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Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

aqueous phase reactions↗

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

FINAL REPORT - Development of High Pressure Hydrogen Storage Tank for Storage and Gaseous Truck Delivery

The “Development of High Pressure Hydrogen Storage Tanks for Storage and Gaseous Truck Delivery” project [DE-FG36-08GO18062] was initiated on 01 July 2008. Hexagon Lincoln (then Lincoln Composites) received grant funding from the U.S. Department of Energy to support the design and development of an improved bulk hauling and storage solution for hydrogen in terms of cost, safety, weight and volumetric efficiency. The development of this capability required parallel development and qualification of large all-composites pressure vessels, a custom ISO container to transport and store said tanks, and performance of trade studies to identify optimal operating pressure for the system. Qualification of the 250 bar TITAN® module was completed in 2009 with supervision from the American Bureau of Shipping [ABS], and the equipment has been used internationally for bulk transportation of fuel gases since 2010. Phase 1 of the project was successfully completed in 2012 with the issuance of USDOT SP 14951, the special permit authorizing the manufacture, marking, sale and use of TITAN® Mobile Pipeline® equipment in the United States. The introduction of tube trailers with light weight composite tankage has meant that 2 to 3 times as much gaseous fuel can be transported with each trip. This increased hauling efficiency offers dramatically reduced operating costs and has enabled a profitable business model for over-the-road compressed natural gas delivery. The economic drivers of this business opportunity vary from country to country and region to region, but in many places gas distribution companies have realized profitable operations. Additional testing was performed in 2015 to characterize hydrogen-specific operating protocols for use of TITAN® systems in CHG service at 250 bar. This program demonstrated that existing compression and decompression methodologies can efficiently and safely fill and unload lightweight bulk hauling systems. Hexagon Lincoln and U.S. DOE agreed to continue into Phase 2 of the project without pursuing the development of higher pressure capabilities as originally planned. At 250 bar, development of equipment for hydrogen transport is supported by strong activity in the adjacent natural gas transportation sector. Trade studies performed since 2011 indicate optimization of hauling efficiency and system cost for hydrogen transport at about 350 bar (5076 psi). However, due to reduced efficiency of compression of natural gas above 250 bar, 350 bar operation is not an attractive option for natural gas transportation. The CHG market is not developed at this time, and it is difficult to forecast the arrival of significant revenues. On the investment side, the cost to fully qualify a large tank module at 350 bar is estimated at $3MM to $5MM. There is insufficient CHG market definition to support a stand-alone business case for this investment without near term revenue in the adjacent CNG transportation market. Therefore development of a 350 bar TITAN® system was deferred and not pursued under this project. Hexagon Lincoln continues to support the development of tankage and equipment for operation at 350 bar and above; with 700 bar vehicle tanks and 950 bar tanks for ground storage applications. Phase 2 activities were focused on reducing system cost, increasing system capacity, increasing system safety and characterization of polymer material performance specific to hydrogen pressure vessel usage. With the successful launch of TITAN® modules and trailers in natural gas transportation, over 600 units have been produced through the end of 2016, resulting in improved purchasing power for raw materials and manufactured components. This has allowed Hexagon Lincoln to approach the current project goals for system cost. At $590/kg of compressed hydrogen delivered, the system cost of the baseline TITAN® module is below the project’s 2015 target of $730/kg H2 delivered, and very close to the project’s 2020 target of $575/kg H2 delivered. [Based on product pricing in 1Q2017.] Emphasis was placed on configuration of larger capacity systems within the vehicle weights and dimensions allowed on federal and state highways in the United States and other countries. These activities resulted in the design and development of integrated tube trailer systems that have increased delivery capacities by 45%. The hydrogen delivery capacity of our largest system is 845 kg, exceeding the project’s 2015 target of 700 kg H2 delivered. Emerging technologies offering improvement of the safety systems used on the equipment were investigated, with particular focus on improving the reliability and cost of the emergency venting system for fire protection. Finally, investment in our materials laboratory improved detection and characterization of hydrogen-induced damage in polymer materials, supporting the development of operational protocols to avoid damage to pressure vessel liners and valve components.

