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Theoretical study of the spectroscopy of ZrO

The absorption bands of ZrO have been observed in stars, particularly S stars. Here, theoretical transition probabilities are presented for the dipole-allowed transitions between the six lowest singlet and triplet states of ZrO. The results should be sufficiently reliable to provide opacity data for use in modeling stellar atmospheres. The theoretical radiative lifetime for the e 3Pi state is less than the experimental value as measured by the decay of resonant fluorescence. However, the theoretical electronic transition moments for the gamma system and the B 1Pi - X 1Sigma(+) system are much smaller than those deduced from emission studies. The calculated lifetime for the C 1Sigma(+) state is in excellent agreement with the laser-induced fluorescence studies. The as yet unobserved E 1Phi - A 1Delta band system is found to be relatively strong.

Langhoff, Stephen R.↗

Thermochemistry of Calcium-Magnesium-Aluminum-Silicate (CMAS) and Components of Advanced Thermal and Environmental Barrier Coating Systems

There is increasing interest in the degradation mechanism studies of thermal and environmental barrier coatings (TEBCs) of gas turbines by molten CaO-MgO-Al(exp. 2)O(exp. 3)-SiO(exp. 2) CMAS). CMAS minerals are usually referred as silicon-containing sand dust and volcano ash materials that are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits often react at high temperatures (greater than 1200 degrees C) with the engine turbine coating systems and components. The high temperature reactions causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some results of the reactions between the CMAS and Rare-Earth (RE = Y, Yb, Dy, Gd, Nd and Sm) - oxide stabilized ZrO(exp. 2) or HfO(exp. 2) systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples (outside diameter = 4.7 mm, wall thickness = 0.76 mm and = 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 degrees C for 5h. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, and cross-section electron microscopy analysis and energy dispersive X-ray spectroscopy. It was found that CMAS penetrated the samples at the grain boundaries and dissolved the TEBC materials to form silicate phases containing the rare-earth elements. Furthermore, it was found that apatite crystalline phases were formed in the samples with total rare-earth content higher than 12 mol% in the reaction zone for the ZrO(exp. 2) system. In general, samples with the nominal compositions (30YSZ), HfO(exp. 2)-7Dy(exp. 2)O(exp. 2) and ZrO(exp. 2)-9.5Y(exp. 2)O(exp. 3)-2.25Gd(exp. 2)O(exp. 3)-2.25Yb(exp. 2)O(exp. 3) exhibited lower reactivity or more resistance to CMAS than the other coating compositions of this work.

degradation↗

A search for FeH in M and S giants

The strongest lines of FeH in the visible spectrum fall in the domain of TiO and ZrO bands. Analysis exists for TiO, but nothing is yet available for the weak but important ZrO lines. Using plate measurements and microphotometer tracings, high dispersion spectra of the following cool stars have been searched for FeH lines: Beta Peg, Mu UMa, Alpha Her, Omicron Cet, Chi Cyg, HR 105, HR 8714, R And, R Cyg, R Cam, T Sgr, R CMi, Cy Cyg, and RU Cam. The strongest FeH lines are unimpressive in R Cyg, where the strong infrared bands of FeH have already been identified. Identification of the blue-green FeH lines in other spectra must be considered inconclusive until a rotational analysis of the FeH spectrum is available.

Davis-Locanthi, D.↗

Short-Term Elevated Temperature Mechanical Performance and Microstructure of A Niobium-Zirconium Alloy Produced via Laser Powder Bed Fusion In-Situ Alloying

Nb-1Zr is a readily fabricable, dispersion-strengthened niobium alloy with improved elevated temperature properties compared to commercially pure niobium. This low to moderate strength niobium alloy is desirable in thermal management systems for fission power and propulsion applications; however, pre-alloyed spherical feedstock for powder-based additive manufacturing processes is generally unavailable. Laser powder bed fusion (L-PBF) in-situ alloying of a Nb-1Zr chemistry was performed using a high-purity niobium feedstock coated with 1 wt% of zirconium-based ceramic compound nano-powders: ZrO 2 , ZrC, and ZrH 2 . The additively manufactured material was mechanically tested at elevated temperatures within a controlled environment in the as-built condition. For comparison, traditionally manufactured wrought feedstock was also tested within an identical environment. Examination of the materials’ microstructure and short-term elevated temperature mechanical response determined: in-situ alloying of spherical Nb powder feedstock with Zr-based ceramic nanoparticles can be successfully implemented; the ZrO 2 addition offered the greatest elevated temperature stability and strength but exhibited brittle behavior; the ZrC addition achieved a balance of room temperature ductility and elevated temperature strength; and the ZrH 2 -modified material had the lowest as-built interstitial content and showed high ductility with mechanical performance most similar to wrought Nb-1Zr.

