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At least 37 records · Page 2

Sm 0.5 Sr 0.5 CoO 3-δ Surface Modification of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ -Ce 0.9 Gd0.1 2-δ Composite Oxygen Electrodes for Solid Oxide Electrochemical Cells

La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3- δ -Ce 0.9 Gd 0.1 O 2- δ (LSCF-GDC) composite oxygen electrodes have been widely used in intermediate temperature (<700 °C) solid oxide cells, with composite usually providing better electrochemical performance than single-phase LSCF. However, LSCF-based electrodes are often observed to degrade over time due to Sr segregation. Here we present an impedance spectroscopy study comparing the degradation behaviors of LSCF-GDC and Sm 0.5 Sr 0.5 CoO 3- δ (SSC) infiltrated LSCF-GDC electrodes. The LSCF-GDC polarization resistance increases by ~5 times over ~1000 h at 650 °C. In contrast, the SSC-infiltrated electrode shows similar initial polarization resistance but much more stable performance. The impedance modeling results show that the improved stability is associated with the low frequency oxygen dissociative adsorption/desorption process. The results suggest that this adsorption/desorption process slows due to increased Sr segregation on LSCF over time, and that SSC does not degrade significantly due to Sr surface segregation.

Electrochemistry↗

Internal Rb-Sr Age and Initial Sr-87/Sr-86 of a Silicate Inclusion from the Campo Del Cielo Iron Meteorite

The largest group of iron meteorites, IAB, is distinguished by the presence of diverse silicate inclusions. In principle, Rb-Sr and Sm-Nd radiometric dating of these silicate inclusions by internal isochron techniques can determine both the times of melting and parent/daughter ratios in the precursor materials via initial Sr-87/Sr-86 and Nd-143/Nd-144 ratios. The Sr-87/Sr-86 and Nd-143/Nd-144 ratios could distinguish chondritic precursors from already differentiated silicates. We reported Rb-Sr and Sm-Nd internal ischron ages of 4.52+/-0.03 Ga and 4.50+/-0.04 Ga, respectively, for plagioclase-diopside-rich material in the Caddo County IAB iron meteorite. These results are essentially identical to literature values of its Ar-Ar age of 4.520+/-0.005 Ga and its Sm-Nd age of 4.53+/-0.02 Ga. The purpose of this study is to evaluate the formation and evolution of silicate inclusions in IAB iron meteorites by determination of their initial Sr-87/Sr-86 ratios combined with higher-resolution chronology and mineralogical and geochemical studies.

Liu, Y.↗

Sol-Gel Synthesis of La(0.6)Sr(0.4)CoO(3-x) and Sm(0.5)Sr(0.5)CoO(3-x) Cathode Nanopowders for Solid Oxide Fuel Cells

Nanopowders of La(0.6)Sr(0.4)CoO(3-x) (LSC) and Sm(0.5)Sr(0.5)CoO(3-x) (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC) with La(Sr)Ga(Mg)O(3-x) (LSGM) as the electrolyte, were synthesized by low-temperature sol-gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by x-ray diffraction. Solgel powders calcined at 550 to 1000 C consisted of a number of phases. Single perovskite phase La(0.6)Sr(0.4)CoO(3-x) or Sm(0.5)Sr(0.5)CoO(3-x) powders were obtained at 1200 and 1300 C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average particle size of the powders was approx.15 nm after 700 C calcinations and slowly increased to 70 to 100 nm after heat treatments at 1300 to 1400 C.

