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Preparation and Dielectric Measurements of the Rare Earth Green Phases R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb)

It has been demonstrated that R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb) does not undergo significant densification unless the sintering temperatures are near the incongruent melting point or the sintering times are long. Good quality powders of Y2BaCuO(5-x) have been synthesized by using oxide raw materials or precursors such as acetates and nitrates. The acetates- and the nitrates-derived yttrium green phase resulted in finer particle sizes, acceptable dielectric properties and lower melting temperatures than those processed via oxide raw materials. The hot pressing technique has been employed to produce a dense R2BaCuO(5-x) (R=Y,Gd) substrate with satisfactory dielectric properties. Reactivity to reducing conditions, i.e. graphite die, limited the optimization of the properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO,.,,. Oxygen treatment at 950 OC has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO(5-x). Oxygen treatment at 950 C has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. The dielectric constants of the rare earth green phases R2BaCuO(5-x) were found to be low. Relaxation peaks were detected at low temperatures (T less than 150 K) and at high temperatures (150 less than T greater than 420 K). The dielectric losses and conductivities at 77 K were measured to be in the range of 10(exp -4) and 10(exp -12) (Omega-cm)(exp -1), respectively. Many parameters were found to exhibit dependencies on the rare earth cation sizes.

Gonzalez-Titman, Carlos↗

Disruption of the Globular Cluster Pal 5

Orbit calculations suggest that the sparse globular cluster, Pal 5, will pass within 7 kpc of the Galactic center the next time it crosses the plane, where it might be destroyed by tidal stresses. We study this problem, treating Pal 5 as a self-consistent dynamical system orbiting through an external potential that represents the Galaxy. The first part of the problem is to find suitable analytic approximations to the Galactic potential. They must be valid in all regions the cluster is likely to explore. Observed velocity and positional data for Pal 5 are used as initial conditions to determine the orbit. Methods we used for a different problem some 12 years ago have been adapted to this problem. Three experiments have been run, with M/L= 1, 3, and 10, for the cluster model. The cluster blew up shortly after passing through the Galactic plane (about 130 Myrs after the beginning of the run) with M/L=1. At M/L = 3 and 10 the cluster survived, although it got quite a kick in the fundamental mode on passing through the plane. But the fundamental mode oscillation died out in a couple of oscillation cycles at M/L=10. Pal 5 will probably be destroyed on its next crossing of the Galactic plane if M/L=1, but it can survive (albeit with fairly heavy damage) if NI/L=3. We haven't tried to trap the mass limits more closely than that. Pal 5 comes through pretty well unscathed at M/L=10. An interesting follow-up experiment would be to back the cluster up along its orbit to look at its previous passage through the Galactic plane, to see what kind of object it might have been at earlier times.

Miller, R. H.↗

Effect of dinucleoside pyrophosphates on the oligomerization of activated mononucleotides on Na(+)-montmorillonite: reaction of 5'-phosphoro-4-(dimethylamino)pyridinium [4-(CH3)2NpypA] with A5'ppA

The oligomerization of adenosine 5'-phosphoro-4-(dimethylamino)pyridinium (4-(CH3)2-NpypA) and diadenosine 5',5'-pyrophosphate (A5'ppA) (9:1) on Na(+)-montmorillonite was studied. The oligomers were isolated and analyzed by selective enzymatic hydrolyses and the oligomeric composition and the percent of 3',5'-phosphodiester linkages present in each fraction was determined. The longest oligomers formed (11-mers) are slightly shorter than those produced in the absence of A5'ppA (12-mers). Smaller amounts of A5'ppA are incorporated into the oligomers than in the ImpA/A5'ppA reaction. The regioselectivity of 3',5'-phosphodiester bond formation is comparable to that of the oligomerization of 4-(CH3)2NpypA alone. An explanation of these data is proposed and the possible effect of dinucleoside pyrophosphate on prebiotic RNA formation is discussed.

Non-NASA Center↗

Titan's 5 micrometers spectral window: carbon monoxide and the albedo of the surface

We have measured the spectrum of Titan near 5 micrometers and have found it to be dominated by absorption from the carbon monoxide 1-0 vibration-rotation band. The position of the band edge allows us to constrain the abundance of CO in the atmosphere and/or the location of the reflecting layer in the atmosphere. In the most likely case, 5 micrometers radiation is reflected from the surface and the mole fraction of CO in the atmosphere is qCO=10(+10/-5) ppm, significantly lower than previous estimates for tropospheric CO. The albedo of the reflecting layer is approximately 0.07(+0.02/-0.01) in the 5 micrometers continuum outside the CO band. The 5 micrometers albedo is consistent with a surface of mixed ice and silicates similar to the icy Galilean satellites. Organic solids formed in simulated Titan conditions can also produce similar albedos at 5 micrometers.