Niobium Alloy↗

Molecular column densities in selected model atmospheres

From an examination of predicted column densities, the following conclusions were drawn: (1) The SiO ought to be visible in carbon stars which were generated from triple alpha burning, but absent from carbon stars generated from the CNO bi-cycle. (2) Variation in the observed relative strengths of TiO and ZrO is indicative of real differences in the ratio Ti/Zr. (3) The TiO/ZrO ratio shows a small variation as C/O and effective temperature is changed. (4) Column density of silicon dicarbide (SiC2) is sensitive to abundance, temperature, and gravity; hence all relationships between the strength of SiC2 and other stellar parameters will show appreciable scatter. There is however, a substantial luminosity effect present in the SiC2 column densities. (5) Unexpectedly, SiC2 is anti-correlated with C2. (6) The presence of SiC2 in a carbon star eliminates the possibility of these stars having temperatures greater than or equal to 3000 K, or being produced through the CNO bi-cycle.

Johnson, H. R.↗

Photometric observations of unidentified bands in S stars

Scanner and eight-color observations are reported for unidentified bands occurring in the spectra of pure S stars. Correlations of an unidentified band measured at 7120 A with the band strengths of ZrO and LaO show a simple temperature dependence. A close correlation of molecular band strengths with color temperature suggests that the pure S stars are a fairly homogeneous group.

Piccirillo, J.↗

Thermal barrier coating life prediction model

This is the second annual report of the first 3-year phase of a 2-phase, 5-year program. The objectives of the first phase are to determine the predominant modes of degradation of a plasma sprayed thermal barrier coating system and to develop and verify life prediction models accounting for these degradation modes. The primary TBC system consists of an air plasma sprayed ZrO-Y2O3 top coat, a low pressure plasma sprayed NiCrAlY bond coat, and a Rene' 80 substrate. Task I was to evaluate TBC failure mechanisms. Both bond coat oxidation and bond coat creep have been identified as contributors to TBC failure. Key property determinations have also been made for the bond coat and the top coat, including tensile strength, Poisson's ratio, dynamic modulus, and coefficient of thermal expansion. Task II is to develop TBC life prediction models for the predominant failure modes. These models will be developed based on the results of thermmechanical experiments and finite element analysis. The thermomechanical experiments have been defined and testing initiated. Finite element models have also been developed to handle TBCs and are being utilized to evaluate different TBC failure regimes.

Hillery, R. V.↗

Theoretical studies of the monoxides and monosulfides of Y, Zr, and Nb

Modified-CPF and CASSCF/multireference-CI theoretical calculations are presented for the ground and low-lying states of YO and YS, ZrO and ZS, and NbO and NbS. The techniques employed are explained, and the calculated spectroscopic constants are presented in extensive tables. Good agreement is found with published experimental data on the oxides, and it is inferred that the sulfide results are accurate as well. Particular attention is given to the high-lying quartet manifold of states in YO and the (1) 3Pi-a3Delta transition of ZrS (possibly the source of the IR Keenan bands seen in S-star spectra).

Langhoff, Stephen R.↗

Thermal barrier coating life prediction model

The objectives of this research were to determine the predominant modes of degradation of a plasma sprayed thermal barrier coating (TBC) system, and then to develop and verify life prediction models accounting for these degradation modes. The TBC system consists of a low pressure plasma sprayed (LPPS) bond coat layer of Ni-22Cr-10Al-O.3Y, an air plasma sprayed (APS) yttria partially stabilized zirconia (ZrO sub 2-8Y sub 2 O sub 3) top coat on a conventionally cast Rene 80 (Ni base) substrate. Thermal cycle testing of TBCs was employed to evaluate the effect of coating edges, bond coat oxidation, bond coat creep, top coat thickness, and bond coat thickness.

Pilsner, B.↗

Sequentially evaporated thin Y-Ba-Co-O superconducting films on microwave substrates

The development of high T sub c superconducting thin films on various microwave substrates is of major interest in space electronic systems. Thin films of YBa2Cu3O(7-Delta) were formed on SrTiO3, MgO, ZrO2 coated Al2O3, and LaAlO3 substrates by multi-layer sequential evaporation and subsequent annealing in oxygen. The technique allows controlled deposition of Cu, BaF2 and Y layers, as well as the ZrO buffer layers, to achieve reproducibility for microwave circuit fabrication. The three layer structure of Cu/BaF2/Y is repeated a minimum of four times. The films were annealed in an ambient of oxygen bubbled through water at temperatures between 850 C and 900 C followed by slow cooling (-2 C/minute) to 450 C, a low temperature anneal, and slow cooling to room temperature. Annealing times ranged from 15 minutes to 5 hrs. at high temperature and 0 to 6 hr. at 450 C. Silver contacts for four probe electrical measurements were formed by evaporation followed with an anneal at 500 C. The films were characterized by resistance-temperature measurements, energy dispersive X-ray spectroscopy, X-ray diffraction, and scanning electron microscopy. Critical transition temperatures ranged from 30 K to 87 K as a function of the substrate, composition of the film, thicknesses of the layers, and annealing conditions. Microwave ring resonator circuits were also patterned on these MgO and LaAlO3 substrates.