08 HYDROGEN↗

The PROSPECT physics program

The precision reactor oscillation and spectrum experiment, PROSPECT, is designed to make a precise measurement of the antineutrino spectrum from a highly-enriched uranium reactor and probe eV-scale sterile neutrinos by searching for neutrino oscillations over a distance of several meters. The subject of this paper, PROSPECT, is conceived as a 2-phase experiment utilizing segmented 6 Li-doped liquid scintillator detectors for both efficient detection of reactor antineutrinos through the inverse beta decay reaction and excellent background discrimination. PROSPECT Phase I consists of a movable 3 ton antineutrino detector at distances of 7–12 m from the reactor core. It will probe the best-fit point of the ν e disappearance experiments at 4σ in 1 year and the favored region of the sterile neutrino parameter space at > 3σ in 3 years. With a second antineutrino detector at 15–19 m from the reactor, Phase II of PROSPECT can probe the entire allowed parameter space below 10 eV 2 at 5σ in 3 additional years. Finally, the measurement of the reactor antineutrino spectrum and the search for short-baseline oscillations with PROSPECT will test the origin of the spectral deviations observed in recent θ 13 experiments, search for sterile neutrinos, and conclusively address the hypothesis of sterile neutrinos as an explanation of the reactor anomaly.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Impact of window temperature variations on ITER toroidal interferometer and polarimeter (TIP) measurements

Abstract The toroidal interferometer and polarimeter (TIP) is one of the primary electron density diagnostics on ITER. To meet measurement requirements over several thousand seconds, environmental factors such as changes in the window temperature, air temperature, and humidity, which can cause uncompensated phase drifts, must be minimized. This paper reports measurements of the phase shift induced by ZnSe and BaF₂ windows as their temperature is varied utilizing the TIP prototype. To accomplish these measurements, test pieces of BaF₂ and ZnSe are placed in a small oven that is located in one leg of the 10.59/5.22 micron two-color interferometer TIP prototype. The oven temperature was varied from room temperature to ∼90 °C, which is slightly higher than the expected window temperatures on ITER. The vibration compensated phase shifts measured for these two materials are dϕᵥ꜀ /dT/L = 0.0121 and −0.275 deg. /°C/cm −1 for BaF₂ and ZnSe, respectively. From these measurements, it was concluded that temperature variations of the environmental/secondary confinement barrier window and primary vacuum window have to be suppressed within approximately 1°C and 2°C, respectively, in order to passively meet the electron density measurement requirements in ITER.

Akiyama, T (ORCID:0000000198469795)↗

Combustion of liquid fuels in a flowing combustion gas environment at high pressures

The combustion of fuel droplets in gases which simulate combustion chamber conditions was considered both experimentally and theoretically. The fuel droplets were simulated by porous spheres and allowed to gasify in combustion gases produced by a burner. Tests were conducted for pressures of 1-40 atm, temperatures of 600-1500 K, oxygen concentrations of 0-13% (molar) and approach Reynolds numbers of 40-680. The fuels considered in the tests included methanol, ethanol, propanol-1, n-pentane, n-heptane and n-decane. Measurements were made of both the rate of gasification of the droplet and the liquid surface temperature. Measurements were compared with theory, involving various models of gas phase transport properties with a multiplicative correction for the effect of forced convection.

Canada, G. S.↗

Technology advancement of the static feed water electrolysis process

A program to advance the technology of oxygen- and hydrogen-generating subsystems based on water electrolysis was studied. Major emphasis was placed on static feed water electrolysis, a concept characterized by low power consumption and high intrinsic reliability. The static feed based oxygen generation subsystem consists basically of three subassemblies: (1) a combined water electrolysis and product gas dehumidifier module; (2) a product gas pressure controller and; (3) a cyclically filled water feed tank. Development activities were completed at the subsystem as well as at the component level. An extensive test program including single cell, subsystem and integrated system testing was completed with the required test support accessories designed, fabricated, and assembled. Mini-product assurance activities were included throughout all phases of program activities. An extensive number of supporting technology studies were conducted to advance the technology base of the static feed water electrolysis process and to resolve problems.