Saturn↗

Jake Garn Mission Simulator and Training Facility, Building 5, Historical Documentation

In response to President George W. Bush's announcement in January 2004 that the Space Shuttle Program (SSP) would end in 2010, the National Aeronautics and Space Administration (NASA) completed a nation-wide historical survey and evaluation of NASA-owned facilities and properties (real property assets) at all its Centers and component facilities. The buildings and structures which supported the SSP were inventoried and assessed as per the criteria of eligibility for listing in the National Register of Historic Places (NRHP) in the context of this program. This study was performed in compliance with Section 110 of the National Historic Preservation Act (NHPA) of 1966 (Public Law 89-665), as amended; the National Environmental Policy Act (NEPA) of 1969 (Public Law 91-190); Executive Order (EO) 11593: Protection and Enhancement of the Cultural Environment; EO 13287, Preserve America, and other relevant legislation. As part of this nation-wide study, in September 2006, historical survey and evaluation of NASA-owned and managed facilities at was conducted by NASA's Lyndon B. Johnson Space Center (JSC) in Houston, Texas. The results of this study are presented in a report entitled, "Survey and Evaluation of NASA-owned Historic Facilities and Properties in the Context of the U.S. Space Shuttle Program, Lyndon B. Johnson Space Center, Houston, Texas," prepared in November 2007 by NASA JSC's contractor, Archaeological Consultants, Inc. As a result of this survey, the Jake Gam Mission Simulator and Training Facility (Building 5) was determined eligible for listing in the NRHP, with concurrence by the Texas State Historic Preservation Officer (SHPO). The survey concluded that Building 5 is eligible for the NRHP under Criteria A and C in the context of the U.S. Space Shuttle program (1969-2010). Because it has achieved significance within the past 50 years, Criteria Consideration G applies. At the time of this documentation, Building 5 was still used to support the SSP as an astronaut training facility. This documentation package precedes any undertaking as defined by Section 106 of the NHPA, as amended, and implemented in 36 CFR Part 800, as NASA JSC has decided to proactively pursue efforts to mitigate the potential adverse affects of any future modifications to the facility. It includes a historical summary of the Space Shuttle program; the history of JSC in relation to the SSP; a narrative of the history of Building 5 and how it supported the SSP; and a physical description of the structure. In addition, photographs documenting the construction and historical use of Building 5 in support of the SSP, as well as photographs of the facility documenting the existing conditions, special technological features, and engineering details, are included. A contact sheet printed on archival paper, and an electronic copy of the work product on CD, are also provided.

Slovinac, Trish↗

Environmental Barrier Coating Surface Temperature Mapping Using a Compatible Er-Doped Sc 2 SiO 5 Temperature-Sensing Layer

Accurate surface temperature-mapping capabilities in the 1300 to 1500 °C range are needed for SiC/SiC ceramic matrix composites protected by environmental barrier coatings (EBCs) under testing in turbine engine environment facilities. The strong background thermal radiation at these higher temperatures is a challenging issue. Er-doped Y 2 SiO 5 was previously shown to be capable of achieving luminescence lifetime-based temperature mapping up to 1560 °C as a standalone material. However, compatibility issues between an Er-doped Y 2 SiO 5 surface temperature sensing layer and an underlying Sc 2 Si 2 O 7 -based EBC topcoat limited temperature mapping of the EBC surface to a maximum of 1380 °C. Therefore, an Er-doped Sc 2 SiO 5 temperature sensing layer has been subsequently developed with better compatibility with the Sc2Si2O7-based EBC topcoat. Localized spot temperature measurements as well as luminescence lifetime imaging-based temperature mapping were demonstrated up to 1535 °C from a 15 µm thick Er-doped Sc 2 SiO 5 layer at the surface of a Sc2Si2O7-based EBC topcoat, a significant improvement over the Er-doped Y2SiO5 layer 1380 °C temperature sensing limit. No degradation of the Er-doped Sc 2 SiO 5 temperature sensing surface layer was observed.

