Business Opportunities Website Posting 1115 - Electro Static Discharge (ESD) Eng. Support. Support the development of products with Class O-ESD-sensitive levels.
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Fresquez, Jacqueline L. V.↗
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NASA Supportability Engineering Implementation Utilizing DoD Practices and Processes
The Ares I design and development program made the determination early in the System Design Review Phase to utilize DoD ILS and LSA approach for supportability engineering as an integral part of the system engineering process. This paper is to provide a review of the overall approach to design Ares-I with an emphasis on a more affordable, supportable, and sustainable launch vehicle. Discussions will include the requirements development, design influence, support concept alternatives, ILS and LSA planning, Logistics support analyses/trades performed, LSA tailoring for NASA Ares Program, support system infrastructure identification, ILS Design Review documentation, Working Group coordination, and overall ILS implementation. At the outset, the Ares I Project initiated the development of the Integrated Logistics Support Plan (ILSP) and a Logistics Support Analysis process to provide a path forward for the management of the Ares-I ILS program and supportability analysis activities. The ILSP provide the initial planning and coordination between the Ares-I Project Elements and Ground Operation Project. The LSA process provided a system engineering approach in the development of the Ares-I supportability requirements; influence the design for supportability and development of alternative support concepts that satisfies the program operability requirements. The LSA planning and analysis results are documented in the Logistics Support Analysis Report. This document was required during the Ares-I System Design Review (SDR) and Preliminary Design Review (PDR) review cycles. To help coordinate the LSA process across the Ares-I project and between programs, the LSA Report is updated and released quarterly. A System Requirement Analysis was performed to determine the supportability requirements and technical performance measurements (TPMs). Two working groups were established to provide support in the management and implement the Ares-I ILS program, the Integrated Logistics Support Working Group (ILSWG) and the Logistics Support Analysis Record Working Group (LSARWG). The Ares I ILSWG is established to assess the requirements and conduct, evaluate analyses and trade studies associated with acquisition logistic and supportability processes and to resolve Ares I integrated logistics and supportability issues. It established a strategic collaborative alliance for coordination of Logistics Support Analysis activates in support of the integrated Ares I vehicle design and development of logistics support infrastructure. A Joint Ares I - Orion LSAR Working Group was established to: 1) Guide the development of Ares-I and Orion LSAR data and serve as a model for future Constellation programs, 2) Develop rules and assumptions that will apply across the Constellation program with regards to the program's LSAR development, and 3) Maintain the Constellation LSAR Style Guide.
Smith, David A.↗
The IOAG Recommendations on Spacecraft Emergency Cross Support
In 2014, the Inter-agency Operations Advisory Group (IOAG) chartered a multi-agency team effort to study how to best handle spacecraft emergency as part of cross support among network assets. The original intent is to put in place for the first time a process and guidelines to make emergency support as part of a permanent cross-support capability between space agencies. From the perspective of space communications service providers, a few key issues, common to all agencies, concerning the Spacecraft Emergency Cross Support (SECS) have been explored. They are: context of emergency support, provision of emergency support under a cross-support agreement, provision of emergency support with no cross-support agreement, legal and liability issues, response time, support priority, services provided, sustaining emergency support capabilities, and charge for the support. The positions of the various participating agencies with respect to these issues have been collected, analyzed, and finally harmonized to form the recommended IOAG positions. A central challenge most communications service providers are facing is that since the spacecraft emergency is an unplanned critical event, it typically requires fast response to the emergency call, hence lacking an international standard process for the operational interfaces seems to exacerbate the difficulty in providing SECS. For reducing the response time, i.e. from the time of accepting a request for SECS to the readiness for support, it is recommended that a “cross-support emergency system” be established by IOAG member agencies. Along with it, the IOAG core services, just-in-time ground communications line, cross support service management (CSSM), and standard operations procedures (SOP) for operational interfaces form the basic foundation of the “cross support emergency system”. Of the above, new to the cross support conducted thus far in the IOAG community is the concept of the SOP specifically for the interfaces between the service provider and service user during the SECS. Use cases, salient features, and definition of the key operational activities/tasks relevant to the interfaces are addressed by the effort. Underpinning such a system is the availability of the RF license granted by the local authority, at national and/or regional level, for a given ground station to communicate with and track the spacecraft in emergency mode at the uplink and downlink frequencies assigned to that spacecraft. That means it is critical for the IOAG member agencies to obtain a priori all-band licenses (for the entire X-band or S-band) for some, if not all, of their ground stations that are most capable of or likely to provide SECS. It is also recommended that certain prior arrangements be made with the relevant local licensing authorities for a process that will allow expedited authorization to transmit/receive signals to/from the declared spacecraft over the declared ground stations specifically and solely for the emergency case. Our analysis of the SECS has also uncovered a few fundamental programmatic issues. Recognizing any IOAG positions reached on these issues do not necessarily lead to any binding authority, it is recommended that they, along with those key attributes of the cross support emergency system, be explicitly stated as multi-agency guidelines to guide the implementation and provision of the SECS. The paper will present the results of the working group on Spacecraft Emergency Cross Support and, in particular, its findings, products and recommendations. It will also identify the next steps of this work that may include the production of some international standards as an extension of this work, or the process to make this emergency system usable by other spacecraft operators beyond the space agencies.
