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At least 307 records · Page 17

Stability and Phase Noise Tests of Two Cryo-Cooled Sapphire Oscillators

A cryocooled Compensated Sapphire Oscillator (CSO), developed for the Cassini Ka-band Radio Science experiment, and operating in the 8K - 10K temperature range was previously demonstrated to show ultra-high stability of sigma(sub y) = 2.5 x 10 (exp -15) for measuring times 200 seconds less than or equal to tau less than or equal to 600 seconds using a hydrogen maser as reference. We present here test results for a second unit which allows CSO short-term stability and phase noise to be measured for the first time. Also included are design details of a new RF receiver and an intercomparison with the first CSO unit. Cryogenic oscillators operating below about 10K offer the highest possible short term stability of any frequency sources. However, their use has so far been restricted to research environments due to the limited operating periods associated with liquid helium consumption. The cryocooled CSO is being built in support of the Cassini Ka-band Radio Science experiment and is designed to operate continuously for periods of a year or more. Performance targets are a stability of 3-4 x 10 (exp -15) (1 second less than or equal to tau less than or equal to 100 seconds) and phase noise of -73dB/Hz @ 1Hz measured at 34 GHz. Installation in 5 stations of NASA's deep space network (DSN) is planned in the years 2000 - 2002. In the previous tests, actual stability of the CSO for measuring times tau less than or equal to 200 seconds could not be directly measured, being masked by short-term fluctuations of the H-maser reference. Excellent short-term performance, however, could be inferred by the success of an application of the CSO as local oscillator (L.O.) to the JPL LITS passive atomic standard, where medium-term stability showed no degradation due to L.O. instabilities at a level of (sigma)y = 3 x 10 (exp -14)/square root of tau. A second CSO has now been constructed, and all cryogenic aspects have been verified, including a resonator turn-over temperature of 7.907 K, and Q of 7.4 x 10 (exp 8). These values compare to a turn-over of 8.821 K and Q of 1.0 x 10 (exp 9) for the first resonator. Operation of this second unit provides a capability to directly verify for the first time the short-term (1 second less than or equal to tau less than or equal to 200 seconds) stability and the phase noise of the CSO units. The RF receiver used in earlier tests was sufficient to meet Cassini requirements for tau greater than or equal to 10 seconds but had short-term stability limited to 2-4 x 10 (exp -14) at tau = 1 second, a value 10 times too high to meet our requirements. A new low-noise receiver has been designed to provide approximately equal to 10-15 performance at 1 second, and one receiver is now operational, demonstrating again short-term CSO performance with H maser-limited stability. Short-term performance was degraded in the old receiver due to insufficient tuning bandwidth in a 100MHZ quartz VCO that was frequency-locked to the cryogenic sapphire resonator. The new receivers are designed for sufficient bandwidth, loop gain and low noise to achieve the required performance.

Dick, G. John↗

High-Resolution Electron Energy-Loss Spectroscopy (HREELS) Using a Monochromated TEM/STEM

A 200 keV FEI TF20 XT monochromated (scanning) transmission electron microscope funded by NASA's SRLIDAP program is undergoing installation at Lawrence Livermore National Laboratory. Instrument specifications in STEM mode are Cs =1.0 mm, Cc =1.2 mm, image resolution =0.18 nm, and in TEM mode Cs =1.3 mm, Cc =1.3 mm, information limit =0.14 nm. Key features of the instrument are a voltage-stabilized high tension (HT) supply, a monochromator, a high-resolution electron energy-loss spectrometer/energy filter, a high-resolution annular darkfield detector, and a solid-state x-ray energy-dispersive spectrometer. The high-tension tank contains additional sections for 60Hz and high frequency filtering, resulting in an operating voltage of 200 kV plus or minus 0.005V, a greater than 10-fold improvement over earlier systems. The monochromator is a single Wien filter design. The energy filter is a Gatan model 866 Tridiem-ERS high resolution GIF spec d for less than or equal to 0.15 eV energy resolution with 29 pA of current in a 2 nm diameter probe. 0.13 eV has already been achieved during early installation. The x-ray detector (EDAX/Genesis 4000) has a take-off angle of 20 degrees, an active area of 30 square millimeters, and a solid angle of 0.3 steradians. The higher solid angle is possible because the objective pole-piece allows the detector to be positioned as close as 9.47 mm from the specimen. The voltage-stabilized HT supply, monochromator and GIF enable high-resolution electron energy-loss spectroscopy (HREELS) with energy resolution comparable to synchrotron XANES, but with approximately 100X better spatial resolution. The region between 0 and 100 eV is called the low-loss or valence electron energy-loss spectroscopy (VEELS) region where features due to collective plasma oscillations and single electron transitions of valence electrons are observed. Most of the low-loss VEELS features we are detecting are being observed for the first time in IDPs. A major focus of our research is to understand the origin and significance of these features and how they might be exploited to gain insight about IDPs and other meteoritic materials.

