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Diurnal Lightning Distributions as Observed by the Optical Transient Detector (OTD) and the Lightning Imaging Sensor (LIS)

Data obtained from the OTD (April 1995 to March 2000) and LIS (December 1997 to December 2005) satellites (70 and 35 degree inclination low earth orbits, respectively) are used to statistically determine the number of flashes in the diurnal cycle both as a function of local and universal time. Also included are global flash density maps. The data are further subdivided by season, continental versus oceanic, night time versus day time, northern versus southern hemisphere, and other regions of interest. The data include corrections for detection efficiency and instrument view time. The data are compared with both the "Carnegie Curve" and the diurnal global thunderstorm contributions from thunderday statistics from different continents, and are found to agree closely in phase and amplitude with the global thunderday statistics. The analysis also indicates that the southern hemisphere spring (September to November) has larger amplitude than the southern hemisphere fall (March to May). This may be due to differences in the contribution from the Brazilian rain forest during these periods. In general, as highlighted by a difference analysis, more lightning is observed in local springtime than the fall for continental locations, while oceanic regions display an opposite effect. For some areas of the world, the peak of diurnal curve appears to be shifted to later in the evening.

Bailey, Jeff C.↗

Optically Thin Liquid Water Clouds: Their Importance and Our Challenge

Many of the clouds important to the Earth's energy balance, from the tropics to the Arctic, are optically thin and contain liquid water. Longwave and shortwave radiative fluxes are very sensitive to small perturbations of the cloud liquid water path (LWP) when the liquid water path is small (i.e., < g/sq m) and, thus, the radiative properties of these clouds must be well understood to capture them correctly in climate models. We review the importance of these thin clouds to the Earth's energy balance, and explain the difficulties in observing them. In particular, because these clouds are optically thin, potentially mixed-phase, and often (i.e., have large 3-D variability), it is challenging to retrieve their microphysical properties accurately. We describe a retrieval algorithm intercomparison that was conducted to evaluate the issues involved. The intercomparison included eighteen different algorithms to evaluate their retrieved LWP, optical depth, and effective radii. Surprisingly, evaluation of the simplest case, a single-layer overcast cloud, revealed that huge discrepancies exist among the various techniques, even among different algorithms that are in the same general classification. This suggests that, despite considerable advances that have occurred in the field, much more work must be done, and we discuss potential avenues for future work.

Turner, D. D.↗

Guaranteeing Pointing Performance of the SDO Sun-Pointing Controllers in Light of Nonlinear Effects

The Solar Dynamics Observatory (SDO) mission is the first Space Weather Research Network mission, part of NASA s Living With a Star program.1 This program seeks to understand the changing Sun and its effects on the Solar System, life, and society. To this end, the SDO spacecraft will carry three Sun-observing instruments to geosynchronous orbit: Helioseismic and Magnetic Imager (HMI), led by Stanford University; Atmospheric Imaging Assembly (AIA), led by Lockheed Martin Space and Astrophysics Laboratory; and Extreme Ultraviolet Variability Experiment (EVE), led by the University of Colorado. Links describing the instruments in detail may be found through the SDO web site.2 The basic mission goals are to observe the Sun for a very high percentage of the 5-year mission (10-year goal) with long stretches of uninterrupted observations and with constant, high-data-rate transmission to a dedicated ground station. These goals guided the design of the spacecraft bus that will carry and service the three-instrument payload. At the time of this publication, the SDO spacecraft bus is well into the integration and testing phase at the NASA Goddard Space Flight Center (GSFC). A three-axis stabilized attitude control system (ACS) is needed both to point at the Sun accurately and to keep the roll about the Sun vector correctly positioned. The ACS has four reaction wheel modes and 2 thruster actuated modes. More details about the ACS in general and the control modes in particular can be found in Refs. [3-6]. All four of SDO s wheel-actuated control modes involve Sun-pointing controllers, as might be expected from such a mission. Science mode, during which most science data is collected, uses specialized guide telescopes to point accurately at the Sun. Inertial mode has two sub-modes, one tracks a Sun-referenced target orientation, and another maintains an absolute (star-referenced) target orientation, that both employ a Kalman filter to process data from a digital Sun sensor and two star trackers. However, this paper is concerned only with the other two modes: Safe Hold (SH) and Sun Acquisition (SA).

