Impact of Lu-Substitution in Yb 14– x Lu x ZnSb 11 : Thermoelectric Properties and Oxidation Studies
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Andrew P. Justl↗
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The effects of RF plasma ashing on zinc orthotitanate/potassium silicate thermal control coatings
Samples of YB-71, a white thermal control coating composed of zinc orthotitanate pigment in a potassium silicate binder, were exposed in air plasma and in oxygen plasma to determine optical property and surface chemistry changes. Results show that YB-71 undergoes a significant reflectance decrease upon exposure to the simulated LEO atomic oxygen environment provided by an air plasma asher. YB-71 samples exposed to the same effective fluence in oxygen plasma, or in a UV screening Faraday cage in air or oxygen, do not undergo as severe reflectance decreases as the samples exposed in the air plasma asher environment. The UV and VUV radiation present in the plasma ashers affects the YB-71 degradation. It is noted that, when using plasma ashers to determine LEO degradation, it is necessary to take into account the sensitivity of the material to the synergistic effects of atomic oxygen and accelerated UV radiation.
Dever, Joyce A.↗
Effects of Doping on Thermal Conductivity of Pyrochlore Oxides for Advanced Thermal Barrier Coatings
Pyrochlore oxides of general composition, A2B2O7, where A is a 3(+) cation (La to Lu) and B is a 4(+) cation (Zr, Hf, Ti, etc.) have high melting point, relatively high coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high-temperature thermal barrier coatings. The effect of doping at the A site on the thermal conductivity of a pyrochlore oxide La2Zr2O7, has been investigated. Oxide powders of various compositions La2Zr2O7, La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 were synthesized by the citric acid sol-gel method. These powders were hot pressed into discs and used for thermal conductivity measurements using a steady-state laser heat flux test technique. The rare earth oxide doped pyrochlores La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 had lower thermal conductivity than the un-doped La2Zr2O7. The Gd2O3 and Yb2O3 co-doped composition showed the lowest thermal conductivity.
Bansal, Narottam P.↗
Growth and characterization of materials for tunable lasers in the near infrared spectral region
During this reporting period, work proceeded in two directions. The first was the development of crystal growth procedures for rare earth doped LiYF4 crystals. The procedures for growth and pre-growth treatment of starting materials for undoped LiYF4 crystals were established and good optical quality materials were grown. A significant amount of time was spent trying to establish the optimum growth parameters for Yb(3+)-doped crystals. Unfortunately, it has proven difficult to obtain large size boules of high optical quality crystals of LiYF4 with doping concentrations of Yb(3+) of several percent. Because of these problems, this research is to be changed to attempt doping with other trivalent rare earth ions such as Ho, Er, and Tm. The second research area was investigating the potential of LiNbO3:Mg,Cr and LiNbO3:Mg,Cr,Yb as possible laser materials. The results are summarized.
Powell, Richard C.↗
Fiber Amplifier Report for NEPP 2008
Ongoing qualification activities of LiNbO3 modulators. Passive (unpumped) radiation testing of Er-, Yb-, and Er/Yb-doped fibers: a) Yb-doped fibers exhibit higher radiation resistance than Er-doped fibers; b) Er/Yb co-doped fibers exhibit largest radiation resistance. Active (pumped) radiation testing of Yb-doped fibers conducted at NASA GSFC: a) Typical decay behavior observed; b) No comparison could be made to other fibers due to problems with test setup. Development of new high power fiber terminations.