Tai, Wallace S.↗
The IOAG Recommendations on Spacecraft Emergency Cross Support
In 2014, the Inter-agency Operations Advisory Group (IOAG) chartered a multi-agency team effort to study how to best handle spacecraft emergency as part of cross support among network assets. The original intent is to put in place for the first time a process and guidelines to make emergency support as part of a permanent cross-support capability between space agencies. From the perspective of space communications service providers, a few key issues, common to all agencies, concerning the Spacecraft Emergency Cross Support (SECS) have been explored. They are: context of emergency support, provision of emergency support under a cross-support agreement, provision of emergency support with no cross-support agreement, legal and liability issues, response time, support priority, services provided, sustaining emergency support capabilities, and charge for the support. The positions of the various participating agencies with respect to these issues have been collected, analyzed, and finally harmonized to form the recommended IOAG positions. A central challenge most communications service providers are facing is that since the spacecraft emergency is an unplanned critical event, it typically requires fast response to the emergency call, hence lacking an international standard process for the operational interfaces seems to exacerbate the difficulty in providing SECS. For reducing the response time, i.e. from the time of accepting a request for SECS to the readiness for support, it is recommended that a “cross-support emergency system” be established by IOAG member agencies. Along with it, the IOAG core services, just-in-time ground communications line, cross support service management (CSSM), and standard operations procedures (SOP) for operational interfaces form the basic foundation of the “cross support emergency system”. Of the above, new to the cross support conducted thus far in the IOAG community is the concept of the SOP specifically for the interfaces between the service provider and service user during the SECS. Use cases, salient features, and definition of the key operational activities/tasks relevant to the interfaces are addressed by the effort. Underpinning such a system is the availability of the RF license granted by the local authority, at national and/or regional level, for a given ground station to communicate with and track the spacecraft in emergency mode at the uplink and downlink frequencies assigned to that spacecraft. That means it is critical for the IOAG member agencies to obtain a priori all-band licenses (for the entire X-band or S-band) for some, if not all, of their ground stations that are most capable of or likely to provide SECS. It is also recommended that certain prior arrangements be made with the relevant local licensing authorities for a process that will allow expedited authorization to transmit/receive signals to/from the declared spacecraft over the declared ground stations specifically and solely for the emergency case. Our analysis of the SECS has also uncovered a few fundamental programmatic issues. Recognizing any IOAG positions reached on these issues do not necessarily lead to any binding authority, it is recommended that they, along with those key attributes of the cross support emergency system, be explicitly stated as multi-agency guidelines to guide the implementation and provision of the SECS. The paper will present the results of the working group on Spacecraft Emergency Cross Support and, in particular, its findings, products and recommendations. It will also identify the next steps of this work that may include the production of some international standards as an extension of this work, or the process to make this emergency system usable by other spacecraft operators beyond the space agencies.
