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DOE OSTI2024

Phase Transformation Driven by Oxygen Vacancy Redistribution as the Mechanism of Ferroelectric Hf 0.5 Zr 0.5 O 2 Fatigue

As a promising candidate for nonvolatile memory devices, the hafnia-based ferroelectric system has recently been a hot research topic. Although significant progress has been made over the past decade, the endurance problem is still an obstacle to its final application. In perovskite-based ferroelectrics, such as the well-studied Pb[Zr x Ti 1-x ]O 3 (PZT) family, polarization fatigue has been discussed within the framework of the interaction of charged defects (such as oxygen vacancies) with the moving domains during the switching process, particularly at the electrode-ferroelectric interface. Armed with this background, a hypothesis is set out to test that a similar mechanism can be in play with the hafnia-based ferroelectrics. The conducting perovskite La-Sr-Mn-O is used as the contact electrode to create La 0.67 Sr 0.33 MnO 3 / Hf 0.5 Zr 0.5 O 2 (HZO)/ La 0.67 Sr 0.33 MnO 3 capacitor structures deposited on SrTiO 3 -Si substrates. Nanoscale X-ray diffraction is performed on single capacitors, and a structural phase transition from polar o-phase toward non-polar m-phase is demonstrated during the bipolar switching process. The energy landscape of multiphase HZO has been calculated at varying oxygen vacancy concentrations. Based on both theoretical and experimental results, it is found that a polar to non-polar phase transformation caused by oxygen vacancy redistribution during electric cycling is a likely explanation for fatigue in HZO.

36 MATERIALS SCIENCE↗

DOE OSTI2019

LANL Phase 3 Test Plan For Container Loading to Support the Fire-Induced Pressure Response and Failure Characterization of PCV/SCV/3013 Containers

Fire testing of 3013 containers loaded with surrogate materials and water will be conducted to determine the response of 3013 containers stored in K-Area Complex (KAC) to a facility fire. Based on the proposal for the test configuration and loading, the objectives of the fire test are as follows: 1. “To increase understanding about the pressure and temperature conditions at which failure occurs; 2. To determine the allowable moisture for which failure will not occur under specified fire conditions, and 3. To increase understanding regarding the effects of salts on the pressurization, corrosion, and potential failure of the container.” Surrogate materials will be prepared at Los Alamos National Laboratory (LANL) and loaded in the 3013 containers. The containers will then be welded at LANL and shipped to Savannah River Site (SRS) for the installation of fittings and leak testing.

42 ENGINEERING↗

NASA NTRS1970

Hypersonic research engine project. Phase 2: Aerothermodynamic integration model development

The analytical effort was directed towards (1) completing the design of the combustor exit instrumentation assembly, (2) analyzing the coolant flow distribution of the cowl leading edge tip section, (3) determining effects of purge gas pressure on AIM performance analysis, and (4) analyzing heat transfer and associated stress problems related to the cowl leading edge tip section and the nozzle shroud assembly for test conditions.

Jilly, L. F.↗

DOE OSTI2020

Promoting the cleavage of C-O bonds at the interface between a metal oxide cluster and a Co(0001) support

As a first step toward the rational design of Co-based catalysts with a higher activity and selectivity, we determine how one can activate a C-O bond at the interface between a metal oxide cluster and a Co(0001) support. The hypothesis here is that the metal ions in metal oxide clusters on a Co(0001) support enhance the adsorption of CO and weaken the C-O bond strength, which can then facilitate the dissociation of the CO reactant. To test this hypothesis, we developed three computational models of Ti4O8/Co(0001), Zr4O8/Co(0001), and Mn8O8/Co(0001). We quantify the CO adsorption behavior at the interface sites between an oxide cluster and the Co(0001) support as well as the corresponding IR spectra. We correlate the computed CO stretch frequencies with their CO adsorption energies, as well as the CO stretch frequency with the C-O bond length, and related these findings to the changes in the chemical bonding in the bound CO. The interface is the most favorable site for CO adsorption. Adsorption results in an increase of the C-O bond length and a decrease in its vibrational frequency. From a chemical bonding analysis, the bond order in CO at this site drops from 3 (in the gas phase) to 1. This decrease in bond order is a necessary precursor stage for CO dissociation. The experimental measurements of the corresponding FTIR spectra support this point. The favorability of CO adsorption at the interface sites is due to an electron transfer from the metal ion in the metal oxide cluster to the O atom in CO. We establish a linear relationship between C-O bond length and CO frequency and this relationship is found to be independent of the support, type of metal oxide cluster, or the adsorption site.

