generation area can be well approximated by a Gaussian exp(-0.5 x r (exp 2)/r(sub 0)(exp 2)), with the characteristic scale r(sub 0) around 300 km. Waves detected by the two spacecraft were found to be coherent in phase at distances up to 400 km.

Agapitov, O.↗
NASA NTRS2017

Lunar Advanced Volatile Analysis Subsystem: Pressure Transducer Trade Study

In Situ Resource Utilization (ISRU) is a key factor in paving the way for the future of human space exploration. The ability to harvest resources on foreign astronomical objects to produce consumables and propellant offers potential reduction in mission cost and risk. Through previous missions, the existence of water ice at the poles of the moon has been identified, however the feasibility of water extraction for resources remains unanswered. The Resource Prospector (RP) mission is currently in development to provide ground truth, and will enable us to characterize the distribution of water at one of the lunar poles. Regolith & Environment Science and Oxygen & Lunar Volatile Extraction (RESOLVE) is the primary payload on RP that will be used in conjunction with a rover. RESOLVE contains multiple instruments for systematically identifying the presence of water. The main process involves the use of two systems within RESOLVE: the Oxygen Volatile Extraction Node (OVEN) and Lunar Advanced Volatile Analysis (LAVA). Within the LAVA subsystem, there are multiple calculations that depend on accurate pressure readings. One of the most important instances where pressure transducers (PT) are used is for calculating the number of moles in a gas transfer from the OVEN subsystem. As a critical component of the main process, a mixture of custom and commercial off the shelf (COTS) PTs are currently being tested in the expected operating environment to eventually down select an option for integrated testing in the LAVA engineering test unit (ETU).

Kang, Edward Shinuk↗
NASA NTRS2018

Effect of Silicon on the Activity Coefficient of Rhenium in Fe-Si Liquids: Implications for HSE and Os Isotopes in Planetary Mantles

Metallic cores contain light alloying elements that can be a combination of S, C, Si, and O, all of which have important chemical and physical influences. For Earth, Si may be the most abundant light element in the core. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE), and thus the partitioning behavior of those elements between core and mantle. The effect of Si on the highly siderophile elements is only beginning to be studied and the effects on Au, Pd and Pt are significant. Here we report new experiments designed to quantify the effect of Si on the partitioning of Re between metal and silicate melt. A solid understanding of Re partitioning is required for a complete understanding of the Re-Os isotopic systems. The results will be applied to understanding the HSEs and Os isotopic data for planetary mantles, and especially Earth.

Righter, K.↗
NASA NTRS2018

Ag Isotopic Evolution of the Mantle During Accretion: New Constraints from Pd and Ag Metal-Silicate Partitioning

Decay of (sup 107) Pd to (sup 107) Ag has a half-life of 6.5 times 10 (sup 6) mega-annums. Because these elements are siderophile but also volatile, they offer potential constraints on the timing of core formation as well as volatile addition. Initial modelling has shown that the Ag isotopic composition of the bulk silicate Earth (BSE) can be explained if accretion occurs with late volatile addition. These arguments were tested for sensitivity for pre-cursor Pd/Ag contents, and for a fixed Pd/Ag ratio of the BSE of 0.1. New Ag and Pd partitioning data has allowed a better understanding of the partitioning behavior of Pd and Ag during core formation. The effects of S, C and Si, and the effect of high temperature and pressure has been evaluated. We can now calculate D(Ag) and D(Pd) over the wide range of PT conditions and variable metallic liquid compositions that are known during accretion. We then use this new partitioning information to revisit the Ag isotopic composition of the BSE during accretion.

Righter, K.↗
NASA NTRS2019

Quantifying the Influence of Redox Conditions on the Seismic Properties of Olivine

A series of eight olivine specimens were fabricated by hot-pressing at 1200 degrees Celsius and 300 megapascals (MPa). Each hot-pressed specimen was then wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2), and interrogated via forced torsional oscillation. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Celsius to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform InfraRed spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom ppm (parts per million) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900 degrees Celsius (G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dG (sub U)/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples (but not a hydrous and oxidized Fe-free sample) we observe deficits of G (sub UR), and increased values of dG (sub U)/dT, relative to the expected elastic (anharmonic) behavior of Fo90 olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress in reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, Christopher, II↗
NASA NTRS2018

Novel Applications of Focused Ion Beam Technique for Planetary Sample Analyses

We are using innovative FIB techniques to prepare samples of planetary materials for different types of coordinated analyses using ion microprobes, synchrotron beamlines, and specialized transmission electron microscopy (TEM) techniques. In these cases, the FIB sample preparation is the critical step in enabling these specialized analyses. We discuss several examples below utilizing the FEI Quanta3D instrument at the NASA Johnson Space Center. Trace element analyses utilizing synchrotron x-ray fluorescence. The trace element content of mineral grains in comet dust provides important clues on their formation and processing in the early solar system. We preformed coordinated analyses of a comet dust particle that had been prepared using ultramicrotomy for TEM analysis. Following the TEM analyses, we extracted a 70 nm thick section from a region of the carbon (C) film of the TEM grid, for additional analyses. A carbon ring ~2-3 μm thick was deposited on top of the C film using the FIB. The C film on the outer rim of the ring was milled away using various patterns to uniformly release the stresses on the film, preventing rupture and collapse, and was attached to the micromanipulator needle. We then isolated the ring completely and transferred the section to a silicon sample holder for analysis using the HXN (hard X-ray nanoprobe) beamline at NSLSII at Brookhaven National Lab. Coordinated Analyses of Presolar Grains. Rare sub-m presolar grains that originate in evolved stars and supernovae, occur in primitive astromaterials and are identified by their exotic isotopic compositions. Coordinated analyses of these grains using NanoSIMS, TEM, and other techniques on the same grain is enabled by innovative FIB sample preparation. In order to obtain subsequent isotopic analyses of Mg and Fe, contributions from surrounding grains were minimized. We precisely deposited a protective cap of Pt on top of the grain to preserve the grain of interest and then milled away about 5 μm diameter of the surrounding material. Following the isotopic analyses, the spindle was extracted and thinned to electron transparency for TEM microstructural analyses. In situ heating TEM experiments on lunar samples. We extracted a FIB thin section from Apollo 17 lunar rock 76015. To avoid ion-beam damage, e-beam deposition was used to deposit the first 500 nm of the C strap, followed by ion beam-assisted deposition of ~3 μm carbon. We performed an ex situ lift-out of the section and placed the section on one of the elements of a microelectromechanical systems (MEMS) - specialized heating substrate and attached the section to the substrate by depositing small C straps with the FIB. The heating chips utilize silicon nitride windows to support the samples and provide uniform heating while enabling TEM imaging. The heating chip was loaded into a Hitachi “Blaze” heating holder and analyzed using a Hitachi HF5000 at the University of Arizona.