Tai, Wallace S.↗
Uncrewed Lunar Surface Operations and Support Activities
Sustained human presence on the surface of the Moon and future missions to Mars require increased independence from surface crews and Earth-based mission control to operate efficiently, safely, and reliably. The time for surface crews to perform tasks will be limited. Extravehicular activities by surface personnel are burdensome and time-consuming, even when a continuous human presence on the surface occurs. Identifying and balancing human/automation roles and tasks and infusing automation and autonomy practices early in a system’s lifecycle will be essential to achieve mission objectives. Among these objectives are attaining a sustained human presence, improving performance and mission effectiveness, reducing operations and maintenance (O&M) costs, and ensuring operations that are robust to communication delays. To achieve these objectives, an operational shift toward increased automation and autonomy with less reliance on humans is needed. Uncrewed lunar surface operations and support activities occur when surface crews are not present or are independent of surface crew timeline activities requiring no surface crew oversight or intervention. These uncrewed surface opportunities can also be planned to minimize crew workload that avoids routine maintenance and support tasks, thus maximizing crew exploration time. Uncrewed preparations such as staging and prepositioning equipment and materials before the crew arrives could improve crew task efficiency. Additional opportunities exist to conduct uncrewed science, exploration, and utilization. Uncrewed surface architecture functions can include science and exploration; habitation; launch and landing support; surface communication and navigation; surface power generation and distribution; human surface mobility; lifting, handling, manipulating; excavation, construction, and site preparation; logistics management; maintenance and repair; surface resource utilization; integrated site operations and shared support services (e.g., site scheduling/prioritization, dust mitigation/contamination control, and surface safety). Early robotic lunar surface campaigns will provide information on the availability of resources, such as oxygen and water, and demonstrate surface-based technologies. After the Artemis III human lunar return mission, a series of landers will deliver surface systems, cargo, supplies, science packages, spare parts, and commodities. A balance of crewed and uncrewed surface operations will enable a sustained lunar surface presence at the South Pole of the Moon at a site that will be known as the Artemis Base Camp (ABC). It is envisioned that base camp operations on and around the Moon will then help prepare for the mission durations and activities needed to support the first human mission to Mars. Before long-duration crew missions to the base camp can occur, the necessary surface infrastructure will be pre-deployed and verified operational. Surface assets will be teleoperated and remotely managed from Earth. Additionally, robotic and short-duration crewed missions to the ABC will ensure the site’s merit to achieve long-term science objectives, availability of usable resources, and that terrain, seasonal variations, and illumination conditions are acceptable. ABC will consist of different areas where specific functions and services are rendered, including: • Launch and Landing Area • Habitation Area • Power Production Area • Resource Areas Launch and Landing Area—The launch and landing area will support associated functions for the arrival and departure of vehicles, such as crewed landing and ascent and uncrewed cargo deliveries and offloading. It will evolve from an unimproved site at the beginning of the exploration campaign to a more sustainable landing and launch area that can support repeated arrivals and departures. Initial uncrewed Lunar Terrain Vehicle (LTV) surface operations may include emplacement of navigation beacons and communication equipment, real-time video and photography of landing/liftoff events, and element repositioning, such as portable utility power (PUP) (applicable for other landed assets at other areas). Site preparations, such as surface leveling, soil compaction, and berm/path construction, may be needed for a more sustainable launch and landing area capable of accommodating vehicles that are increasingly more reusable and reduce the effects of plume surface interactions and ejecta impacts on nearby surface assets. During the ABC missions, cargo and logistics will be delivered to the lunar surface via robotic cargo landers before the crew arrives. These shipments, which can arrive in pressurized logistics carriers, will deliver the logistics necessary to support a crewed mission and include items such as food, water, equipment spares, etc. Providing the capability to retrieve, offload, and transport the logistics closer to the ABC site before the arrival of the crew will increase the overall efficiency of crew operations once they arrive. In the sustained phase of exploration, other supporting services may be needed, such as lander propellant servicing, surface power services, commodity refreshes, and additional inspection, maintenance, and repair capabilities, to sustain a cadence of extended personnel stays and cargo arrivals and departures. Habitation Area—Uncrewed support to surface habitation could involve supporting activation and pre-entry operations of the habitat while the crew is in orbit at the Gateway outpost preparing for a surface landing. Surface Habitat (SH) uncrewed operations may include bringing the cabin environment to a habitable temperature and air mix and activating other critical crew support systems. Potential crop production uncrewed tasks in the SH could also include autonomous watering and tending. Additionally, when the crew departs, the SH enters dormancy for the long period of uncrewed operation. A logistical staging area could also be collocated near the SH. If so, staging operations for crew supplies, waste re-location, and recycling operations may be opportunities for uncrewed operations. Power Production Area—The Fission Surface Power (FSP) element and its supporting distribution equipment provide power to surface elements as needed across the ABC to supplement day-to-day operations and survive lunar nights. Uncrewed support of this power system includes any initial LTV-assisted deployments of cables and other distributed equipment, associated electrical connections, and system testing and activation operations. Robotically performing some inspections, maintenance, or repair tasks on the power distribution equipment