Schubert, F. H.↗

Reliable thermodynamic estimators for screening caloric materials

Reversible, diffusionless, first-order solid-solid phase transitions accompanied by caloric effects are critical for applications in the solid-state cooling and heat-pumping devices. Accelerated discovery of caloric materials requires reliable but faster estimators for predictions and high-throughput screening of system-specific dominant caloric contributions. We assess reliability of the computational methods that provide thermodynamic properties in relevant solid phases at or near a phase transition. Here, we test the methods using the well-studied B2 FeRh alloy as a “fruit fly” in such a materials genome discovery, as it exhibits a metamagnetic transition which generates multicaloric (magneto-, elasto-, and baro-caloric) responses. For lattice entropy contributions, we find that the commonly-used linear-response and small-displacement phonon methods are invalid near instabilities that arise from the anharmonicity of atomic potentials, and we offer a more reliable and precise method for calculating lattice entropy at a fixed temperature. Then, we apply a set of reliable methods and estimators to the metamagnetic transition in FeRh (predicted 346 ± 12 K, observed 353 ± 1 K) and calculate the associated caloric properties, such as isothermal entropy and isentropic temperature changes.

36 MATERIALS SCIENCE↗

Solar Thermochemical Redox Cycling Using Ga- and Al-Doped LSM Perovskites for Renewable Hydrogen Production

Solar thermochemical hydrogen production using redox-active metal oxides is a promising pathway for the production of green hydrogen and synthetic fuel precursors. Herein, the perovskite material (La 0.6 Sr 0.4 ) 0.95 Mn 0.8 Ga 0.2 O 3–δ (LSMG6482) is identified as a promising metal oxide for thermochemical water splitting. LSMG6482, along with more-established water splitters ceria and (La 0.6 Sr 0.4 ) 0.95 Mn x Al 1–x O 3–δ (LSMA) perovskites, is experimentally characterized via thermogravimetric (TGA) analysis and high-temperature water splitting in a reactor simulating solar concentrating conditions. TGA analysis demonstrated that LSMG6482 has high and stable oxygen exchange capacity under controlled pO 2 redox cycling, demonstrated by large changes in oxygen nonstoichiometry (δ) relative to ceria. Water splitting experiments using laser heating (T red = 1400 °C, T ox = 1200 °C) resulted in H 2 yields of 165.1 μmol g –1 for the candidate LSMG6482 composition, exceeding that of all benchmark materials tested. Under high conversion oxidation conditions, where H 2 is cointroduced with H 2 O (150 ≤ nH 2 O/nH 2 ≤ 500), H 2 yields were greatest for LSMG6482 and LSMA6482, up to four times that of ceria at the highest nH 2 O/nH 2 conditions. Crystallographic analysis showed that over the course of experimentation, there is some secondary phase growth for all perovskite compositions, except for LSMA6482, but there was no observable degradation in H 2 yields.

08 HYDROGEN↗

Realistic operation of two residential cordwood-fired outdoor hydronic heater appliances—Part 3: Optical properties of black and brown carbon emissions

Residential biomass combustion is a source of carbonaceous aerosol. Inefficient combustion, particularly of solid fuels produces large quantities of black and brown carbon (BC and BrC). These particle types are important as they have noted effects on climate forcing and human health. One method of measuring these quantities is by measurement of aerosol light-absorption and scattering, which can be performed using an aethalometer and nephelometer, respectively. These instruments are widely deployed in the study of ambient air and are frequently used in air quality modeling and source apportionment studies. In this study, we will describe (1) a method for measuring primary BC and BrC emissions from two residential log-fired wood hydronic heaters and (2) the BC and BrC emission from these devices over a wide range of operating conditions, such as cold-starts, warm-starts, four different levels of output ranging from 15% to 100% maximum rated output, and periods of repeated cycling. The range in flue-gas BC concentrations, measured using an aethalometer at the 880 nanometer (nm) wavelength, were between 5.09 × 10 2 and 2.24 × 10 4 micrograms per cubic meter (µg/m 3 ) while the scattering coefficient of the flue-gas, measured by a nephelometer at 880 nm, ranged between 2.20 × 10 3 and 8.56 × 10 5 inverse megameters (Mm –1 ). The BrC concentrations, measured using the 370 nm wavelength of an aethalometer, were between 9.10 × 10 1 and 3.56 × 10 4 µg/m 3 . The calculated Angstrom Absorption Exponent (AAE) of the flue-gas aerosol ranged between 1.54 and 3.63. Performing a comparison between the measured BC concentration and an external particulate matter (PM) concentration showed that overall BC makes up roughly a quarter of the PM emitted by either of the two appliances. Further for both appliances, the cold-start and the test phase immediately following it had the highest BC and BrC concentrations, the highest measured scattering coefficient, as well as a low AAE.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Technical Note: PLASTIMATCH MABS, an open source tool for automatic image segmentation