Thomes, Joe↗
Exploring the Effect of EBC Composition on CMAS Wetting Behavior
Rare-earth disilicate (REDS) materials are existing materials used in environmental barrier coating (EBC) for the protection of structural materials in the hot-section of turbine engines. REDS interactions with molten calcium-magnesium-aluminosilicate (CMAS) debris are of interest to understand molten CMAS attack and improve CMAS mitigation strategies. This work assesses the effect of REDS composition on CMAS wetting by investigating wetting angle, spreading, and reactivity. Freestanding atmospheric plasma spray (APS) REDS coatings (for RE = Y, La, Nd, Gd, Yb, Lu) were exposed to 10 mg of CMAS (Ca33-Mg9-Al13-Si45 in single cation mol%) in stagnant lab air at 1250C. APS YbDS was compared to a dense spark plasma sintered (SPS) phase-pure Yb2Si2O7 and a nominal 20 vol% phase-mixture of Yb 2 SiO 5 in Yb 2 Si 2 O 7 (20YbMS/YbDS). CMAS mass was held constant but specimen surface areas varied, yielding a range of loading between ~6 and 10 mg/cm2. CMAS was loaded as a cylindrical rod atop the specimen surface, polished to 4000 grit, and heated to temperature in a Linseis L74/HS/1700 heating microscope. The heating microscope measured the evolution of molten CMAS diameter, height, and contact angle. Molten CMAS diameter at 1150C and contact angle measurements after two hours of exposure at 1250C yielded a positive trend with rare-earth cation size. There was no statistically significant difference in CMAS wetting behavior between SPS YbDS and 20YbMS/YbDS. Post-exposure specimens were examined in plan view and cross-section with XRD, SEM, and EDS. CMAS spreading was cross-examined using plan view SEM, while reactivity utilized plan view XRD and cross-sectional SEM/EDS.
Clark Luckhardt↗
Thermochemical Stability of Ca2Yb8(SiO4)6O2 Apatite in Presence of Molten Calcium-Magnesium-AluminoSilicate (CMAS)
Thermochemical stability of ytterbium silicon oxyapatite Ca 2 Yb 8 (SiO 4 ) 6 O 2 (CYbS) in the presence of molten calcium-magnesium aluminosilicate (CMAS) has been investigated at elevated temperatures. CYbS apatite powder was synthesized from the constituent oxides via solid state reaction method. Hot pressed apatite substrates were exposed to molten CMAS at 1200, 1300, and 1400 °C for 1, 10, and 50 h. Development of phases in the interaction region of the heat-treated specimens was monitored using scanning electron microscopy, transmission electron microscopy, high angle annular dark field imaging, selected area electron diffraction and energy dispersive X-ray spectroscopy. Monoclinic cyclosilicate Ca 3 Yb 2 (Si 3 O 9 ) 2 formed from interaction of CYbS apatite with CaO in the CMAS melt at the apatite-CMAS reaction front and continued to nucleate and grow within the residual CMAS in diffusion couples annealed for 1-50 h at 1200 °C and those heat treated at 1300 °C for 1 h. Residual CMAS was Ca-depleted when cyclosilicate was present. Dendritic wollastonite CaSiO 3 was observed within the residual CMAS in couples annealed at 1200 and 1300 °C. Ingress of molten CMAS, because of its exponential decrease in viscosity, occurred through open pores and along the grain boundaries of the apatite substrates without any detectable chemical reaction at 1300 and 1400 °C. Results of this study indicate that Ca 2 Yb 8 (SiO 4 ) 6 O 2 apatite has the potential to mitigate the CMAS corrosion up to about 1200 °C but not at higher temperatures.
X-ray diffraction↗
Thermochemical Stability of Ca2Yb8(SiO4)6O2 Apatite in Presence of Molten Calcium-Magnesium-Aluminosilicate (CMAS)
Thermochemical stability of ytterbium silicon oxyapatite Ca 2 Yb 8 (SiO 4 ) 6 O 2 (CYbS) in the presence of molten calcium-magnesium aluminosilicate (CMAS) has been investigated at elevated temperatures for consideration as a thermal and environmental barrier coating (T/EBC) material. CYbS apatite powder was synthesized from the constituent oxides via a solid-state reaction method. Hot-pressed apatite substrates were exposed to molten CMAS at 1200, 1300, and 1400 °C for 1, 10, and 50 h. Development of phases in the interaction region of the heat-treated specimens was monitored using scanning electron microscopy, transmission electron microscopy, high-angle annular dark-field imaging, selected area electron diffraction, and energy dispersive x-ray spectroscopy. Monoclinic cyclosilicate Ca 3 Yb 2 (Si 3 O 9 ) 2 formed from interaction of CYbS apatite with CaO in the CMAS melt at the apatite-CMAS reaction front and continued to nucleate and grow within the residual CMAS in diffusion couples annealed for 1 to 50 h at 1200 °C as well as in those heat treated at 1300 °C for 1 h. Residual CMAS was depleted of Ca when cyclosilicate was present. Dendritic wollastonite (CaSiO3) was observed within the residual CMAS in couples annealed at 1200 and 1300 °C. Ingress of molten CMAS, because of its exponential decrease in viscosity, occurred through open pores and along the grain boundaries of the apatite substrates without any detectable chemical reaction at 1300 and 1400 °C. Results of this study indicate that Ca 2 Yb 8 (SiO 4 ) 6 O 2 apatite has the potential to mitigate the CMAS corrosion up to about 1200 °C but not at higher temperatures.