Starin, Scott R.↗

Integrated Formation Optical Communication and Estimation System

An architecture has been designed that integrates formation estimation methodologies, precision formation sensing, and high-bandwidth formation communication into a robust, strap-on system that meets knowledge and communication requirements for the majority of planned, precision formation missions. Specifically, the integrated system supports (a) sub-millimeter metrology, (b) multiple greater than 10 Mbps communication channels over a large, 10 deg field-of-view (FOV), and (c) generalized formation estimation methodologies. The sensing sub-system consists of several absolute, metrology gauges with up to 0.1 mm precision that use amplitude-modulated lasers and a LISA-heritage phase meter. Since amplitude modulation is used, inexpensive and robust diode lasers may be used instead of complex, frequency-stabilized lasers such as for nanometer-level metrology. The metrology subsystem laser transceivers consist of a laser diode, collecting optics, and an avalanche photo diode (APD) for detecting incoming laser signals. The APD is necessary since received power is small due to the large (for optical applications) FOV. The phase meter determines the phase of the incoming amplitude modulations as measured by the APD. This phase is equivalent to time-of-flight and, therefore, distance. By placing three laser transceivers on each spacecraft, 18 clock-offset-corrupted distances are calculated. These measurements are communicated and averaged to obtain nine correct distances between the transceivers. From these correct distances, the range and bearing between spacecraft and their relative attitude are determined. Next, communication is integrated on the laser carrier through spectral separation. Metrology amplitude modulations are limited to the 45-50 MHz band, leaving 0-45 MHz for communication. Through careful design of coding scheme, error correction, and filters, six independent 10 Mbps receive channels are possible. Hence, a spacecraft can simultaneously broadcast at 10 Mbps and listen to six other spacecraft. The integrated sensing and communication architecture has been developed, as have formation estimation methodologies that allow the sensing topology to reconfigure as spacecraft maneuver. A bench-top implementation of the integrated sensing and communication architecture is in progress. The final, multiple sensing/communication systems will be tied together via formation estimation algorithms that are also undergoing further development.

Scharf, Daniel↗

Interpretable machine learning models classify minerals via spectroscopy

Developing methods to identify mineral species confidently and rapidly from Raman spectral analysis is critical to numerous fields. Traditionally, analysis relies on pattern matching the Raman spectrum of an unknown dataset with a supporting library of well-characterized spectral data, which may prove difficult for environmental samples that are poorly crystalline or phase mixtures. Here, we developed interpretable machine learning models that can classify uranium minerals by secondary oxyanion chemistry and other physicochemical properties based solely on Raman spectra. This new ML method produces a mineral profile of physical and chemical properties for an unknown sample and can rapidly classify or identify unknown minerals from Raman data, without the need for an exact pattern match in a spectral library. Training models are validated by 1. Strong correlation of high confidence model regions with published spectroscopic assignments and 2. Correct classification of a mineral not present in training data. Training data are from the Compendium of Uranium Raman and Infrared Experimental Spectra and available crystallographic information files within the open-source Smart Spectral Matching scientific framework. Physically meaningful classifier models can rapidly identify key structural and chemical information about unknown uranium minerals and the overall methodology is broadly applicable for mineral phases.

Machine learning↗

Phased Acoustic Array Measurements of a 5.75 Percent Hybrid Wing Body Aircraft

Detailed acoustic measurements of the noise from the leading-edge Krueger flap of a 5.75 percent Hybrid Wing Body (HWB) aircraft model were recently acquired with a traversing phased microphone array in the AEDC NFAC (Arnold Engineering Development Complex, National Full Scale Aerodynamics Complex) 40- by 80-Foot Wind Tunnel at NASA Ames Research Center. The spatial resolution of the array was sufficient to distinguish between individual support brackets over the full-scale frequency range of 100 to 2875 Hertz. For conditions representative of landing and take-off configuration, the noise from the brackets dominated other sources near the leading edge. Inclusion of flight-like brackets for select conditions highlights the importance of including the correct number of leading-edge high-lift device brackets with sufficient scale and fidelity. These measurements will support the development of new predictive models.