Bansal, Narottam P.↗

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN↗

Role of Sr doping and external strain on relieving bottleneck of oxygen diffusion in La 2- x Sr x CuO 4-δ

In many complex oxides, the oxygen vacancy formation is a promising route to modify the material properties such as a superconductivity and an oxygen diffusivity. Cation substitutions and external strain have been utilized to control the concentration and diffusion of oxygen vacancies, but the mechanisms behind the controls are not fully understood. Using first-principles calculations, we find how Sr doping and external strain greatly enhances the diffusivity of oxygen vacancies in La 2-x Sr x CuO 4-δ (LSCO) in the atomic level. In hole-doped case (2x > δ), the formation energy of an apical vacancy in the LaO layer is larger than its equatorial counterpart by 0.2 eV that the bottleneck of diffusion process is for oxygen vacancies to escape equatorial sites. Such an energy difference can be reduced and even reversed by either small strain (< 1.5%) or short-range attraction between Sr and oxygen vacancy, and in turn, the oxygen diffusivity is greatly enhanced. For fully compensated hole case (2x ≦ δ), the formation energy of an apical vacancy becomes too high that most oxygen vacancies cannot move but would be trapped at equatorial sites. From our electronic structure analysis, we found that the contrasting change in the formation energy by Sr doping and external strain is originated from the different localization natures of electron carrier from both types of oxygen vacancies.

25 ENERGY STORAGE↗

Boosting the performance of reversible solid oxide electrochemical cells with a novel hybrid oxygen electrode, Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ

Solid oxide electrochemical cells (SOECs) stand out as a highly promising clean energy technology that offers several benefits, showing significant potential to play a pivotal role in the transition towards a sustainable and low-carbon energy future. SOECs can efficiently convert the chemical energy stored in fuels to electricity in fuel cell mode, and produce various chemicals from abundant feedstocks (e.g., CO 2 , H 2 O) and intermittent solar/wind-based renewable electricity. Despite extensive efforts that have been devoted to designing novel materials and optimizing SOEC manufacturing processes, aiming to achieve enhanced energy efficiency, the current SOECs still suffer from poor performance, which is mainly due to the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics. To address this challenge, in this work, we have successfully designed an in situ formed hybrid oxygen electrode material (Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ ), which significantly improves the surface oxygen exchange coefficient and bulk oxygen-ion diffusion coefficient, enhancing the OER and ORR electrocatalytic activities. Further, the SOECs equipped with this newly developed oxygen electrode achieved exceptional performance for power generation using both hydrogen and propane as the fuels. At 750 °C, a peak power density of 2.4 W cm -2 was obtained with H 2 as the fuel. Additionally, the SOECs attain unprecedented performance in steam electrolysis mode. A current density of 4.4 A cm -2 was achieved at 1.3 V and 750 °C, which represents the highest performance among all yttria-stabilized zirconia (YSZ) electrolyte-based SOECs. The SOECs also deliver remarkable stability during the accelerated stability testing, highlighting the great potential of Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ as a high-performance oxygen electrode for next generation SOECs.

08 HYDROGEN↗

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

Nyquist, L.aurenceE.↗

Atomic-Layer Engineering of La 2-x Sr x CuO 4 —La 2-x Sr x ZnO 4 Heterostructures

The fabrication of trilayer superconductor-insulator-superconductor (SIS) Josephson junctions with high-temperature superconductor (HTS) electrodes requires atomically perfect interfaces. Therefore, despite great interest and efforts, this remained a challenge for over three decades. Here, we report the discovery of a new family of metastable materials, La 2-x Sr x ZnO 4 (LSZO), synthesized by atomic-layer-by-layer molecular beam epitaxy (ALL-MBE). We show that LSZO is insulating and epitaxially compatible with an HTS compound, La 2-x Sr x CuO 4 (LSCO). Since the “parent” compound La 2-x Sr x ZnO 4 (LZO) is easier to grow, here we focus on this material as our insulating layer. Growing LZO at very low temperatures to reduce cation interdiffusion makes LSCO/LZO interfaces atomically sharp. We show that in LSCO/LZO/LSCO trilayers, the superconducting properties of the LSCO electrodes remain undiminished, unlike in previous attempts with insulator barriers made of other materials. This opens prospects to produce high-quality HTS tunnel junctions.