Fischer-Tropsch Synthesis, Heterogeneous Catalysis↗

DOE OSTI2024

A $C^1$-Conforming Arbitrary-Order Two-Dimensional Virtual Element Method for the Fourth-Order Phase-Field Equation

We present a two-dimensional conforming virtual element method for the fourth-order phase-field equation. Our proposed numerical approach to the solution of this high-order phase-field (HOPF) equation relies on the design of an arbitrary-order accurate, virtual element space with $C^1$ global regularity. Such regularity is guaranteed by taking the values of the virtual element functions and their full gradient at the mesh vertices as degrees of freedom. Attaining high-order accuracy requires also edge polynomial moments of the trace of the virtual element functions and their normal derivatives. In this work, we detail the scheme construction, and prove its convergence by deriving error estimates in different norms. A set of representative test cases allows us to assess the behavior of the method.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1976

Flight service evaluation of an advanced composite empennage component on commercial transport aircraft. Phase 1: Engineering development

The empennage component selected for this program is the vertical fin box of the L-1011 aircraft. The box structure extends from the fuselage production joint to the tip rib and includes the front and rear spars. Various design options were evaluated to arrive at a configuration which would offer the highest potential for satisfying program objectives. The preferred configuration selected consists of a hat-stiffened cover with molded integrally stiffened spars, aluminum trussed composite ribs, and composite miniwich web ribs with integrally molded caps. Material screening tests were performed to select an advanced composite material system for the Advanced Composite Vertical Fin (ACFV) that would meet the program requirements from the standpoint of quality, reproducibility, and cost. Preliminary weight and cost analysis were made, targets established, and tracking plans developed. These include FAA certification, ancillary test program, quality control, and structural integrity control plans.

Ary, A.↗

NASA NTRS1989

Thermal barrier coating life prediction model development, phase 1

The objective of this program was to establish a methodology to predict thermal barrier coating (TBC) life on gas turbine engine components. The approach involved experimental life measurement coupled with analytical modeling of relevant degradation modes. Evaluation of experimental and flight service components indicate the predominant failure mode to be thermomechanical spallation of the ceramic coating layer resulting from propagation of a dominant near interface crack. Examination of fractionally exposed specimens indicated that dominant crack formation results from progressive structural damage in the form of subcritical microcrack link-up. Tests conducted to isolate important life drivers have shown MCrAlY oxidation to significantly affect the rate of damage accumulation. Mechanical property testing has shown the plasma deposited ceramic to exhibit a non-linear stress-strain response, creep and fatigue. The fatigue based life prediction model developed accounts for the unusual ceramic behavior and also incorporates an experimentally determined oxide rate model. The model predicts the growth of this oxide scale to influence the intensity of the mechanic driving force, resulting from cyclic strains and stresses caused by thermally induced and externally imposed mechanical loads.

Demasi, Jeanine T.↗

DOE OSTI2018

Study of Material Compatibility for a Thermal Energy Storage System with Phase Change Material

The suitability of stainless steel 316L and Inconel 625 for use in a latent heat thermal energy storage (TES) system was investigated. A NaCl–NaF eutectic mixture with a melting temperature of 680 °C was used as the phase change material (PCM). Containers were filled with the PCM prior to heating to 750 °C, then examined after 100 and 2500 h of high-temperature exposure by analyzing the material surface and cross-section areas. A small amount of corrosion was present in both samples after 100 h. Neither sample suffered significant damage after 2500 h. The undesirable inter-granular grain boundary attack found in SS316L samples was in the order of 1–2 µm in depth. On Inconel 625 sample surface, an oxide complex formed, resisting material dissolution into the PCM. The surface morphology of tested samples remained largely unchanged after 2500 h, but the corrosion pattern changed from an initially localized corrosion penetration to a more uniform type. After 2500 h, the corrosion depth of Inconel 625 remained at roughly 1–2 µm, indicating that the corrosion rate decelerated. Both materials demonstrated good compatibility with the chosen NaF–NaCl eutectic salt, but the low corrosion activity in Inconel 625 samples shows a performance advantage for long term operation.