Krueger noise↗

Phase Field Modeling of Corrosion for Design of Next-Generation Magnesium-Aluminum Vehicle Joints

In this study, WPI and its partners sought to understand galvanic corrosion in Mg-Al friction stir weld (FSW) joints. Unlike fusion welds, FSW is done in the solid state. This limits (but does not eliminate) the formation of brittle Al-Mg intermetallics, resulting in better joint strength and corrosion resistance. This study aimed to understand corrosion behavior of Mg-Al FSW joints by using a Cahn-Hilliard phase field electrochemistry model based on the work of Pongsaksawad et al. Its context challenge problem was an ultra-light door designed by Magna with 6061-Al sheet outer and ZEK100-Mg sheet inner panels, joined by an adhesive and FSW. Unlike most FSW joints, which weld through the softer material into the harder one, the Al sheet’s hem joint around Mg required the FSW tool to through the harder Al into the softer Mg, which was itself a challenge. Despite this challenge, PNNL succeeded in consistently making very strong FSW lap joints, by using a triflute tool and power control. Characterization showed mostly separate Al and Mg regions in the weld, usually with a hook protruding from Al into Mg, which likely contributed to high joint strength. Nanohardness mapping showed higher hardness in thin Mg swirls into the Al nugget, likely due to the intermetallics. The study used the industry standard SAE J2334 Cyclic Corrosion Test (CCT) to simulate corrosion conditions over the life of a vehicle, as well as linear polarization testing and ASTM G71 pitting corrosion testing. Corrosion reactions were: H 2 O + ½O 2 + 2e - → 2OH - at the Al cathode, and either Mg → Mg 2+ + 2e - or Mg + 2OH - → Mg(OH) 2 + 2e - at the Mg anode, with electron transfer through the joint. Mass loss increased with Al section length, supporting the hypothesis that galvanic corrosion in Al-Mg joints is limited by the cathodic reaction. Both pitting corrosion (first anode reaction) and hydroxide film formation (second reaction) were observed. The J2334 CCT test method was slightly modified, adding a chromium solution cleaning step after each week of corrosion testing, in order to remove Mg oxides and hydroxides and accurately measure mass loss over time. That said, FSW joints treated in this way did not did not exhibit significant reduction in lap shear strength of the joints vs. newly welded samples which had not undergone corrosion. Corrosion appeared to consist mainly of pitting in Mg in a way which did not directly affect the bond between the materials where the joints failed. A Cahn-Hilliard phase field model coupled with electrical potential described the electronically mediated galvanic corrosion electrochemical reactions described above in the four-component Al-Mg-H 2 O-(H 2 O+½O 2 ) system. This 2-D model successfully predicted Mg(OH)₂ formation at the anode in some circumstances, and Mg pitting corrosion in others, and showed the correct electric field directions in both cases. The model predicted Mg pit corrosion depth within a factor of two of measured pits.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

In-Flight Operation of the Dawn Ion Propulsion System Through Start of the Vesta Cruise Phase

The Dawn mission, part of NASA's Discovery Program, has as its goal the scientific exploration of the two most massive main-belt asteroids, Vesta and Ceres. The Dawn spacecraft was launched from Cape Canaveral Air Force Station on September 27, 2007 on a Delta-II 7925H-9.5 (Delta-II Heavy) rocket that placed the 1218 kg spacecraft into an Earth-escape trajectory. On-board the spacecraft is an ion propulsion system (IPS) which will provide most of the delta V needed for heliocentric transfer to Vesta, orbit capture at Vesta, transfer to Vesta science orbits, departure and escape from Vesta, heliocentric transfer to Ceres, orbit capture at Ceres, and transfer to Ceres science orbits. The Dawn ion design is based on the design validated on NASA's Deep Space 1 (DS1) mission. However, because of the very substantial (11 km/s) delta V requirements for this mission Dawn requires two engines to complete its mission objectives. The power processor units (PPU), digital control and interface units (DCIU) slice boards and the xenon control assembly (XCA) are derivatives of the components used on DS1. The DCIUs and thrust gimbal assemblies (TGA) were developed at the Jet Propulsion Laboratory. The spacecraft was provided by Orbital Sciences Corporation, Sterling, Virginia, and the mission is managed by and operated from the Jet Propulsion Laboratory. Dawn partnered with Germany, Italy and Los Alamos National Laboratory for the science instruments. The mission is led by the principal investigator, Dr. Christopher Russell, from the University of California, Los Angeles. The first 80 days after launch were dedicated to the initial checkout of the spacecraft followed by cruise to Mars. Cruise thrusting leading to a Mars gravity assist began on December 17, 2007 and was successfully concluded as planned on October 31, 2008. During this time period the Dawn IPS was operated mostly at full power for approximately 6500 hours, consumed 71.7 kg of xenon and delivered approximately 1.8 km/s of delta V to the spacecraft. The thrusting to Mars was followed by a coasting period of approximately 3.5 months that included a Mars flyby in February of 2009. The Mars flyby provided a gravity assist (MGA) for a plane change and approximately 1 km/s of heliocentric energy increase and is the only part of the mission following launch in which a needed velocity change is not accomplished by the IPS. During the coast period IPS was operated for a trajectory correction maneuver and for engineering tests but was not operated for primary propulsion. Closest approach to Mars occurred as planned on February 17, 2009 and was followed by another coasting period of just under 4 months in duration. During this last coasting phase IPS was operated only for routine maintenance activities and for system engineering tests. Deterministic thrusting for heliocentric transfer to Vesta resumed on June 8, 2009. IPS will be operated for over two years at throttled power levels leading to arrival at Vesta in September of 2011 and arrival at Ceres in February 2015. This paper provides an overview of Dawn's mission objectives and the results of Dawn IPS mission operations through the start of deterministic thrusting to Vesta.