Narottam P Bansal↗
Investigation of the growth of garnet films by liquid phase epitaxy
Liquid phase expitaxy was investigated to determine its applicability to fabricating magnetic rare earth garnet films for spacecraft data recording systems. Two mixed garnet systems were investigated in detail: (1) Gd-Y and (2) Eu-Yb-Y. All films were deposited on Gd3Ga5012 substrates. The uniaxial anisotropy of the Gd-Y garnets is primarily stress-induced. These garnets are characterized by high-domain wall mobility, low coercivity and modest anisotropy. Characteristic length was found to be relatively sensitive to temperature. The Eu-Yb-Y garnets exhibit acceptable mobilities, good temperature stability and reasonable quality factors. The uniaxial anisotropy of these garnets is primarily growth-induced. The system is well suited for compositional "tailoring" to optimize specific desirable properties. Liquid phase epitaxy can be used to deposit Gd3Ga5012 spacing layers on magnetic garnet films and this arrangement possesses certain advantages over more conventional magnetic filmspacing layer combinations. However, it cannot be used if the magnetic film is to be ion implanted.
Moody, J. W.↗
Genesis of the Smartville arc-ophiolite, Sierra Nevada foothills, California
Rare earth element analyses of metavolcanic rocks from the Smartville, Calif. ophiolite divide the uniform suite of pillowed and massive lavas into the lower part consisting of massive, brecciated tholeiites, an intrusive dike-sill complex, and part of a plutonic suite. The tholeiites are light REE depleted with a (Ce)N range of 6.5 to 26.0 and (Yb)N of 6.0 to 30.0; it is suggested that the tholeiites were produced by partial melting of a LREE depleted source similar to MORB. The upper part of the volcanic pile is comprised of basaltic-andesitic flows and interbedded coarse to fine volcanic sediments; these 'calc-alkaline' rocks are light REE enriched with the (Ce)N range of 17.0-28.0 and (Yb)N of 8.0 to 12.0. Finally, petrographic investigations of volcanic sediments and sulfide ore deposits in the lava show that the ophiolite formed near a group of active submarine and subareal volcanoes.
Menzies, M.↗
The chemistry of rare earth elements in the solar nebula
The high concentration of rare earth elements (REE) in primitive CaS suggests that the REE along with the other normally lithophile elements form stable sulfides under the unusual conditions which existed during the formation of enstatite chrondites. In order to acquire a more quantitative framework in which to interpret these data, the behavior of the REE in systems with solar, or slightly fractionated solar, composition is being studied. These new data introduce modest changes in the behavior of some of the REE when compared to previous studies. For example, the largest differences are in the stabilities of the gaseous monoxides of Ce, Eu, Tb, Ho, and Tm, all of which now appear to be less stable than previously thought, and YbO(g) which is somewhat more stable. Much more significant are the changes in REE distribution in the gas phase in fractionated systems, especially those made more reducing by changing the C/O ratio from the solar value of 0.6 to about 1.0. In almost all cases, the exceptions being Eu, Tm and Yb whose elemental gaseous species dominate, the monosulfides become more abundant. Moreover, the solid oxides of Eu, Tm and Yb become less stable under more reducing conditions which, in effect, should reduce the condensation temperature of all REE in more reduced systems.