Sai, Z. R.↗

Pore-Space Partition and Optimization for Propane-Selective High-Performance Propane/Propylene Separation

The development of effective propane (C 3 H 8 )-selective adsorbents for the purification of propylene (C 3 H 6 ) from C 3 H 8 /C 3 H 6 mixture is a promising alternative to replace the energy-intensive cryogenic distillation. However, few materials possess the dual desirable features of propane selectivity and high uptake capacity. Here, we report a family of pore-space-partitioned crystalline porous materials (CPM) with remarkable C 3 H 8 uptake capacity (up to 10.9 mmol/g) and the highly desirable, yet uncommon C 3 H 8 selectivity (up to 1.54 at 0.1 bar and 1.44 at 1bar). The selectivity-capacity synergy endows them with record-performing C 3 H 8 /C 3 H 6 separation potential (i.e., C 3 H 6 recovered from the mixture). Moreover, these CPMs exhibit outstanding properties including high stability, low regeneration energy, and multi-modular chemical and geometrical tunability within the same isoreticular framework. Furthermore, the high C 3 H 8 /C 3 H 6 separation performance was further confirmed by the breakthrough experiments.

36 MATERIALS SCIENCE↗

Effects of external stores on the air combat capability of a delta wing fighter

Delta wing point-design fighters with two pylon mounted missiles and aft tail controls (similar to several Soviet designs) have been investigated for a Mach number range from about 0.6 to 2.0. Whereas minimum drag penalties that are expected with the addition of external stores do occur, the effects at higher lifts, corresponding to maneuvering flight, are less severe and often favorable. The drag-due-to-lift factor is less with stores on although the lift curve slope is unaffected. The longitudinal stability level is reduced by the addition of stores while the pitch control effectiveness is unchanged. The directional stability was generally reduced at subsonic speeds and increased at supersonic speeds by the addition of stores but sufficiently high stability levels are obtainable that are compatible with the longitudinal maneuvering limits. Some examples of the potential maneuvering capability in terms of normal acceleration and turn radius are included.

Spearman, M. L.↗

Additive Runge-Kutta Schemes for Convection-Diffusion-Reaction Equations

Additive Runge-Kutta (ARK) methods are investigated for application to the spatially discretized one-dimensional convection-diffusion-reaction (CDR) equations. First, accuracy, stability, conservation, and dense output are considered for the general case when N different Runge-Kutta methods are grouped into a single composite method. Then, implicit-explicit, N = 2, additive Runge-Kutta ARK2 methods from third- to fifth-order are presented that allow for integration of stiff terms by an L-stable, stiffly-accurate explicit, singly diagonally implicit Runge-Kutta (ESDIRK) method while the nonstiff terms are integrated with a traditional explicit Runge-Kutta method (ERK). Coupling error terms are of equal order to those of the elemental methods. Derived ARK2 methods have vanishing stability functions for very large values of the stiff scaled eigenvalue, z(exp [I]) goes to infinity, and retain high stability efficiency in the absence of stiffness, z(exp [I]) goes to zero. Extrapolation-type stage-value predictors are provided based on dense-output formulae. Optimized methods minimize both leading order ARK2 error terms and Butcher coefficient magnitudes as well as maximize conservation properties. Numerical tests of the new schemes on a CDR problem show negligible stiffness leakage and near classical order convergence rates. However, tests on three simple singular-perturbation problems reveal generally predictable order reduction. Error control is best managed with a PID-controller. While results for the fifth-order method are disappointing, both the new third- and fourth-order methods are at least as efficient as existing ARK2 methods while offering error control and stage-value predictors.