Purpose: Multiatlas based segmentation is largely used in many clinical and research applications. Due to its good performances, it has recently been included in some commercial platforms for radiotherapy planning and surgery guidance. Anyway, to date, a software with no restrictions about the anatomical district and image modality is still missing. In this paper we introduce PLASTIMATCH MABS, an open source software that can be used with any image modality for automatic segmentation. Methods: PLASTIMATCH MABS workflow consists of two main parts: (1) an offline phase, where optimal registration and voting parameters are tuned and (2) an online phase, where a new patient is labeled from scratch by using the same parameters as identified in the former phase. Several registration strategies, as well as different voting criteria can be selected. A flexible atlas selection scheme is also available. To prove the effectiveness of the proposed software across anatomical districts and image modalities, it was tested on two very different scenarios: head and neck (H&N) CT segmentation for radiotherapy application, and magnetic resonance image brain labeling for neuroscience investigation. Results: For the neurological study, minimum dice was equal to 0.76 (investigated structures: left and right caudate, putamen, thalamus, and hippocampus). For head and neck case, minimum dice was 0.42 for the most challenging structures (optic nerves and submandibular glands) and 0.62 for the other ones (mandible, brainstem, and parotid glands). Time required to obtain the labels was compatible with a real clinical workflow (35 and 120 min). Conclusions: The proposed software fills a gap in the multiatlas based segmentation field, since all currently available tools (both for commercial and for research purposes) are restricted to a well specified application. Furthermore, it can be adopted as a platform for exploring MABS parameters and as a reference implementation for comparing against other segmentation algorithms.

60 APPLIED LIFE SCIENCES↗

Durable and High-Performance SOECs Based on Proton Conductors for Hydrogen Production

Proton-conducting solid oxide electrolysis cells (P-SOECs) are a promising technology for cost-effective and efficient production of green hydrogen. Breakthroughs in materials development, optimization of cell structure, and achievement of high performance and durability are essential to significantly increase the commercial competitiveness of these technologies. The main objective of this project is to gain scientific knowledge for the rational design, fabrication, and demonstration of a robust, highly efficient, and low-cost SOEC technology based on a proton-conducting electrolyte membrane for hydrogen production. We focused on better understanding the degradation mechanisms of proton-conducting electrolytes, air electrodes, and catalyst materials under electrolysis mode to develop an effective strategy for rationalizing new materials that are vital for enhancing cell performance and durability. The scope includes enhancing the performance and durability of the electrolyte and electrode materials under realistic operating conditions, developing highly active and robust catalysts to minimize electrode losses while improving tolerance to contaminant poisoning, revealing the mechanism of enhanced activity and stability of the catalyst, and understanding the underlying degradation mechanisms. In addition, various characterization techniques were employed to gain a fundamental understanding of the materials’ behavior and their impact on cell performance, providing vital information to guide materials discovery and cell design. After defect chemistry engineering, the optimized donor and acceptor co-doped electrolytes BaMo/W 0.03 Ce 0.71 Yb 0.26 O 3-δ (BM/W03) showed substantially improved chemical stability against high concentrations of CO 2 and H 2 O compared to the state-of-the-art electrolyte (BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , BZCYYb1711) while maintaining comparable ionic conductivity and ionic transference number. To bypass the inherent trade-off between conductivity and chemical stability, we fabricated a bi-layer electrolyte composed of BZCYYb1711 coated with a highly-stable thin layer of BaHf 0.83 Yb 0.17 O 3-δ (BHYb). This bi-layer electrolyte displayed excellent chemical stability against high concentration CO 2 ; there was no detectable formation of BaCO 3 after exposure to 97% CO 2 (with 3% H 2 O) at 500 °C for 1000 hours and the rate of degradation in resistance was about 0.4% per 1,000 hours (kh). In contrast, the same BZCYYb1711 electrolyte without a BHYb coating degraded significantly under the same testing conditions; the degradation rate was increased to 5.1%/kh. In addition, a triple conducting air electrode Ba 0.9 Pr 0.1 Hf 0.1 Y0.1Co 0.8 O 3-δ (BPHYC) was developed by heavily doping transition metal ions into a proton-conducting material. This air electrode material, composed of 3 distinct phases, exhibits superior electrocatalytic activity due to the synergistic effect from the three component phases. Moreover, an active and durable catalyst, La 2 Ni 0.5 Fe 0.5 O 4+δ (LNF), was developed, showing excellent catalytic activity and contaminant tolerance, with a degradation rate of only 0.49%/kh when exposed to high concentrations of steam and Cr. Finally, single cells were constructed from the best electrolytes, electrodes, and catalyst coatings developed in this project. These cells demonstrated superior high current density at a given cell voltage, high roundtrip efficiency, and remarkable durability (up to 1000 hours of operation).