temperature measurement↗

Materials Data on Rb4Ge9(H3N)5 by Materials Project

Rb4(NH3)5(Ge)9 crystallizes in the monoclinic P2_1/c space group. The structure is two-dimensional and consists of thirty-six germanium molecules and two Rb4(NH3)5 sheets oriented in the (0, 0, 1) direction. In each Rb4(NH3)5 sheet, there are four inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 5-coordinate geometry to four N3- and three H+0.47- atoms. There are a spread of Rb–N bond distances ranging from 3.09–3.41 Å. There are a spread of Rb–H bond distances ranging from 3.07–3.28 Å. In the second Rb1+ site, Rb1+ is bonded in a bent 150 degrees geometry to one N3- and one H+0.47- atom. The Rb–N bond length is 2.98 Å. The Rb–H bond length is 3.01 Å. In the third Rb1+ site, Rb1+ is bonded in a 1-coordinate geometry to three N3- and four H+0.47- atoms. There are one shorter (3.18 Å) and two longer (3.25 Å) Rb–N bond lengths. There are a spread of Rb–H bond distances ranging from 3.04–3.24 Å. In the fourth Rb1+ site, Rb1+ is bonded in a 3-coordinate geometry to one N3- and two H+0.47- atoms. The Rb–N bond length is 3.13 Å. There are one shorter (2.90 Å) and one longer (3.05 Å) Rb–H bond lengths. There are five inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal non-coplanar geometry to two Rb1+ and three H+0.47- atoms. All N–H bond lengths are 1.03 Å. In the second N3- site, N3- is bonded in a trigonal non-coplanar geometry to one Rb1+ and three H+0.47- atoms. All N–H bond lengths are 1.03 Å. In the third N3- site, N3- is bonded in a trigonal non-coplanar geometry to one Rb1+ and three H+0.47- atoms. There is one shorter (1.02 Å) and two longer (1.03 Å) N–H bond length. In the fourth N3- site, N3- is bonded in a trigonal non-coplanar geometry to two Rb1+ and three H+0.47- atoms. All N–H bond lengths are 1.03 Å. In the fifth N3- site, N3- is bonded in a trigonal non-coplanar geometry to three Rb1+ and three H+0.47- atoms. There is one shorter (1.02 Å) and two longer (1.03 Å) N–H bond length. There are fifteen inequivalent H+0.47- sites. In the first H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the second H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the third H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the fourth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the fifth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the sixth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the seventh H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the eighth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the ninth H+0.47- site, H+0.47- is bonded in a single-bond geometry to two Rb1+ and one N3- atom. In the tenth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the eleventh H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the twelfth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the thirteenth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one N3- atom. In the fourteenth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom. In the fifteenth H+0.47- site, H+0.47- is bonded in a single-bond geometry to one Rb1+ and one N3- atom.

36 MATERIALS SCIENCE↗

Materials Data on Zr2Ti3(PbO3)5 by Materials Project

Zr2Ti3(PbO3)5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are two inequivalent Zr4+ sites. In the first Zr4+ site, Zr4+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Zr–O bond distances ranging from 1.97–2.52 Å. In the second Zr4+ site, Zr4+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Zr–O bond distances ranging from 1.97–2.52 Å. There are three inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Ti–O bond distances ranging from 1.75–2.08 Å. In the second Ti4+ site, Ti4+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Ti–O bond distances ranging from 1.75–2.09 Å. In the third Ti4+ site, Ti4+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Ti–O bond distances ranging from 1.75–2.09 Å. There are five inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.52–2.98 Å. In the second Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.51–2.94 Å. In the third Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.47–2.91 Å. In the fourth Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.46–2.92 Å. In the fifth Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pb–O bond distances ranging from 2.48–2.98 Å. There are fifteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zr4+ and four Pb2+ atoms. In the second O2- site, O2- is bonded in a single-bond geometry to one Ti4+ and four Pb2+ atoms. In the third O2- site, O2- is bonded in a single-bond geometry to one Ti4+ and four Pb2+ atoms. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Ti4+ and four Pb2+ atoms. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Zr4+ and four Pb2+ atoms. In the sixth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two equivalent Zr4+ and two Pb2+ atoms. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to two equivalent Ti4+ and two Pb2+ atoms. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to two equivalent Ti4+ and two Pb2+ atoms. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to two equivalent Ti4+ and two Pb2+ atoms. In the tenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two equivalent Zr4+ and two Pb2+ atoms. In the eleventh O2- site, O2- is bonded in a 4-coordinate geometry to two Zr4+ and two equivalent Pb2+ atoms. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to one Zr4+, one Ti4+, and two equivalent Pb2+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ti4+ and two equivalent Pb2+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ti4+ and two equivalent Pb2+ atoms. In the fifteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Zr4+, one Ti4+, and two equivalent Pb2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on BaNd4(CoO3)5 by Materials Project