Kennedy, Christopher A.↗

Thin-Film Ceramic Thermocouples Fabricated and Tested

The Sensors and Electronics Technology Branch of the NASA Glenn Research Center is developing thin-film-based sensors for surface measurement in propulsion system research. Thin-film sensors do not require special machining of the components on which they are mounted, and they are considerably thinner than wire- or foil-based sensors. One type of sensor being advanced is the thin-film thermocouple, specifically for applications in high-temperature combustion environments. Ceramics are being demonstrated as having the potential to meet the demands of thin-film thermocouples in advanced aerospace environments. The maximum-use temperature of noble metal thin-film thermocouples, 1500 C (2700 F), may not be adequate for components used in the increasingly harsh conditions of advanced aircraft and next-generation launch vehicles. Ceramic-based thermocouples are known for their high stability and robustness at temperatures exceeding 1500 C, but are typically in the form of bulky rods or probes. As part of ASTP, Glenn's Sensors and Electronics Technology Branch is leading an in-house effort to apply ceramics as thin-film thermocouples for extremely high-temperature applications as part of ASTP. Since the purity of the ceramics is crucial for the stability of the thermocouples, Glenn's Ceramics Branch and Case Western Reserve University are developing high-purity ceramic sputtering targets for fabricating high-temperature sensors. Glenn's Microsystems Fabrication Laboratory, supported by the Akima Corporation, is using these targets to fabricate thermocouple samples for testing. The first of the materials used were chromium silicide (CrSi) and tantalum carbide (TaC). These refractory materials are expected to survive temperatures in excess of 1500 C. Preliminary results indicate that the thermoelectric voltage output of a thin-film CrSi versus TaC thermocouple is 15 times that of the standard type R (platinum-rhodium versus platinum) thermocouple, producing 20 mV with a 200 C temperature gradient. The photograph on the left shows the CrSi-TaC thermocouple in a test fixture at Glenn, and the resulting output signal is shown on the right. The temperature differential across the sample, from the center of the sample inside the oven to the sample mount outside the oven, is measured using a type R thermocouple on the sample.

Wrbanek, John D.↗

Interplay between Intrinsic Thermal Stability and Expansion Properties of Functionalized UiO-67 Metal–Organic Frameworks

The UiO family of metal-organic frameworks (MOFs) has been extensively studied for several applications owing to their high stability rendered by their robust secondary building units. The efficient design and use of these materials require a fundamental understanding of their thermal stability and its impact on chemical and structural functionality. In this work, we provide a detailed characterization of the intrinsic thermal behavior of the UiO-67 and functional analogues, UiO-67-NH 2 and UiO-67-CH 3 . Using in situ temperature-programmed X-ray diffraction, we find that distortion of the carboxylate group on the organic linker leads to negative thermal expansion (NTE) of the UiO-67 MOFs during heating. This NTE behavior is correlated with rich and reversible thermal changes observed in the MOF infrared spectral signature as samples are heated to the sample activation temperature (473 K). We find that in the absence of oxygen, activated UiO-67 samples show higher thermal stability compared to ambient or inert environments, with temperature-programmed desorption revealing an overall stability trend: UiO-67 > UiO-67- CH 3 > UiO-67-NH 2 . Two stages of change are observed during thermal treatment above 473 K, which are directly related to deformation of the inorganic node and the isotropic NTE behavior of these materials. Ultimately, these results provide a real-time interpretation of the fundamental thermoresponsive behavior of UiO-67 MOFs and offer a foundation for accurate interpretation of MOF interactions with guest molecules and their temperature dependence.