08 HYDROGEN↗

Efficiency and Emissions Characteristics of an HCCI Engine Fueled by Primary Reference Fuels

Here, this article investigates the effects of various primary reference fuel (PRF) blends, compression ratios, and intake temperatures on the thermodynamics and performance of homogeneous charge compression ignition (HCCI) combustion in a Cooperative Fuels Research (CFR) engine. Combustion phasing was kept constant at a CA50 phasing of 5° after top dead center (aTDC) and the equivalence ratio was kept constant at 0.3. Meanwhile, the compression ratio varied from 8:1 to 15:1 as the PRF blends ranged from pure n-heptane to nearly pure isooctane. The intake temperature was used to match CA50 phasing. In addition to the experimental results, a GT-Power model was constructed to simulate the experimental engine and the model was validated against the experimental data. The GT-Power model and simulation results were used to help analyze the energy flows and thermodynamic conditions tested in the experiment. The results indicate that an increase of compression ratio causes higher thermal efficiency and fuel conversion efficiency; however, at the same compression ratio, an increase in PRF number results in lower efficiency due to the required increase in intake temperature and the associated decrease in charge density. While the efficiency does increase with compression ratio, the results show that the effect of increased expansion work is partially offset by higher heat transfer losses and lower ratios of specific heats at higher compression ratios. The results indicate that the maximum pressure rise rate (MPRR) in HCCI significantly increases with compression ratio. Combustion efficiency shows a strong trend with peak temperature regardless of the PRF number or compression ratio, indicating that the CO-to-CO2 conversion is independent of the parent fuel chemistry in the case of the PRFs, whereas the unburned hydrocarbon emissions showed the opposite trend, depending mostly on the parent fuel’s autoignition tendency.

33 ADVANCED PROPULSION SYSTEMS↗

An Induced Environment Contamination Monitor for the Space Shuttle

The Induced Environment Contamination Monitor (IECM), a set of ten instruments integrated into a self-contained unit and scheduled to fly on shuttle Orbital Flight Tests 1 through 6 and on Spacelabs 1 and 2, is described. The IECM is designed to measure the actual environment to determine whether the strict controls placed on the shuttle system have solved the contamination problem. Measurements are taken during prelaunch, ascent, on-orbit, descent, and postlanding. The on-orbit measurements are molecular return flux, background spectral intensity, molecular deposition, and optical surface effects. During the other mission phases dew point, humidity, aerosol content, and trace gas are measured as well as optical surface effects and molecular deposition. The IECM systems and thermal design are discussed. Preflight and ground operations are presented together with associated ground support equipment. Flight operations and data reduction plans are given.