BaNd4(CoO3)5 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Ba2+ is bonded to twelve O2- atoms to form distorted BaO12 cuboctahedra that share corners with two equivalent BaO12 cuboctahedra and faces with eight CoO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.60–3.06 Å. There are two inequivalent Nd3+ sites. In the first Nd3+ site, Nd3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Nd–O bond distances ranging from 2.35–2.78 Å. In the second Nd3+ site, Nd3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Nd–O bond distances ranging from 2.36–2.77 Å. There are three inequivalent Co+3.20+ sites. In the first Co+3.20+ site, Co+3.20+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO6 octahedra and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 15–26°. There are a spread of Co–O bond distances ranging from 1.89–2.05 Å. In the second Co+3.20+ site, Co+3.20+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO6 octahedra and faces with two equivalent BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 10–26°. There are a spread of Co–O bond distances ranging from 1.93–2.02 Å. In the third Co+3.20+ site, Co+3.20+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six CoO6 octahedra and faces with two equivalent BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 18–26°. There are a spread of Co–O bond distances ranging from 1.94–2.04 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a 5-coordinate geometry to one Ba2+, two equivalent Nd3+, and two Co+3.20+ atoms. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Ba2+, two equivalent Nd3+, and two Co+3.20+ atoms. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, two Nd3+, and two Co+3.20+ atoms. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to one Ba2+, two Nd3+, and two Co+3.20+ atoms. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to two Nd3+ and two equivalent Co+3.20+ atoms. In the sixth O2- site, O2- is bonded in a 5-coordinate geometry to one Ba2+, two Nd3+, and two Co+3.20+ atoms. In the seventh O2- site, O2- is bonded in a 5-coordinate geometry to three Nd3+ and two Co+3.20+ atoms. In the eighth O2- site, O2- is bonded in a 6-coordinate geometry to two equivalent Ba2+, two equivalent Nd3+, and two equivalent Co+3.20+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Dy12(ReC3)5 by Materials Project

Dy12(ReC3)5 crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are three inequivalent Dy3+ sites. In the first Dy3+ site, Dy3+ is bonded to five C+3.47- atoms to form distorted DyC5 square pyramids that share corners with three equivalent DyC5 square pyramids, edges with four equivalent DyC8 hexagonal bipyramids, and an edgeedge with one DyC5 square pyramid. There are a spread of Dy–C bond distances ranging from 2.34–2.57 Å. In the second Dy3+ site, Dy3+ is bonded to eight C+3.47- atoms to form distorted DyC8 hexagonal bipyramids that share corners with four equivalent DyC8 hexagonal bipyramids, edges with two equivalent DyC8 hexagonal bipyramids, and edges with eight equivalent DyC5 square pyramids. There are a spread of Dy–C bond distances ranging from 2.58–2.79 Å. In the third Dy3+ site, Dy3+ is bonded in a rectangular see-saw-like geometry to four C+3.47- atoms. There are two shorter (2.52 Å) and two longer (2.55 Å) Dy–C bond lengths. There are two inequivalent Re+3.20+ sites. In the first Re+3.20+ site, Re+3.20+ is bonded in a distorted T-shaped geometry to three C+3.47- atoms. There are one shorter (1.95 Å) and two longer (2.06 Å) Re–C bond lengths. In the second Re+3.20+ site, Re+3.20+ is bonded in a trigonal planar geometry to three equivalent C+3.47- atoms. All Re–C bond lengths are 1.91 Å. There are four inequivalent C+3.47- sites. In the first C+3.47- site, C+3.47- is bonded to five Dy3+ and one Re+3.20+ atom to form a mixture of distorted edge and corner-sharing CDy5Re octahedra. The corner-sharing octahedra tilt angles range from 5–44°. In the second C+3.47- site, C+3.47- is bonded in a 6-coordinate geometry to four Dy3+, one Re+3.20+, and one C+3.47- atom. The C–C bond length is 1.36 Å. In the third C+3.47- site, C+3.47- is bonded in a 5-coordinate geometry to four Dy3+ and one C+3.47- atom. In the fourth C+3.47- site, C+3.47- is bonded to four Dy3+ and two equivalent Re+3.20+ atoms to form CDy4Re2 octahedra that share corners with four equivalent CDy4Re2 octahedra and edges with four equivalent CDy5Re octahedra. The corner-sharing octahedra tilt angles range from 5–26°.