Garner, Charles E.↗

Significance of the structural configuration of B2 disorder in Co and Ti based Heusler alloys

We investigate here structural (at local and global levels) and transport properties for 𝑋 2 ⁢MnAl (𝑋= Co and Ti). Additionally, the magnetic properties were also studied for Ti 2 ⁢MnAl. Our x-ray diffraction results show that both the compounds stabilize in B2 disordered phase with cubic structure of 𝑃⁢𝑚⁢$\overline{3}$⁢𝑚 space group. Further, the structural configuration of the above disordered phase for both the compounds was identified using combined studies of x-ray absorption spectroscopy and multiple scattering calculations at the transition metal 𝐾 edges. Upon such identification, in the case of Co 2 ⁢Mn 1−𝑦⁢ Cr 𝑦 ⁢Al (𝑦= 0, 0.05, 0.1, 0.2) with change in 𝑦, we are able to establish a better connection quantitatively between the inverse of Mn-Co bonds and peak in the temperature-dependent resistivity. This highlights the crucial importance of a detailed understanding of the nature of B2 disorder. In the case of 𝑦=0, in the temperature range of study, the resistivity is driven by the functional form associated with (a) three-dimensional enhanced electron-electron Coulomb interaction scattering mechanism and (b) an unconventional one-magnon process. For Ti 2 ⁢MnAl, the transport shows metallic glasslike behavior at high temperature, while at low temperature it follows both the Cote-Meisel's model and quantum correction model. In this compound, the magnetic studies suggest the formation of superparamagnetic clusters in the paramagnetic matrix at low temperatures. Our density functional theory results are in line with the transport and magnetic properties. In literature, the spin polarization percentage (𝑃) for 𝑋= Co in B2 disordered phase is 76%. However, the present results emphasize the fact that in B2 disordered phase, the value of 𝑃 can range from 90% to 71% depending on the structural configuration introduced by swapping of the atomic positions of Mn and Al. For the compound under study, the value of percentage spin polarization obtained ranges between 82% to 85%. In addition, we also identify the origin of the difference in the shape of the Mn 3⁢𝑑 density of states for both the alloys. In conclusion, our results for 𝑋= Co alloy highlights the importance of identifying the specific structural configuration associated with a particular disorder category especially in the estimation of 𝑇 𝑐 and 𝑃 and for 𝑋= Ti, the physical properties can be tuned by varying the position of 𝐸 𝐹 and thereby its utilization in device applications.

36 MATERIALS SCIENCE↗

Systematic quark/gluon identification with ratios of likelihoods

Discriminating between quark- and gluon-initiated jets has long been a central focus of jet substructure, leading to the introduction of numerous observables and calculations to high perturbative accuracy. At the same time, there have been many attempts to fully exploit the jet radiation pattern using tools from statistics and machine learning. We propose a new approach that combines a deep analytic understanding of jet substructure with the optimality promised by machine learning and statistics. After specifying an approximation to the full emission phase space, we show how to construct the optimal observable for a given classification task. This procedure is demonstrated for the case of quark and gluons jets, where we show how to systematically capture sub-eikonal corrections in the splitting functions, and prove that linear combinations of weighted multiplicity is the optimal observable. In addition to providing a new and powerful framework for systematically improving jet substructure observables, we demonstrate the performance of several quark versus gluon jet tagging observables in parton-level Monte Carlo simulations, and find that they perform at or near the level of a deep neural network classifier. Combined with the rapid recent progress in the development of higher order parton showers, we believe that our approach provides a basis for systematically exploiting subleading effects in jet substructure analyses at the Large Hadron Collider (LHC) and beyond.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Role of chemical production and depositional losses on formaldehyde in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM)