Valco, G. J.↗

Thermal Testing of High Performance: Thermal Barrier Coatings for Turbine Blades

A 350 micron thick 7 wt.% Y 2 O 3 -ZrO 2 (7YSZ) ceramic Thermal Barrier Coating (TBC) was manufactured in an argon atmosphere and with a strictly controlled substrate temperature on flat IN 600 samples and on IN 100 aircraft turbine blades. This new atmosphere and temperature controlled spraying (ATCS) allows the reduction of the residual stresses and an improvement in the microstructure and in the mechanical properties of the coating. The good performance of these new TBC's was assessed in thermal fatigue and in thermal shock tests carried out in air at 1100°C and at 1280°C respectively. The oxidation rate of the metal-ceramic interface was measured at 1100°C. Failure of the TBC's was induced only by the deterioration (like oxidation, cracking, ...) of the uncoated parts of the samples, as testing temperature was too severe for the base metals. Spalling was thereafter driven by compressive stresses near the aluminum oxide layer at the metal-ceramic interface. The results of these tests underline the good quality of the ceramic coating manufactured by the new ATCS technology.

L Bertamini↗

Magnesium-Aluminum-Zirconium Oxide Amorphous Ternary Composite: A Dense and Stable Optical Coating

In the present work, the process parameter dependent optical and structural properties of MgO-Al(2)O(3)-ZrO(2) ternary mixed-composite material have been investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases and process dependent material composition of films have been investigated through the use of Atomic Force Microscopy (AFM), X-ray diffraction analysis and Energy Dispersive X- ray (EDX) analysis. EDX analysis made evident the correlation between the optical constants and the process dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

Sahoo, N. K.↗

Ceramic Spheres From Cation Exchange Beads

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

Dynys, F. W.↗

Continuous Tuning and Calibration of Vibratory Gyroscopes

A method of control and operation of an inertial reference unit (IRU) based on vibratory gyroscopes provides for continuously repeated cycles of tuning and calibration. The method is intended especially for application to an IRU containing vibratory gyroscopes that are integral parts of microelectromechanical systems (MEMS) and that have cloverleaf designs, as described in several previous NASA Tech Briefs articles. The method provides for minimization of several measures of spurious gyroscope output, including zero-rate offset (ZRO), angle random walk (ARW), and rate drift. These benefits are afforded both at startup and thereafter during continuing operation, in the presence of unknown rotation rates and changes in temperature. A vibratory gyroscope contains a precision mechanically resonant structure containing two normal modes of vibration nominally degenerate in frequency and strongly coupled via a Coriolis term. In the case of the cloverleaf design MEMS gyro, these normal modes of vibration are plate rocking modes. The rocking motion of the plate is described by giving two angles, theta(sub 1) and theta(sub 2). A proof mass consisting of a post orthogonal to the plate ensures a high degree of Coriolis coupling of vibratory energy from one mode into the other under inertial rotation. The plate is driven and sensed capacitively across a few-microns-wide gap, and the normal mode frequencies can be tuned electrostatically by DC voltages applied across this gap. In order to sense rotation, the resonator plate is caused to rock in the theta(sub 1) direction, then any small motions in the theta(sub 2) direction are sensed, rebalanced, and interpreted as inertial rotation. In this scenario, the "drive" has been assigned to the theta(sub 1) direction, and the "sense" has been assigned to the theta(sub 2) direction.

Hayworth, Ken↗

Reduced-Gravity Measurements of the Effect of Oxygen on Properties of Zirconium

The influence of oxygen on the thermophysical properties of zirconium is being investigated using MSL-EML (Material Science Laboratory - Electromagnetic Levitator) on ISS (International Space Station) in collaboration with NASA, ESA (European Space Agency), and DLR (German Aerospace Center). Zirconium samples with different oxygen concentrations will be put into multiple melt cycles, during which the density, viscosity, surface tension, heat capacity, and electric conductivity will be measured at various undercooled temperatures. The facility check-up of MSL-EML and the first set of melting experiments have been successfully performed in 2015. The first zirconium sample will be tested near the end of 2015. As part of ground support activities, the thermophysical properties of zirconium and ZrO were measured using a ground-based electrostatic levitator located at the NASA Marshall Space Flight Center. The influence of oxygen on the measured surface tension was evaluated. The results of this research will serve as reference data for those measured in ISS.

Zhao, J.↗