36 MATERIALS SCIENCE↗

Materials Data on Tb12(ReC3)5 by Materials Project

Tb12(ReC3)5 crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are three inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded to five C+3.47- atoms to form distorted TbC5 square pyramids that share a cornercorner with one CTb4ReC octahedra, corners with three equivalent TbC5 square pyramids, edges with four equivalent TbC8 hexagonal bipyramids, and an edgeedge with one TbC5 square pyramid. The corner-sharing octahedral tilt angles are 42°. There are a spread of Tb–C bond distances ranging from 2.36–2.59 Å. In the second Tb3+ site, Tb3+ is bonded to eight C+3.47- atoms to form distorted TbC8 hexagonal bipyramids that share corners with four equivalent TbC8 hexagonal bipyramids, corners with two equivalent CTb4ReC octahedra, edges with two equivalent TbC8 hexagonal bipyramids, and edges with eight equivalent TbC5 square pyramids. The corner-sharing octahedral tilt angles are 98°. There are a spread of Tb–C bond distances ranging from 2.59–2.80 Å. In the third Tb3+ site, Tb3+ is bonded in a rectangular see-saw-like geometry to four C+3.47- atoms. There are two shorter (2.54 Å) and two longer (2.57 Å) Tb–C bond lengths. There are two inequivalent Re+3.20+ sites. In the first Re+3.20+ site, Re+3.20+ is bonded in a distorted T-shaped geometry to three C+3.47- atoms. There are one shorter (1.95 Å) and two longer (2.06 Å) Re–C bond lengths. In the second Re+3.20+ site, Re+3.20+ is bonded in a trigonal planar geometry to three equivalent C+3.47- atoms. All Re–C bond lengths are 1.91 Å. There are four inequivalent C+3.47- sites. In the first C+3.47- site, C+3.47- is bonded to five Tb3+ and one Re+3.20+ atom to form a mixture of corner and edge-sharing CTb5Re octahedra. The corner-sharing octahedra tilt angles range from 5–74°. In the second C+3.47- site, C+3.47- is bonded to four Tb3+, one Re+3.20+, and one C+3.47- atom to form distorted CTb4ReC octahedra that share corners with two equivalent TbC8 hexagonal bipyramids, corners with six CTb5Re octahedra, corners with two equivalent TbC5 square pyramids, and edges with six CTb5Re octahedra. The corner-sharing octahedra tilt angles range from 42–74°. The C–C bond length is 1.35 Å. In the third C+3.47- site, C+3.47- is bonded in a 5-coordinate geometry to four Tb3+ and one C+3.47- atom. In the fourth C+3.47- site, C+3.47- is bonded to four Tb3+ and two equivalent Re+3.20+ atoms to form CTb4Re2 octahedra that share corners with four equivalent CTb4Re2 octahedra and edges with six CTb5Re octahedra. The corner-sharing octahedra tilt angles range from 5–27°.

36 MATERIALS SCIENCE↗

Converter Compressor Building, SWMU 089, Hot Spot Areas 1, 2, and 5 Operations, Maintenance, and Monitoring Report, Kennedy Space Center, Florida

This Operations, Maintenance, and Monitoring Report (OMMR) presents the findings, observations, and results from operation of the air sparging (AS) interim measure (IM) for Hot Spot (HS) Areas 1, 2, and 5 at the Converter Compressor Building (CCB) located at Kennedy Space Center (KSC), Florida. The objective of the IM at CCB HS Areas 1, 2, and 5 is to decrease concentrations of volatile organic compounds (VOCs) in groundwater in the treatment zones via AS to levels that will enable a transition to a monitored natural attenuation (MNA) phase. This OMMR presents system operations and maintenance (O&M) information and performance monitoring results since full-scale O&M began in June 2014 (2 months after initial system startup in April 2014), including quarterly performance monitoring events in July and October 2014 and January and May 2015. Based on the results to date, the AS system is operating as designed and is meeting the performance criteria and IM objective. The performance monitoring network is adequately constructed for assessment of IM performance at CCB HS Areas 1, 2, and 5. At the March 2014 KSC Remediation Team (KSCRT) Meeting, team consensus was reached for the design prepared for expansion of the system to treat the HS 4 area, and at the November 2014 KSCRT Meeting, team consensus was reached that HS 3 was adequately delineated horizontally and vertically and for selection of AS for the remedial approach for HS 3. At the July 2015 KSCRT meeting, team consensus was reached to continue IM operations in all zones until HSs 3 and 4 is operational, once HS 3 and 4 zones are operational discontinue operations in HS 1, 2, and 5 zones where concentrations are less than GCTLs to observe whether rebounding conditions occur. Team consensus was also reached to continue quarterly performance monitoring to determine whether operational zones achieve GCTLs and to continue annual IGWM of CCB-MW0012, CCBMW0013, and CCB-MW0056, located south of the treatment area. The next performance monitoring event is scheduled for July 2015.