25 ENERGY STORAGE↗

DOE OSTI2024

Understanding EBC Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. The goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aero-turbine applications. To provide data for the lifetime model, laboratory testing used plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air-steam environments and reaction kinetics were assessed from 700°-1350°C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

Ridley, Mackenzie↗

DOE OSTI2023

Aculeaxanthones A–E, new xanthones from the marine-derived fungus Aspergillus aculeatinus WHUF0198

Introduction Dimeric natural products are widespread in plants and microorganisms, which usually have complex structures and exhibit greater bioactivities than their corresponding monomers. In this study, we report five new dimeric tetrahydroxanthones, aculeaxanthones A−E ( 4−8 ), along with the homodimeric tetrahydroxanthone secalonic acid D ( 1 ), chrysoxanthones B and C ( 2 and 3 ), and 4−4’-secalonic acid D ( 9 ), from different fermentation batches of the title fungus. Methods A part of the culture was added to a total of 60 flasks containing 300 ml each of number II fungus liquid medium and culture 4 weeks in a static state at 28˚C. The liquid phase (18 L) and mycelia was separated from the fungal culture by filtering. A crude extract was obtained from the mycelia by ultrasound using acetone. To obtain a dry extract (18 g), the liquid phase combined with the crude extract were further extracted by EtOAc and concentrated in vacuo. The MIC of anaerobic bacteria was examined by a broth microdilution assay. To obtain MICs for aerobic bacteria, the agar dilution streak method recommended in Clinical and Laboratory Standards Institute document (CLSI) M07-A10 was used. Compounds 1−9 was tested against the Bel-7402, A-549 and HCT-116 cell lines according to MTT assay. Results and Discussion The structures of these compounds were elucidated on the base of 1D and 2D NMR and HR-ESIMS data, and the absolute configurations of the new xanthones 4−8 were determined by conformational analysis and time-dependent density functional theory-electronic circular dichroism (TDDFT-ECD) calculations. Compounds 1–9 were tested for cytotoxicity against the Bel-7402, A549, and HCT-116 cancer cell lines. Of the dimeric tetrahydroxanthone derivatives, only compound 6 provided cytotoxicity effect against Bel-7402 cell line (IC50, 1.96 µM). Additionally, antimicrobial activity was evaluated for all dimeric tetrahydroxanthones, including four Gram-positive bacteria including Enterococcus faecium ATCC 19434, Bacillus subtilis 168, Staphylococcus aureus ATCC 25923 and MRSA USA300; four Gram-negative bacteria, including Helicobacter pylori 129, G27, as well as 26,695, and multi drug-resistant strain H. pylori 159, and one Mycobacterium M. smegmatis ATCC 607. However, only compound 1 performed activities against H. pylori G27, H. pylori 26695, H. pylori 129, H. pylori 159, S. aureus USA300, and B. subtilis 168 with MIC values of 4.0, 4.0, 2.0, 2.0, 2.0 and 1.0 μg/mL, respectively.

Wu, Jun↗

NASA NTRS1976

Detailed design specification for the ALT Shuttle Information Extraction Subsystem (SIES)

The approach and landing test (ALT) shuttle information extraction system (SIES) is described in terms of general requirements and system characteristics output products and processing options, output products and data sources, and system data flow. The ALT SIES is a data reduction system designed to satisfy certain data processing requirements for the ALT phase of the space shuttle program. The specific ALT SIES data processing requirements are stated in the data reduction complex approach and landing test data processing requirements. In general, ALT SIES must produce time correlated data products as a result of standardized data reduction or special purpose analytical processes. The main characteristics of ALT SIES are: (1) the system operates in a batch (non-interactive) mode; (2) the processing is table driven; (3) it is data base oriented; (4) it has simple operating procedures; and (5) it requires a minimum of run time information.