Abstract. Formaldehyde (HCHO) is an important air pollutant with direct cancer risk and ozone-forming potential. HCHO sources are complex because HCHO is both directly emitted and produced from oxidation of most gas-phase reactive organic carbon. We update the secondary production of HCHO in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) in the Community Multiscale Air Quality (CMAQ) model. Production of HCHO from isoprene and monoterpenes is increased, correcting an underestimate in the current version. Simulated June–August surface HCHO during peak photochemical production (11:00–15:00 LT, local time) increased by 0.6 ppb (32 %) over the southeastern USA and by 0.2 ppb (13 %) over the contiguous USA. The increased HCHO compares more favorably with satellite-based observations from the TROPOspheric Monitoring Instrument (TROPOMI) and from aircraft-based observations. Evaluation against hourly surface observations indicates a missing nighttime sink that can be improved by increased nighttime deposition, which reduces June–August nocturnal (20:00–04:00 LT) surface HCHO by 1.1 ppb (36 %) over the southeastern USA and 0.5 ppb (29 %) over the contiguous USA. The ability of CRACMM to capture peak levels of HCHO at midday is improved, particularly at sites in the northeastern USA, while peak levels at sites in the southeastern USA are improved, although still lower than observed. Using established risk assessment methods, lifetime exposure of the population in the contiguous USA (∼ 320 million) to ambient HCHO levels predicted here may result in 6200 lifetime cancer cases, with 40 % from controllable anthropogenic emissions of nitrogen oxides and reactive organic compounds. Chemistry updates will be available in CRACMM version 2 (CRACMM2) in CMAQv5.5.

Skipper, T. Nash↗

Solution convergence study during launch phase using limited tracking data

Orbit determination accuracies during critical phases at launch, when data are available from only one station, can be enhanced using angle data with conventional Doppler and range data. A study performed on the forthcoming Japanese ETS-5 mission indicates that this requires correct handling of the angle biases. This was verified using actual tracking data received from the BS-2B launch.

Premkumar, R. I.↗

Effects of Weightlessness on Human Fluid and Electrolyte Physiology

The changes that occur in human fluid and electrolyte physiology during the acute and adaptive phases of adaptation to spaceflight are summarized. A number of questions remain to be answered. At a time when plasma volume and extracellular fluid volume are contracted and salt and water intake is unrestricted. ADH does not correct the volume deficit and serum sodium decreases. Change in secretion or activity of a natriuretic factor during spaceflight is one possible explanation. Recent identification of a polypeptide hormone produced in cardiac muscle cells which is natiuretic, is hypotensive, and has an inhibitory effect on renin and aldosterone secretion has renewed interest in the role of a natriuretic factor. The role of this atrial natriuretic factor (ANF) in both long- and short-term variation in extracellular volumes and in the inability of the kidney to bring about an escape from the sodium-retaining state accompanying chronic cardiac dysfunction makes it reasonable to look for a role of ANF in the regulation of sodium during exposure to microgravity. Prostaglandin-E is another hormone that may antagonize the action of ADH. Assays of these hormones will be performed on samples from crew members in the future.

Leach, Carolyn S.↗

A navigation and control system for an autonomous rescue vehicle in the space station environment

A navigation and control system was designed and implemented for an orbital autonomous rescue vehicle envisioned to retrieve astronauts or equipment in the case that they become disengaged from the space station. The rescue vehicle, termed the Extra-Vehicular Activity Retriever (EVAR), has an on-board inertial measurement unit ahd GPS receivers for self state estimation, a laser range imager (LRI) and cameras for object state estimation, and a data link for reception of space station state information. The states of the retriever and objects (obstacles and the target object) are estimated by inertial state propagation which is corrected via measurements from the GPS, the LRI system, or the camera system. Kalman filters are utilized to perform sensor fusion and estimate the state propagation errors. Control actuation is performed by a Manned Maneuvering Unit (MMU). Phase plane control techniques are used to control the rotational and translational state of the retriever. The translational controller provides station-keeping or motion along either Clohessy-Wiltshire trajectories or straight line trajectories in the LVLH frame of any sufficiently observed object or of the space station. The software was used to successfully control a prototype EVAR on an air bearing floor facility, and a simulated EVAR operating in a simulated orbital environment. The design of the navigation system and the control system are presented. Also discussed are the hardware systems and the overall software architecture.