Converter Compressor Building↗

Rare-Earth Permanent Magnet SmCo 5 for Chiral Interfacial Spin-Orbitronics

Interfacially asymmetric magnetic multilayers made of heavy metal/ferromagnet have attracted considerable attention in the spintronics community for accommodating spin-orbit torques (SOTs) and meanwhile for hosting chiral spin textures. In these multilayers, the accompanied interfacial Dzyaloshinskii–Moriya interaction (iDMI) permits the formation of Néel-type spin textures. While significant progresses have been made in Co, CoFeB, Co 2 FeAl, CoFeGd based multilayers, it would be intriguing to identify new magnetic multilayers that could enable spin-torque controllability and meanwhile host nanoscale skyrmions. In this report, first, thin films made of permanent magnet SmCo 5 with perpendicular magnetic anisotropy are synthesized, in which the deterministic SOT switching, enabled by the spin Hall effect, in Pt/SmCo 5 /Ta trilayer is demonstrated. Further, the stabilization of room-temperature skyrmions with diameters ≈100 nm in [Pt/SmCo 5 /Ta] 15 , together with a skyrmionium-like spin texture in [Pt/SmCo 5 /Ir] 15 multilayers is shown. Based on the material specific parameters, micromagnetic simulations are also carried out. The results confirm the presence of chiral spin textures in this new material family. Through interfacial engineering, the results thus demonstrate that rare earth permanent magnets could be a new platform for studying interfacial chiral spintronics.

36 MATERIALS SCIENCE↗

Tuning the Kinetics of Zinc-Ion Insertion/Extraction in V 2 O 5 by In Situ Polyaniline Intercalation Enables Improved Aqueous Zinc-Ion Storage Performance

Rechargeable zinc-ion batteries (ZIBs) are emerging as a promising alternative for Li-ion batteries. However, the developed cathodes suffer from sluggish Zn 2+ diffusion kinetics, leading to poor rate capability and inadequate cycle life. Herein, an in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn 2+ (de)intercalation kinetics in V 2 O 5 . In this way, a remarkably enlarged interlayer distance (13.90 Å) can be constructed alternatively between the V-O layers, offering expediting channels for facile Zn 2+ diffusion. Importantly, the electrostatic interactions between the Zn 2+ and the host O 2- , which is another key factor in hindering the Zn 2+ diffusion kinetics, can be effectively blocked by the unique π-conjugated structure of PANI. As a result, the PANI-intercalated V 2 O 5 exhibits a stable and highly reversible electrochemical reaction during repetitive Zn 2+ insertion and extraction, as demonstrated by in situ synchrotron X-ray diffraction and Raman studies. Further first-principles calculations clearly reveal a remarkably lowered binding energy between Zn 2+ and host O 2- , which explains the favorable kinetics in PANI-intercalated V 2 O 5 . Benefitting from the above, the overall electrochemical performance of PANI-intercalated V 2 O 5 electrode is remarkable improved, exhibiting excellent high rate capability of 197.1 mAh g -1 at current density of 20 A g -1 with capacity retention of 97.6% over 2000 cycles.

36 MATERIALS SCIENCE↗

Direct Catalytic Conversion of Ethanol to C 5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Abstract Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C 5+ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd‐promoted ZnO‐ZrO 2 catalyst. The sequence of reaction steps involved in the C 5+ ketone formation from ethanol was determined. The key reaction steps were found to be the in situ generation of the acetone intermediate and the cross‐aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd–Zn alloy in situ was identified to be the critical factor in maintaining high yield to the C 5+ ketones and the stability of the catalyst. A yield of >70 % to C 5+ ketones was achieved over a 0.1 % Pd‐ZnO‐ZrO 2 mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.