Miller, E. R.↗

The origin of the Kirkwood gaps - A mapping for asteroidal motion near the 3/1 commensurability

A mapping of the phase space onto itself with the same low-order resonance structure as the 3/1 commensurability in the planar-elliptic restricted three-body problem is obtained. This mapping is about 1,000 times faster than the usual method of numerically integrating the averaged equations of motion. It exhibits some surprising behavior that might provide a key to the origin of the Kirkwood gaps. It is noted that a test asteroid placed in the gap may evolve for a million years with low eccentricity (less than 0.05) and then suddenly jump to large eccentricity (greater than 0.3), becoming a Mars crosser. The removal of the asteroid by a close encounter with Mars would then be possible. As a first test of this hypothesis, a distribution of 300 test asteroids in the area of the 3/1 commensurability was evolved for two million years. When the Mars crossers are removed, the distribution of initial conditions reveals a gap at the location of the 3/1 Kirkwood gap.

Wisdom, J.↗

Effect of combined pressure and temperature distortion orientation on high-bypass-ratio turbofan engine stability

Total-temperature, static-pressure and total-pressure distributions were measured in the inlet duct upstream of the engine inlet and within the fan and compressor of a YTF34 turbofan engine. Free-stream and boundary layer yaw angle variations were measured between a rotable screen assembly and the engine inlet. Total pressure distortions were generated using three 180 deg extent screens and total temperature distortions were generated using a rotatable hydrogen burner. Reynolds number index upstream of the rotatable screen assembly was maintained at 0.5 (based on the undistorted sectors at station 1, the inlet flow measuring station). The engine mechanical fan speed at sea level condition was rated at 7005 rpm. The engine was tested at a corrected fan speed of 90 percent of rated condition. Yaw angle increased between the rotatable screen assembly and the engine inlet. The largest variation in free-stream and boundary layer yaw angle occurs when the combined distortions are 180 deg out-of-phase. Static-pressure distortion increased exponentially as flow approached the engine. Total-pressure distortions were attenuated between the engine inlet and the compressor exit. Total-temperature distortion persisted through the compressor for all four combined distortions investigated.

Soeder, R. H.↗

Near-field Testing of the 15-meter Model of the Hoop Column Antenna

The technical results from near-field testing of the 15-meter model of the hoop column antenna at the Martin Marietta Denver Aerospace facility are documented. The antenna consists of a deployable central column and a 15 meter hoop, stiffened by cables into a structure with a high tolerance repeatable surface and offset feed location. The surface has been configured to have four offset parabolic apertures, each about 6 meters in diameter, and is made of gold plated molybdenum wire mesh. Pattern measurements were made with feed systems radiating at frequencies of 7.73, 11.60, 2.27, 2.225, and 4.26 (all in GHz). This report (Volume 1) covers the testing from an overall viewpoint and contains information of generalized interest for testing large antennas. This volume discusses the deployment of the antenna in the Martin Facility and the measurements to determine mechanical stability and trueness of the reflector surface, gives the test program outline, and gives a synopsis of antenna electromagnetic performance. Three techniques for measuring surface mechanical tolerances were used (theodolites, metric cameras, and near-field phase), but only the near-field phase approach is included. The report also includes an error analysis. A detailed listing of the antenna patterns are provided for the 2.225 Ghz feed in Volume 3 of this report, and for all other feeds in Volume 2.

Hoover, J.↗

Biaxial fatigue properties of thin-walled composite tubes

A testing method for obtaining fatigue and fracture data under biaxial loading and for negative R-ratios is described. Thin-walled tubes of 1-in. outer nominal diameter with a tapered grip section were tested in an Axial-Torsion Servohydraulic Testing Machine with a 463 Data Control Processor at frequencies below 10 Hz up to the 1-million cycle range. Room temperature, uniaxial constant amplitude fatigue data for high temperature cure graphite-epoxy material are presented at R = -0.4 for a (+, - 5 deg) fiber orientation. The fatigue curve is almost horizontal. Tests on (+, - 5 deg) 'SP-328' resulted in failures which predominantly originated in the grip section. Presently, a new specimen design is being tested intended to eliminate cracking in the grip section. Biaxial in-phase loading of (0/+, - 45) tubes of Fiberite graphite-epoxy resulted in much steeper fatigue curves than observed under uniaxial loading.

Krempl, E.↗