Clouette, G. L.↗

NASA NTRS1986

Advanced optical smoke meters for jet engine exhaust measurement

Smoke meters with increased sensitivity, improved accuracy, and rapid response are needed to measure the smoke levels emitted by modern jet engines. The standard soiled tape meter in current use is based on filtering, which yields long term averages and is insensitive to low smoke levels. Two new optical smoke meter techniques that promise to overcome these difficulties have been experimentally evaluated: modulated transmission (MODTRAN) and photothermal deflection spectroscopy (PDS). Both techniques are based on light absorption by smoke, which is closely related to smoke density. They are variations on direct transmission measurements which produce a modulated signal that can be easily measured with phase sensitive detection. The MODTRAN and PDS techniques were tested on low levels of smoke and diluted samples of NO2 in nitrogen, simulating light adsorption due to smoke. The results are evaluated against a set of ideal smoke meter criteria that include a desired smoke measurement range of 0.1 to 12 mg cu.m. (smoke numbers of 1 to 50) and a frequency response of 1 per second. The MODTRAN instrument is found to be inaccurate for smoke levels below 3 mg/cu.m. and is able to make a only about once every 20 seconds because of its large sample cell. The PDS instrument meets nearly all the characteristics of an ideal smoke meter: it has excellent sensitivity over a range of smoke levels from 0.1 to 20 mg/cu.m. (smoke numbers of 1 to 60) and good frequency response (1 per second).

Pitz, R. W.↗

NASA NTRS1990

Rapid mix concepts for low emission combustors in gas turbine engines

NASA LeRC has identified the Rich burn/Quick mix/Lean burn (RQL) combustor as a potential gas turbine combustor concept to reduce NOx emissions in High Speed Civil Transport (HSCT) aircraft. To demonstrate reduced NOx levels, NASA LeRC soon will test a flametube version of an RQL combustor. The critical technology needed for the RQL combustor is a method of quickly mixing combustion air with rich burn gases. Two concepts were proposed to enhance jet mixing in a circular cross-section: the Asymmetric Jet Penetration (AJP) concept; and the Lobed Mixer (LM) concept. In Phase 1, two preliminary configurations of the AJP concept were compared with a conventional 12-jet radial-inflow slot design. The configurations were screened using an advanced 3-D Computational Fluid Dynamics (CFD) code named REFLEQS. Both non-reacting and reacting analyses were performed. For an objective comparison, the conventional design was optimized by parametric variation of the jet-to-mainstream momentum flux (J) ratio. The optimum J was then employed in the AJP simulations. Results showed that the three-jet AJP configuration was superior in overall mixedness compared to the conventional design. However, in regards to NOx emissions, the AJP configuration was inferior. The higher emission level for AJP was caused by a single hot spot located in the wake of the central jet as it entered the combustor. Ways of maintaining good mixedness while eliminating the hot spot were identified for Phase 2 study. Overall, Phase 1 showed the viability of using CFD analyses to evaluate quick-mix concepts. A high probability exists that advancing mixing concepts will reduce NOx emissions in RQL combustors, and should be explored in Phase 2, by parallel numerical and experimental work.

Talpallikar, Milind V.↗

NASA NTRS2005

Space-Based Telemetry and Range Safety Project Ku-Band and Ka-Band Phased Array Antenna

The National Aeronautics and Space Administration Space-Based Telemetry and Range Safety study is a multiphase project to increase data rates and flexibility and decrease costs by using space-based communications assets for telemetry during launches and landings. Phase 1 used standard S-band antennas with the Tracking and Data Relay Satellite System to obtain a baseline performance. The selection process and available resources for Phase 2 resulted in a Ku-band phased array antenna system. Several development efforts are under way for a Ka-band phased array antenna system for Phase 3. Each phase includes test flights to demonstrate performance and capabilities. Successful completion of this project will result in a set of communications requirements for the next generation of launch vehicles.

Whiteman, Donald E.↗

NASA NTRS2005

Ku- and Ka-Band Phased Array Antenna for the Space-Based Telemetry and Range Safety Project

Whiteman, Donald E.↗

NASA NTRS2006

NASA's PEM Fuel Cell Power Plant Development Program for Space Applications

NASA embarked on a PEM fuel cell power plant development program beginning in 2001. This five-year program was conducted by a three-center NASA team of Glenn Research Center (lead), Johnson Space Center, and Kennedy Space Center. The program initially was aimed at developing hardware for a Reusable Launch Vehicle (RLV) application, but more recently had shifted to applications supporting the NASA Exploration Program. The first phase of the development effort, to develop breadboard hardware in the 1-5 kW power range, was conducted by two competing vendors. The second phase of the effort, to develop Engineering Model hardware at the 10 kW power level, was conducted by the winning vendor from the first phase of the effort. Both breadboard units and the single engineering model power plant were delivered to NASA for independent testing. This poster presentation will present a summary of both phases of the development effort, along with a discussion of test results of the PEM fuel cell engineering model under simulated mission conditions.