Subramaniam, Senthil↗

Giant Magnetostriction in Ferrimagnetic SmFe 5 As 3

Magnetostrictive materials are of interest not only from a fundamental perspective but also for their potential applications, spanning spintronics to energy harvesting. A new magnetostrictive material—SmFe 5 As 3 —reveals a complex interplay between magnetostriction, magnetic properties, and the crystal structure behavior. The ground state of SmFe 5 As 3 is ferrimagnetic, as evidenced by magnetic susceptibility data, band-structure calculations, and XANES measurements. At T m1 = 28 ± 4 K, part of the Fe sublattice reorients, transitioning into a ferromagnetic state. This is followed by an entrance into the paramagnetic state at T m2 = 76 ± 4 K. The effects observed in the magnetic measurements are accompanied by structural phase transitions. All three phases—below T m1 , between T m1 and T m2 , and above T m2 —are described by the same structural motif of the UCr 5 P 3 type (monoclinic space group P2 1 /m), differing only in the degree of deformation of the Fe–As framework. The new material exhibits giant magnetostriction of 2500 x 10 -6 . Dilatometry measurements on a SmFe 5 As 3 single crystal indicate strongly diverse behavior, exhibiting not only negative, but also zero, as well as positive thermo-elastic effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetocaloric Effect in Lightly‐Doped Fe 5 Si 3 Single Crystals

Abstract Development of promising new materials for above room temperature magnetic cooling applications relies on careful balancing of structure and composition to maximize accessible metastable phases that can drive a strong magnetocaloric effect (MCE). However, the working temperatures of these materials may fall outside of desired application windows. In this work, it is shown that it is possible to control metastable phase stability temperatures of Fe 5 Si 3 through selection of appropriate spin and charge doping. Here, the parent material's desired structure appears only within a narrow temperature range from 1098 to 1303 K. Doping with Mn and P is shown to allow stabilization of the parent's high temperature phase and resulting MCE to room temperature. The structural and magnetic properties, and the magnetocaloric effect of single crystal Fe 4.83 Mn 0.16 Si 2.91 P 0.09 (FMSP) are investigated experimentally and theoretically. A first‐order magneto‐elastic transition is observed at 348 K, where magnetic onset is accompanied by a change in lattice volume without an apparent change in crystal symmetry. Although the trace Mn and P doping are found to decrease the T C , the maximum magnetic entropy change Δ S Max ( T ) and the relative cooling power (RCP) of FMSP are enhanced compared to polycrystalline Fe 5 Si 3 . As a result, an intrinsically broader entropy change over a larger temperature span is generated in the lightly doped single crystal of Fe 5 Si 3 . The magnetic moment of the system is also enhanced. Density functional theory (DFT) calculations are performed to gain microscopic insights into the experimental findings. The results suggest that the hexagonal Fe 5 Si 3 is a new giant room temperature MCE material that is on par with La–Fe–Si and Fe‐Mn‐P‐Si systems.

36 MATERIALS SCIENCE↗

Photodetachment Dynamics and Structural Flexibility of Undercoordinated Iridium Halides IrCl n − (n = 3−5): An Experimental and Theoretical Investigation

Three undercoordinated iridium chloride anions, IrCl n − (n = 3–5), and their neutral counterparts were investigated by cryogenic anion photoelectron spectroscopy and theoretical calculations. Photodetachment of IrCl n − leads to the formation of the corresponding neutral complex, i.e., a triplet ground state for n = 3, a quartet for n = 4, and close-lying singlet and triplet for n = 5. The vertical detachment energies are determined to be 3.89, 4.98, and 5.14 eV for n = 3, 4, and 5, respectively, revealing superhalogen anion properties with increasing electron detachment energies as chloride ligands added. The IrCl 3 − spectrum features an extremely broad, lowest electron binding energy band, attributed to resonant autodetachment with prominent non-Franck–Condon profiles. In IrCl 5 − , detachment prompts a d-orbital rearrangement that drives a structural transformation from a twisted square-based pyramidal to a trigonal–bipyramidal geometry in the singlet state. In conclusion, these findings provide insights into the electronic and structural adaptability of iridium halides, advancing our understanding of ligand exchange reactions and dissociative stability in transition metal complexes.

Tang, Peng [East China Normal Univ. (ECNU), Shangh↗