Larimer, J. W.↗
Crystal/liquid partitioning of REE in basaltic systems Extreme fractionation of REE in olivine
The calculation of partial coefficients for Nd, Sm, Gd, and Yb between olivine and synthetic basaltic melts using the percent level doping technique and microprobe analytical techniques is examined. The experimental and analytical procedures are described. The relationship between rare earth elements (REEs) concentrations and crystal margins caused by Rees X-rays from surrounding glass is discussed. Average olivine/liquid distribution coefficients for Nd, Sm, Gd, and Yb for mare and highlands basaltic melts are presented. The data reveal that the distribution coefficients for light REEs are lower than those obtained in previous studies, and the slope of the olivine/liquid distribution coefficient pattern is steeper; potential sources of error in the previous and present studies which could explain the differences in distribution coefficients and slope are investigated.
Mckay, G. A.↗
Mid to late proterozoic magmatism within Northeastern North America and its iplications for the growth of the continental crust
Recent studies of the mangerite-charnockite-alaskite suite exposed in the Adirondack Highlands strongly suggest that these rocks were emplaced under anorogenic, or mildly extensional, conditions. The characteristic signatures of the rocks are high (FeO/FeO+MgO) and (FeO/Fe2O3); mildly alkaline to subalkaline and metaluminous trends; high Ga/Al2O3; and within plate concentrations of Nb vs Y, Ta vs Yb, Rb vs (Y+Nb), and Rb vs (Yb+Ta). Evolved members of the series are low in CaO and MgO and high in alkalies and halogens. All of these properties are consistent with anorogenic magmatism comprising acidic crustal melts and mantle derived mafic additions to the crust. Major and minor element trends, as well as field evidence, strongly suggest that the anorogenic acidic suite is coeval, but not comagmatic, with closely associated anorthositic massifs. Present outcrop configurations are consistent with the evolution of the acidic and anorthositic rocks in zoned, bimodal magma chambers cored by the mafic constituents and overlain by explosive, caldera-type volcanism. Age determinations indicate that the emplacement of the anorthosite-charnockite suite extended over approximately 500 Ma in the Grenville and adjacent Nain, Provinces.
Mclelland, J. M.↗
The effects of simulated low Earth orbit environments on spacecraft thermal control coatings
Candidate Space Station Freedom radiator coatings including Z-93, YB-71, anodized aluminum and SiO(x) coated silvered Teflon have been characterized for optical properties degradation upon exposure to environments containing atomic oxygen, vacuum ultraviolet (VUV) radiation, and/or silicone contamination. YB-71 coating showed a blue-gray discoloration, which has not been observed in space, upon exposure in atomic oxygen facilities which also provide exaggerated VUV radiation. This is evidence that damage mechanisms occur in these ground laboratory facilities which are different from those which occur in space. Radiator coatings exposed to an electron cyclotron resonance (ECR) atomic oxygen source in the presence of silicone-containing samples showed severe darkening from the intense VUV radiation provided by the ECR and from silicone contamination. Samples exposed to atomic oxygen from the ECR source and to VUV lamps, simultaneously, with in situ reflectance measurement, showed that significantly greater degradation occurred when samples received line-of-site ECR beam exposure than when samples were exposed to atomic oxygen scattered off of quartz surfaces without line-of-site view of the ECR beam. For white paints, exposure to air following atomic oxygen/VUV exposure reversed the darkening due to VUV damage. This illustrates the importance of in situ reflectance measurement.