36 MATERIALS SCIENCE↗

Thorium chelators for targeted alpha therapy: Rapid chelation of thorium-226

We report one of the main challenges in targeted alpha therapy is assuring delivery of the α-particle dose to the targeted cells. Thus, it is critical to identify ligands for α-emitting radiometals that will form complexes that are very stable, both in vitro and in vivo. In this investigation, thorium-227 (t 1/2 = 18.70 days) chelation of ligands containing hydroxypyridinonate (HOPO) or picolinic acid (pa) moieties and the stability of the resultant complexes were studied. Chelation reactions were followed by reversed-phased HPLC and gamma spectroscopy. Studies revealed that high 227 Th chelation yields could be obtained within 2.5 h or less with ligands containing four Me-3,2-HOPO moieties, 1 (83%) and 2 (65%), and also with ligands containing pa moieties, H 4 octapa 3 (65%) and H 4 py4pa 6 (87%). No reaction occurred with H 4 neunpa-p-Bn-NO 2 4, and the chelation reaction with another pa ligand H 4 pypa 5 gave inconsistent yields with a very broad radio-HPLC peak. The ligands spermine-(Me-3,2-HOPO) 4 1, H 4 octapa 3, and H 4 py4pa 6 had high stability (i.e., 87% of 227 Th still bound to the ligand) in phosphate-buffered saline at room temperature over a 6-day period. Preliminary studies with ligand 6 demonstrated efficient chelation of thorium-226 (t 1/2 = 30.57 min) when heated to 80°C for 5 min.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excalibur: A Nonparametric, Hierarchical Wavelength Calibration Method for a Precision Spectrograph

Excalibur is a nonparametric, hierarchical framework for precision wavelength calibration of spectrographs. It is designed with the needs of extreme-precision radial-velocity (EPRV) instruments in mind, which require calibration or stabilization to better than 10{sup −4} pixels. Instruments vary along only a few dominant degrees of freedom, especially EPRV instruments that feature highly stabilized optical systems and detectors. Excalibur takes advantage of this property by using all calibration data to construct a low-dimensional representation of all accessible calibration states for an instrument. Excalibur also takes advantage of laser-frequency combs or etalons, which generate a dense set of stable calibration points. This density permits the use of a nonparametric wavelength solution that can adapt to any instrument or detector oddities better than parametric models, such as a polynomial. We demonstrate the success of this method with data from the Extreme Precision Spectrograph (EXPRES), which uses a laser-frequency comb. When wavelengths are assigned to laser comb lines using excalibur, the rms of the residuals is about one-fifth that of wavelengths assigned using polynomial fits to individual exposures. Radial-velocity measurements of HD 34411 show a reduction in rms scatter over a 10 month time baseline from 1.17 to 1.05 m s{sup −1}.

47 OTHER INSTRUMENTATION↗

Six-Axis Superconducting Accelerometer

Sensitivity and short-term stability high. Design combines superconductivity and magnetic levitation to achieve linear-acceleration sensitivity greater than conventional linear accelerometers, and short-term angular stability better than conventional gyroscopes. Improved accelerometer used to increase precision in inertial navigation and surveying, as sensitive multiple-axis seismic sensor, as component of tensor gravity gradiometer, or to sense accelerations of stabilized platforms or spacecraft.

Paik, Ho Jung↗

Phase transformation and stabilization of a high strength austenite

An investigation of the phase transformation and the austenite stabilization in a high strength austenite has been made. An Fe-29Ni-4.3Ti austenite age-hardened by gamma-prime (Ni3Ti) precipitates showed a further increase of strength after martensitic and reverse martensitic phase transformations. The stability of ausaged austenite as well as ausaged and transformation-strengthened austenite was improved significantly through an isothermal treatment at 500 C. The Ms temperature of the strengthened austenite was restored to nearly that of annealed austenite while the austenite was hardened to R(C) 41 through precipitation and phase transformations. The observed austenite stabilization is attributed to the formation of GP zones or short-range order of less than about 10A in size.

Jin, S.↗

High-Temperature Air Stability of Electrodeposited Copper Cobalt Oxide and Copper Manganese Oxide Absorber Coatings for Concentrating Solar Power