Hoberecht, Mark↗

NASA NTRS2010

CECE: Expanding the Envelope of Deep Throttling in Liquid Oxygen/Liquid Hydrogen Rocket Engines For NASA Exploration Missions

As one of the first technology development programs awarded by NASA under the Vision for Space Exploration, the Pratt & Whitney Rocketdyne (PWR) Deep Throttling, Common Extensible Cryogenic Engine (CECE) program was selected by NASA in November 2004 to begin technology development and demonstration toward a deep throttling, cryogenic engine supporting ongoing trade studies for NASA s Lunar Lander descent stage. The CECE program leverages the maturity and previous investment of a flight-proven hydrogen/oxygen expander cycle engine, the PWR RL10, to develop technology and demonstrate an unprecedented combination of reliability, safety, durability, throttlability, and restart capabilities in a high-energy cryogenic engine. The testbed selected for the deep throttling demonstration phases of this program was a minimally modified RL10 engine, allowing for maximum current production engine commonality and extensibility with minimum program cost. Three series of demonstrator engine tests, the first in April-May 2006, the second in March-April 2007 and the third in November-December 2008, have demonstrated up to 13:1 throttling (104% to 8% thrust range) of the hydrogen/oxygen expander cycle engine. The first two test series explored a propellant feed system instability ("chug") environment at low throttled power levels. Lessons learned from these two tests were successfully applied to the third test series, resulting in stable operation throughout the 13:1 throttling range. The first three tests have provided an early demonstration of an enabling cryogenic propulsion concept, accumulating over 5,000 seconds of hot fire time over 27 hot fire tests, and have provided invaluable system-level technology data toward design and development risk mitigation for the NASA Altair and future lander propulsion system applications. This paper describes the results obtained from the highly successful third test series as well as the test objectives and early results obtained from a fourth test series conducted over March-May 2010

Giuliano, Victor J.↗

NASA NTRS2012

Highlights from a Mach 4 Experimental Demonstration of Inlet Mode Transition for Turbine-Based Combined Cycle Hypersonic Propulsion

NASA is focused on technologies for combined cycle, air-breathing propulsion systems to enable reusable launch systems for access to space. Turbine Based Combined Cycle (TBCC) propulsion systems offer specific impulse (Isp) improvements over rocket-based propulsion systems in the subsonic takeoff and return mission segments along with improved safety. Among the most critical TBCC enabling technologies are: 1) mode transition from the low speed propulsion system to the high speed propulsion system, 2) high Mach turbine engine development and 3) innovative turbine based combined cycle integration. To address these challenges, NASA initiated an experimental mode transition task including analytical methods to assess the state-of-the-art of propulsion system performance and design codes. One effort has been the Combined-Cycle Engine Large Scale Inlet Mode Transition Experiment (CCE-LIMX) which is a fully integrated TBCC propulsion system with flowpath sizing consistent with previous NASA and DoD proposed Hypersonic experimental flight test plans. This experiment was tested in the NASA GRC 10 by 10-Foot Supersonic Wind Tunnel (SWT) Facility. The goal of this activity is to address key hypersonic combined-cycle engine issues including: (1) dual integrated inlet operability and performance issues-unstart constraints, distortion constraints, bleed requirements, and controls, (2) mode-transition sequence elements caused by switching between the turbine and the ramjet/scramjet flowpaths (imposed variable geometry requirements), and (3) turbine engine transients (and associated time scales) during transition. Testing of the initial inlet and dynamic characterization phases were completed and smooth mode transition was demonstrated. A database focused on a Mach 4 transition speed with limited off-design elements was developed and will serve to guide future TBCC system studies and to validate higher level analyses.

Foster, Lancert E.↗