Dever, Joyce A.↗
Thermal control paints on LDEF: Results of M0003 sub-experiment 18
Several thermal control paints were flown on the Long Duration Exposure Facility (LDEF), including the white paints Chemglaze A276, S13GLO, and YB-71, and the black paint D-111. The effects of low earth orbit, which includes those induced by UV radiation and atomic oxygen, varied significantly with each paint and its location on LDEF. For example, samples of Chemglaze A276 located on the trailing edge of LDEF darkened significantly due to UV-induced degradation of the paint's binder, while leading edge samples remained white but exhibited severe atomic oxygen erosion of the binder. Although the response of S13GLO to low earth orbit is much more complicated, it also exhibited greater darkening on trailing edge samples as compared to leading edge samples. In contrast, YB-71 and D-111 remained relatively stable and showed minimal degradation. The performance of these paints as determined by changes in their optical and physical properties, including solar absorptance as well as surface chemical changes and changes in surface morphology is examined. It will also provide a correlation of these optical and physical property changes to the physical phenomena that occurred in these materials during the LDEF mission.
Jaggers, C. H.↗
Hyperfine structure and isotope shifts of transitions in neutral and singly ionized ytterbium
The present experimental investigation of the hyperfine structure and isotopic shifts of transitions in neutral and singly-ionized Yb, which constitute a system of some interest to microwave-frequency standards, used counterpropagating pump and probe laser beams directed through a hollow-cathode discharge lamp. The results obtained are in agreement with previous measurements except in the case of the Yb-173(+) 6 2P0 sub 3/2 state, which is more accurately determined.
Berends, R. W.↗
Anomalous REE patterns in unequilibrated enstatite chondrites: Evidence and implications
We present here a study of Rare Earth Element (REE) microdistributions in unequilibrated enstatite chondrites (EOC's). Although the whole rock REE contents are similar in both unequilibrated and equilibrated chondrites, the host minerals of these refractory elements are different. In the least equilibrated ordinary chondrites (UOC's), the REE reside mainly in glass whereas, in their more equilibrated counterparts, the bulk of the REE is in calcium phosphate, a metamorphic mineral that formed by oxidation of phosphorous originally contained in metal. In the smaller group of enstatite (E) chondrites, calcium phosphate is absent and the phase that contains the highest REE concentrations is a minor mineral, CaS (oldhamite), which contains approximately 50 percent of the total Ca present. In E chondrites, elements typically considered to be lithophiles (such as Ca and Mn) occur in sulfides rather than silicates. This indicates formation under extremely reducing conditions, thus in a region of the solar nebula distinct from those that supplied the more abundant ordinary and carbonaceous chondrites. Previously, we observed a variety of REE patterns in the oldhamite of UEC's; they range from almost flat to some with pronounced positive Eu and Yb anomalies. Here, we searched for complementary REE patterns in other minerals from E chondrites and found them in the major mineral, enstatite. Whenever Eu and Yb anomalies are present in this mineral, they are always negative.
Crozaz, Ghislaine↗
On origin of the olivine inclusions from the Kainsaz CO carbonaceous chondrite
Olivine inclusions and chondrules of Kainsaz were formed in a unique process of dust matter melting. The elemental abundances of four fractions of olivine (01) inclusions from Kainsaz were analyzed by INAA. The inclusions of fraction A (160 less than d less than 260 microns) have Fe-Ni grains, the inclusions of fractions B (100 less than d less than 160 microns), C (160 less than d less than 260 microns), and D (260 less than d less than 360 microns) do not. The average elemental enrichment factors relative to CI chondrite for each fraction and chondrules of Kainsaz is shown. The enrichment factors of siderophile Co, Ni, Ir, Au, and non-refractory Na in all fractions are less than 1. The factors of refractory Ca, Sc, La, Sm, and Yb are comparative with the corresponding values of O1 aggregates of Allende CV (average 4.76). For chondrules of Kainsaz these values are lower. Fraction A is enriched in Co, Ir, Au, and relative Ni and CI chondrites: Ir greater than Au greater than Co. The values of (Me/Ni)inc/(Me/Ni)CI are equal to 3.25 for Ir, 2.1 for Au, and 1.2 for Co. The superabundances in Ir and Au relative to Ni witness to formation of Fe-Ni grains of O1 inclusions by agglomeration of grains enriched in refractory metal with grains enriched in non-refractory metal (Au). The enrichments of fraction A in Ca, Sc, La, Sm, and Yb witness about presence of high-temperature phases in O1 inclusions.
Lavrukhina, A. K.↗