The solar absorptance of a thermal receiver surface significantly affects the photothermal conversion efficiency of concentrating solar power (CSP) plants. The stability of solar receivers and coatings applied to improve solar absorptance at high temperatures is critical for efficient and long-term operation. This study analyzes the high-temperature air stability of multiscale fractal textured electrodeposited copper manganese oxide and copper cobalt oxide solar receiver coatings over a range of temperatures. The study also investigates the effect of high temperature on phase stability, chemical and morphological evolution, and the optical properties of the two solar absorber materials. A computational model is developed to determine the absorptance of the textured absorbers and is shown to match the experimental measurements closely over a range of heat treatment temperatures from 450 °C to 850 °C and durations up to 100 h. Degradation curves and coating stability maps are developed from the study. Copper manganese oxide and copper cobalt oxide coatings exhibit good thermal stability up to ~815 °C and 630 °C, respectively, with minimal changes in their optical and structural properties with thermal efficiency greater than 90%. Furthermore, the study offers valuable insights into the high-temperature annealing effects on the optical and structural properties of multiscale copper alloyed coatings fabricated by electrodeposition and presents a means of designing the optimal temperature range for maximizing absorber efficiency in practical applications.

14 SOLAR ENERGY↗

Platinum/Tantalum Carbide Core–Shell Nanoparticles with Sub‐Monolayer Shells for Methanol and Oxygen Electrocatalysis

Abstract Core–shell architectures provide great opportunities to improve catalytic activity, but achieving nanoparticle stability under electrochemical cycling remains challenging. Herein, core–shell nanoparticles comprising atomically thin Pt shells over earth‐abundant TaC cores are synthesized and used as highly durable electrocatalysts for the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) needed to drive direct methanol fuel cells (DMFCs). Characterization data show that a thin oxidic passivation layer protects the TaC core from undergoing dissolution in the fuel cell‐relevant potential range, enabling the use of partially covered Pt/TaC core–shell nanoparticles for MOR and ORR with high stability and enhanced catalytic performance. Specifically, at the anode the surface‐oxidized TaC further enhances MOR activity compared to conventional Pt nanoparticles. At the cathode, the Pt/TaC catalyst feature increases tolerance to methanol crossover. These results show unique synergistic advantages of the core–shell particles and open opportunities to tailor catalytic properties for electrocatalytic reactions.

Chemistry↗

Solvent‐free Synthesis of Multi‐Module Pore‐Space‐Partitioned Metal‐Organic Frameworks for Gas Separation

Abstract Multi‐module design of framework materials with multiple distinct building blocks has attracted much attention because such materials are more amenable to compositional and geometrical tuning and thus offer more opportunities for property optimization. Few examples are known that use environmentally friendly and cost‐effective solvent‐free method to synthesize such materials. Here, we report the use of solvent‐free method (also modulator‐free) to synthesize a series of multi‐module MOFs with high stability and separation property for C 2 H 2 /CO 2 . The synthesis only requires simple mixing of reactants and short reaction time (2 h). Highly porous and stable materials can be made without any post‐synthetic activation. The success of solvent‐free synthesis of multi‐module MOFs reflects the synergy between different modules, resulting in stable pore‐partitioned materials, despite the fact that other competitive crystallization pathways with simpler framework compositions also exist.

Xiao, Yuchen↗

Solvent–free Synthesis of Multi–Module Pore–Space–Partitioned Metal–Organic Frameworks for Gas Separation

Multi-module design of framework materials with multiple distinct building blocks has attracted much attention because such materials are more amenable to compositional and geometrical tuning and thus offer more opportunities for property optimization. Few examples are known that use environmentally friendly and cost-effective solvent-free method to synthesize such materials. Here, we report the use of solvent-free method (also modulator-free) to synthesize a series of multi-module MOFs with high stability and separation property for C 2 H 2 /CO 2 . The synthesis only requires simple mixing of reactants and short reaction time (2 h). Highly porous and stable materials can be made without any post-synthetic activation. Here, the success of solvent-free synthesis of multi-module MOFs reflects the synergy between different modules, resulting in stable pore-partitioned materials, despite the fact that other competitive crystallization pathways with simpler framework compositions also exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation-Resistant Photon-Counting Detector Package Providing Sub-ps Stability for Laser Time Transfer in Space

We are reporting on a design, construction and performance of photon-counting detector packages based on silicon avalanche photodiodes. These photon-counting devices have been optimized for extremely high stability of their detection delay. The detectors have been designed for future applications in fundamental metrology and optical time transfer in space. The detectors have been qualified for operation in space missions. The exceptional radiation tolerance of the detection chip itself and of all critical components of a detector package has been verified in a series of experiments.

radiation hardness↗