36 MATERIALS SCIENCE↗

Rb-Sr ages and initial Sr-87/Sr-86 for Apollo 17 basalts and KREEP basalt 15386

The Rb-Sr data reported for Apollo 17 mare basalts and for KREEP basalt 15386 is used to determine mineral isochrons. The weighted average age of four Apollo 17 basalts is 3.76 + or - 0.06 AE, while the age determined for 15386 is 3.94 + or - 0.04 AE. The isotopic data for the Apollo 17 basalts are discussed in the context of Sm and Eu data for the same samples. The Sr-isotopic data are fit best by a three-stage model evolution involving evolution of Sr-87/Sr-86 in an environment with Rb/Sr greater than in the basalts, production of mare basalt source regions of lower but variable Rb/Sr sometime in the interval 4.6 to 3.75 AE ago, and extraction of lavas from these sources 3.75 AE ago. Other possibilities are considered.

Nyquist, L. E.↗

Tracer versus trace element diffusion - Diffusional decoupling of Sr concentration from Sr isotope composition

Chemical diffusivities for nonalkali major, minor, and selected trace elements have been measured at 10 kbar, 1300 C during interdiffusion of dacitic and rhyolitic melts. Sr tracer diffusivities were measured at the same conditions in melts of dacitic and rhyolitic composition and in a diffusion couple of these two melts undergoing simultaneous chemical diffusion. Chemical diffusivities of all elements studied are functions of the silica content of the melt, but at any one silica content the chemical diffusivities of all elements studied are within a factor of five of the Si and Al diffusivities. Si diffusivity varies from 2.8 x 10 to the -9th sq cm/s at 65 percent SiO2 to 5.1 x 10 to the -10th sq cm/s at 75 percent SiO2. The diffusivities of minor and trace elements are proposed to be controlled by the ability of the local melt structure to accommodate these elements while maintaining LTE. The measured Sr tracer diffusivities are an order of magnitude above Sr chemical diffusivities.

Baker, Don R.↗

Review of the Constellation Level II Safety, Reliability, and Quality Assurance (SR&QA) Requirements Documents during Participation in the Constellation Level II SR&QA Forum

At the request of the Exploration Systems Mission Directorate (ESMD) and the Constellation Program (CxP) Safety, Reliability; and Quality Assurance (SR&QA) Requirements Director, the NASA Engineering and Safety Center (NESC) participated in the Cx SR&QA Requirements forum. The Requirements Forum was held June 24-26; 2008, at GRC's Plum Brook Facility. The forums purpose was to gather all stakeholders into a focused meeting to help complete the process of refining the CxP to refine its Level II SR&QA requirements or defining project-specific requirements tailoring. Element prime contractors had raised specific questions about the wording and intent of many requirements in areas they felt were driving costs without adding commensurate value. NESC was asked to provide an independent and thorough review of requirements that contractors believed were driving Program costs, by active participation in the forum. This document contains information from the forum.

Cameron, Kenneth D.↗

The enhanced ferroelectricity in Sr 1-δ TiO 3 /BaTiO 3 superlattices with Sr deficiency

Here we report the tunable ferroelectricity in superlattices of (Sr 1-δ TiO 3 )n/(BaTiO 3 ) 8 with δ ≈ 5% and the maximally enhanced ferroelectricity is found in the n = 6 superlattice. The room-temperature remnant polarization of n = 6 is enhanced by 70% and 1120% compared to those of BaTiO 3 and Sr 1-δ TiO 3 thin films, respectively. The ferroelectric transition temperature of n = 6 is 40 K higher than that of the BaTiO 3 film, and is independent of the measurement frequency. The dependence of remnant field 2Pr on n coincides well with the n dependence of γ/α, which is ratio between out-of-plane and in-plane octahedral rotation angles. It thus suggests a strong correlation between the octahedral rotation pattern and the ferroelectric distortion. Furthermore, our study demonstrates the importance of constructing superlattices to enhance the ferroelectric properties of the defect-engineered materials to be better than the pristine materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Reduction Thermodynamics of Sr 1– x Ce x MnO 3 and Ce x Sr 2– x MnO 4 Perovskites for Solar Thermochemical Hydrogen Production