Rahman, Z.↗
NASA NTRS2020

Creating High Temperature Ferroelectrics by Using Ternary Components with Limited Solubility

High temperature ferroelectrics are needed for actuator applications ranging from drilling on the surface of Venus to fuel modulation in jet engines. Machine learning in previous work has dramatically reduced search space and produced new candidates for experimentation. It is possible to create high temperature piezoelectrics by changing the end member of ternary systems. The starting point was near the morphotropic phas boundary between BiScO3(BS) and PbTiO3 (PT) (38%/62%). The third end member was suggested by machine learning to create a high Tc with limited solubility; BiCo0.88Fe0.12O3 (BCF).

Hirt, Benjamin↗
NASA NTRSDate not supplied

Coherence Analysis of the Space Launch System using Unsteady Pressure Sensitive Paint

Transonic buffet during atmospheric ascent is a major source of unsteady loading on launch vehicles that, in the past, has led to structural failures. Thus, determining accurate buffet forcing functions (BFFs) to properly predict the vehicle response to buffet is of vital importance in launch vehicle design. The state of the art for obtaining the BFFs relies on wind-tunnel tests where the fluctuating pressures are measured by pressure transducers (PTs) at sparse locations on a rigid, geometrically-scaled buffet model. To compute the BFFs, the outer mold line (OML) of the vehicle is mapped onto contiguous panels centered at the location of the PTs and the measured fluctuating pressures are integrated over the panels’ areas. To mitigate conservatism due to the assumption that the measured buffet pressures act in phase across each panel, coherence factors are applied, effectively reducing the integration areas and, therefore, the buffet forces. For coherence factors to provide the proper level of BFF attenuation, accurate knowledge of the spatial and temporal correlation of the buffet pressures is paramount. Unfortunately, even with hundreds of unsteady pressure transducers instrumenting the models, compromises must be made on the spatial resolution of the PTs. Typically, the PT layout aims at resolving the pressure correlation along the longitudinal axis of the vehicle, assuming that coherent structures propagate mostly in the longitudinal direction. As a result, the distribution of azimuthal/cross-stream correlation is not well known and its impact on the estimated BFFs is often neglected. To fill this and other knowledge gaps, extremely high spatial-resolution uPSP data were collected for three different production-design configurations of the Space Launch System in the NASA Ames Research Center Unitary Plan Wind Tunnel 11-Foot Transonic Wind Tunnel. Specifically, two cargo configurations, the Block 1 and Block 1B, and one crew configuration, the Block 1B crew, were surveyed at resolutions ranging from 600,000 to over 1 million uPSP measurement locations. To shed light on the temporal and spectral behavior of are presented. Several OML regions and flow features of interest are investigated, from theexpansion/shock on the Orion Multi-Purpose Crew Vehicle, to the terminal shock environment on the core stage, and the Strouhal shedding behind the boosters forward attach. The sensitivity of these environments to the vehicle attitude is examined. Furthermore, for selected panels,coherence factors that accurately capture the azimuthal coherence distribution of the buffetpressures are derived and their impact on the estimated BFFs is discussed. Finally, distributions of the local convection velocity and cross spectrum phase are presented.

buffet↗
NASA NTRS2020

Investigation of a Helicopter Individual Blade Control (IBC) System in Two Full-Scale Wind Tunnel Tests: Volume II—Tabulated Data

This volume presents the tabulated data acquired during the testing of an individual blade control (IBC) system for a full-scale BO-105 helicopter rotor in the NASA Ames 40- by 80-Foot Wind Tunnel. The data are divided into appendices according to the data type. Table 6 in Volume I presents a summary of the data acquired during the 1993 and 1994 IBC wind tunnel tests. The data have been tabulated according to test year, run number, and point number (e.g., 1993 IBC Test, Run 20, pt. 3). The 1993 and 1994 IBC tests were each started with a run number of 1. A new run number was assigned each time the wind tunnel and rotor were restarted, even if no data were acquired during the previous run. For this reason, some run numbers appear to be missing, yet all of the IBC data is included in the tabulated data, with one notable exception. The Fourier series data presented in Appendices H, L, and N are provided only for the data points identified with the ”•“ symbol in the last column of Table 6 in Volume I. This was done to keep the physical size of the data tables reasonable. The table below shows which data were included in these appendices; the data encompass the majority of the IBC inputs tested in the wind tunnel. Data for the points not included in Appendices H, L, and N have been retained in the BO-105 IBC database and are electronically available from NASA Ames Research Center.

Investigation↗
NASA NTRS2020

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

accretion↗