Merkel, Lawrence↗

Multi-Scale Modeling of Magnetospheric Reconnection

One of the major challenges in modeling the magnetospheric magnetic reconnection is to quantify the interaction between large-scale global magnetospheric dynamics and microphysical processes in diffusion regions near reconnection sites. There is still considerable debate as to what degree microphysical processes on kinetic scales affect the global evolution and how important it is to substitute numerical dissipation and/or ad hoc anomalous resistivity by a physically motivated model of dissipation. Comparative studies of magnetic reconnection in small scale geometries demonstrated that MHD simulations that included non-ideal processes in terms of a resistive term $\eta J$ did not produce the fast reconnection rates observed in kinetic simulations. For a broad range of physical parameters in collisionless magnetospheric plasma, the primary mechanism controlling the dissipation in the vicinity of the reconnection site is non-gyrotropic effects with spatial scales comparable with the particle Larmor radius. We utilize the global MHD code BATSRUS and incorporate nongyrotropic effects in diffusion regions in terms of corrections to the induction equation. We developed an algorithm to search for magnetotail reconnection sites, specifically where the magnetic field components perpendicular to the local current direction approaches zero and form an X-type configuration. Spatial scales of the diffusion region and magnitude of the reconnection electric field are calculated selfconsistently using MHD plasma and field parameters in the vicinity of the reconnection site. The location of the reconnection sites is updated during the simulations. To clarify the role of nongyrotropic effects in diffusion region on the global magnetospheric dynamic we perform simulations with steady southward IMF driving of the magnetosphere. Ideal MHD simulations with magnetic reconnection supported by numerical resistivity produce steady configuration with almost stationary near-earth neutral line (NENL). Simulations with non-gyrotropic corrections demonstrate dynamic quasi-periodic response to the steady driving condition. The loading/unloading cycle in non-gyrotropic MHD results has a non-stationary reconnection site in the magnetotail, with the retreating during the stretching phase and then a new NENL forming in the resulting thin plasma sheet. We expect that this model will lead to improved representations of space weather event in the magnetosphere.

Kuznetsova, M. M.↗

Wake Cycle Robustness of the Mars Science Laboratory Flight Software

The Mars Science Laboratory (MSL) is a spacecraft being developed by the Jet Propulsion Laboratory (JPL) for the purpose of in-situ exploration on the surface of Mars. The objective of MSL is to explore and quantitatively assess a local region on the Martian surface as a habitat for microbial life, past or present. This objective will be accomplished through the assessment of the biological potential of at least one target environment, the characterization of the geology and geochemistry of the landing region, an investigation of the planetary process relevant to past habitability, and a characterization of surface radiation. For this purpose, MSL incorporates a total of ten scientific instruments for which functions are to include, among others, atmospheric and descent imaging, chemical composition analysis, and radiation measurement. The Flight Software (FSW) system is responsible for all mission phases, including launch, cruise, entry-descent-landing, and surface operation of the rover. Because of the essential nature of flight software to project success, each of the software modules is undergoing extensive testing to identify and correct errors.

Whitehill, Robert↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Revealing the Phase Separation Behavior of Thermodynamically Immiscible Elements in a Nanoparticle

Phase-separation is commonly observed in multimetallic nanomaterials, yet it is not well understood how immiscible elements distribute in a thermodynamically stable nanoparticle. Herein, we studied the phase-separation of Au and Rh in nanoparticles using electron microscopy and tomography techniques. The nanoparticles were thermally annealed to form thermodynamically stable structures. HAADF-STEM and EDS characterizations reveal that Au and Rh segregate into two domains while their miscibility is increased. Using aberration-corrected HAADF-STEM and atomic electron tomography, we show that the increased solubility of Au in Rh is achieved by forming Au clusters and single atoms inside the Rh domains and on the Rh surface. Furthermore, based on the three-dimensional reconstruction of a AuRh nanoparticle, we can visualize the uneven interface that is embedded in the nanoparticle. Finally, the results advance our understanding on the nanoscale thermodynamic behavior of metal mixtures, which is crucial for the optimization of multimetallic nanostructures for many applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