Herein, the compositional families Sr 1–x Ce x MnO 3 (SCMX, X = 100x, x = 0.10, 0.20, and 0.30) and Ce x Sr 2–x MnO 4 (CSMX, X = 100x, x = 0.10, 0.20, and 0.30) are studied to determine the effects of perovskite structure and cerium content on thermal reduction thermodynamics and the resulting impact on solar thermochemical hydrogen production (STCH). Relying on thermogravimetric results from oxygen nonstoichiometry experiments, fits for various thermodynamic quantities are produced, including defect-reaction specific enthalpy (Δ H) and entropy (Δ S ), as well as the δ-dependent standard partial molar enthalpy, Δh¯$^{°}_{Ο}$, and entropy Δs¯$^{°}_{Ο}$, of oxygen as a function of composition within these two perovskite families. Here, the results of this thermodynamic study are also discussed in the context of structure and cerium dopant level. Experimental hydrogen production results show that the SCM family produces slightly larger amounts of hydrogen per mole of oxide compared with the CSM family under similar reduction and oxidation temperature conditions, however, a direct correlation between structure, cerium content, and water-splitting capacity could not be discerned.

08 HYDROGEN↗

Controlling Magnetization Vector Depth Profiles of La 0.7 Sr 0.3 CoO 3 /La 0.7 Sr 0.3 MnO 3 Exchange Spring Bilayers via Interface Reconstruction

The La 0.7 Sr 0.3 CoO 3–δ /La 0.7 Sr 0.3 MnO 3–δ (LSCO/LSMO) bilayer system is an ideal perovskite oxide platform for investigating interface reconstruction and its effect on their magnetic properties. Previous studies have shown that LSCO can separate into magnetic sublayers, which possess distinct trends as the total LSCO thickness increases. Here, we used polarized neutron reflectometry to quantify changes in the magnetic and chemical depth profiles, and it confirms the formation of ~12 Å-thick interfacial LSCO and LSMO layers, characterized by a decreased nuclear scattering length density compared to the bulk of the layers. This decrease is attributed to the combined effects of oxygen vacancy formation and interfacial charge transfer, which lead to magnetically active Co 2+ ions with ionic radii larger than the Co 3+ /Co 4+ ions typically found in bulk LSCO or single-layer films. The interfacial magnetization values, as well as Co 2+ ion and oxygen vacancy concentrations, depend strongly on the LSCO layer thickness. These results highlight the sensitive interplay of the cation valence states, oxygen vacancy concentration, and magnetization at interfaces in perovskite oxide multilayers, demonstrating the potential to tune their functional properties via careful design of their structure.

36 MATERIALS SCIENCE↗

Tuning In-Plane Magnetic Anisotropy and Interfacial Exchange Coupling in Epitaxial La 2/3 Sr 1/3 CoO 3 /La 2/3 Sr 1/3 MnO 3 Heterostructures

Controlling the in-plane magnetocrystalline anisotropy and interfacial exchange coupling between ferromagnetic (FM) layers plays a key role in next-generation spintronic and magnetic memory devices. In this work, we explored the effect of tuning the magnetocrystalline anisotropy of La 2/3 Sr 1/3 CoO 3 (LSCO) and La 2/3 Sr 1/3 MnO 3 (LSMO) layers and the corresponding effect on interfacial exchange coupling by adjusting the thickness of the LSCO layer (t LSCO ). The epitaxial LSCO/LSMO bilayers were grown on (110) o -oriented NdGaO 3 (NGO) substrates with a fixed LSMO (top layer) thickness of 6 nm and LSCO (bottom layer) thicknesses varying from 1 to 10 nm. Despite the small difference (~0.2%) in lattice mismatch between the two in-plane directions, [001] o and [11̅0] o , a pronounced in-plane magnetic anisotropy was observed. Soft X-ray magnetic circular dichroism hysteresis loops revealed that for t LSCO ≤ 4 nm, the easy axes for both LSCO and LSMO layers were along the [001] o direction, and the LSCO layer was characterized by magnetically active Co 2+ ions that strongly coupled to the LSMO layer. No exchange bias effect was observed in the hysteresis loops. In contrast, along the [11̅0] o direction, the LSCO and LSMO layers displayed a small difference in their coercivity values, and a small exchange bias shift was observed. As t LSCO increased above 4 nm, the easy axis for the LSCO layer remained along the [100] o direction, but it gradually rotated to the [11̅0] o direction for the LSMO layer, resulting in a large negative exchange bias shift. Therefore, we provide a way to control the magnetocrystalline anisotropy and exchange bias by tuning the interfacial exchange coupling between the two FM layers.

36 MATERIALS SCIENCE↗

The Zintl phases A In 2 As 2 (A = Ca, Sr, Ba): new topological insulators and thermoelectric material candidates

Recently, there has been a lot of interest in topological insulators (TIs), being electronic materials, which are insulating in their bulk but with the gapless exotic metallic state on their surface. The surface states observed in such materials behave as a perfect conductor thereby making them more suited for several cutting-edge technological applications such as spintronic devices. Here, we report the synthesis and structural characterization of the Zintl phases AIn 2 As 2 (A = Ca, Sr, Ba), which could become a new class of TIs. Crystal structure elucidation by single-crystal X-ray diffraction reveals that CaIn 2 As 2 and SrIn 2 As 2 are isostructural and crystallize in the EuIn 2 P 2 structure type (space group P6 3 /mmc, no. 194, Z = 2) with unit cell parameters a = 4.1482(6) Å, c = 17.726(4) Å; and a = 4.2222(6) Å, c = 18.110(3) Å, respectively. Their hexagonal structure is made up of alternating [In 2 As 2 ] 2– layers separated by slabs of A 2+ cations. BaIn 2 As 2 on the other hand crystallizes in the monoclinic EuGa 2 P 2 structure type (space group P2/m, no. 10, Z = 4) with unit cell parameters a = 10.2746(11) Å, b = 4.3005(5) Å, c = 13.3317(14) Å and β = 95.569(2)°. This structure is also layered, and it is made up of different type of polyanionic [In 2 As 2 ] 2– units and Ba 2+ cations. The valence electron count for all three compounds adheres to the Zintl-Klemm formalism, and all elements achieve closed-shell electronic configurations. Bulk electronic structure calculations indicate the opening of a bandgap E g ~ 0.03 eV (CaIn 2 As 2 and Sr 2 In 2 As 2 ), and E g ~0.21 eV (BaIn 2 As 2 ) in the absence of strain and spin–orbit coupling (SOC). Furthermore, these results argue in favor of the realization of a nontrivial topological insulator state under the influence of tensile strain and SOC. Preliminary transport properties on BaIn 2 As 2 are suggestive of a degenerate p-type semiconductor—a behavior which is sought after in thermoelectric (TE) materials. Since both TIs and excellent TE materials are known to favor the same material properties such as narrow bandgap, heavy elements, and strong SOC, these three Zintl phases are also projected as candidates TE materials.

36 MATERIALS SCIENCE↗

On the redistribution of charge in La 0.7 Sr 0.3 CrO 3 /La 0.7 Sr 0.3 MnO 3 multilayer thin films

The atomic and electronic structures of La 0.7 Sr 0.3 MnO 3 (LSMO)/La 0.7 Sr 0.3 CrO 3 (LSCO) multilayer thin films are investigated using aberration corrected scanning transmission electron microscopy (STEM) imaging and spectroscopy. Atomic resolution high angle annular dark-field reveals that LSMO layers have an expanded out-of-plane lattice parameter compared to compressed LSCO layers, contrasting with x-ray diffraction measurements. The expansion is found to result from preferential oxygen vacancy formation in LSMO during STEM sample preparation as determined by electron energy-loss spectroscopy. The La/Sr atom column intensity is also found to oscillate by about 4% between the LSMO and LSCO layers, indicative of La/Sr concentration variation. Using energy-dispersive x-ray spectroscopy in combination with image simulations, we confirm the La/Sr inhomogeneity and elucidate the origin of charge redistribution within the multilayer. These results illuminate the sensitivity of the technique to subtle structural, chemical, and electronic features that can arise to compensate charge imbalances in complex oxide heterostructures.

36 MATERIALS SCIENCE↗