could reduce the surface crew workload. Resource Area— Uncrewed resource prospecting, mapping, and characterizing possible resource sites is likely to be time-consuming and represents an opportunity for uncrewed operations between crewed missions. Uncrewed mobile equipment operations will be needed in the extreme environments of permanently shadowed locations where resource extractions occur. As In-Situ Resource Utilization (ISRU) pilot plant operations begin, uncrewed surface support activities with available mobile and portable assets (LTV, PUP, etc.) will better support these operations. Any produced commodities can be stored at a centralized storage location for future use. Also associated with these operations is the use of mobile robotic excavators for resource acquisition and robotic/autonomous regolith processing. The waste tailings generated during excavation and regolith processing would also need to be transported and deposited at a dedicated location. Surface assets will continue operating between crew visits to maintain surface capabilities, conduct lunar surface science, technology demonstrations, and public outreach opportunities. Additionally, certain sustaining tasks that would consume valuable crew time could be performed before crew arrival, or after their departure. This capability may offer more affordable options to construct, activate, test, and maintain a broad set of surface assets. Telerobotically operated human surface mobility systems, such as the LTV and Pressurized Rover (PR), can be utilized for various tasks. Surface environmental conditions pose a distinct challenge for all these activities. Surface illumination and localized shadows are one such factor. Night-survival operations could consist of thermal management, battery pre-charging, and load shedding. Some surface systems may hibernate through the night and then awake and continue nominal operations. Uncrewed mobile assets may use a more adaptive approach to optimize their power and operations; one method is to follow the sunlight. Night-survival operations may be initiated remotely by teleoperation, automated, or accomplished by supervised autonomous operation. The ability to pre-deploy and control remote assets in orbit or on Mars before the arrival of the mission crew is a key capability that can be simulated on the moon. The base camp provides a venue where these advanced operational concepts, technologies, and autonomous methods and techniques, including the incorporation of time delays to simulate Earth-Mars latency can be replicated to help buy down future Mars mission risks. This paper will examine the evolution of uncrewed lunar surface operations and support activities. It will also discuss the lunar surface environmental conditions (thermal, lighting, terrain, topography, communications) along with the challenges they pose on uncrewed surface operations, and the performance of these activities with limited to minimal human interaction and/or teleoperation. Since lunar missions include Mars mission analogs, such investigation provides the framework for future uncrewed Mars mission support.
Mark E Lewis↗
The Catalysis of Uniform Metal Nanoparticles Deposited onto Oxide Supports: The Components of a Catalyst that Control Activity and Selectivity
Model materials consisting of metal nanoparticles loaded onto oxide supports were synthesized, characterized, and investigated in a number of catalytic chemical reactions. By varying the size, shape, and composition of nanoparticle, as well as the material used to support the nanoparticles, it was found that small changes to the catalyst can have enormous changes to the reaction activity and selectivity. Investigation of these carefully synthesized catalysts via in situ characterization, and reaction studies, leads to a deeper understanding of the molecular level parameters that govern catalysis. Through study of the properties of the nanoparticles it was discovered that nanoparticle size and shape have a dominant role in the chemoselective catalysis of furfural over platinum nanoparticles. When vapor phase furfural and hydrogen gas were passed over Pt nanoparticles ranging in size from 1.5 to 7.1 nm, the catalytic selectivity was found to be dominated by the size of the nanoparticle. Large nanoparticles promoted hydrogenation of furfural to furfuryl alcohol, while smaller nanoparticles favored decarbonylation to furan. The same size specific selectivity was found in the hydrogenative reforming (the transformation of hydrocarbons to branched isomers) of C6 hydrocarbons, in which Pt nanoparticle size controls isomerization selectivity. Methylcyclopentane was found to be extremely size dependent at lower temperatures (553 K). It was found that smaller sized nanoparticles favored isomer formation, while larger sizes catalyzed the aromatization reaction more efficiently. n-hexane was found to be much less dependent on particle size, but still showed an increase in isomerization with small particles over larger sized Pt nanoparticles. The composition of PtxRh1-x bimetallic nanoparticles was also studied. These catalysts were characterized under hexane reforming conditions with Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), in order to find the actual surface atomic composition under real catalytic working conditions. By using AP-XPS and catalytic data in tandem, it was found that an optimum Rh loading occurred when the surface ensemble statistically favored one Rh atom surrounded by Pt atoms. By utilizing different oxide materials for catalytic supports the flow of charge can play a role in the reaction at the surface or interface in a phenomenon known as the strong metal-support interaction (SMSI). When Pt nanoparticles were loaded onto mesoporous supports made of Co3O4, NiO, MnO2, Fe2O3, and CeO2 it was found that their activity for carbon monoxide oxidation was greatly enhanced relative to the support alone or Pt loaded onto inert mesoporous silica. This finding demonstrates that the interface of the metallic Pt nanoparticle and the oxide 2 support is able to produce turnovers that are orders of magnitude higher than the two materials separately. When the same type of experiments were investigated with n-hexane as the reactant and macroporous Al2O3, TiO2, Nb2O5, Ta2O5, and ZrO2 were utilized as supports, it was found that the reaction selectivity was greatly altered depending on the catalytic support material. TiO2, Nb2O5, and Ta2O5 (all of which are strong Lewis acids) were found to be much more selective for isomer production than the standard SiO2 mesoporous silica supported Pt nanoparticle catalyst. Finally, an acidified mesoporous silica material was utilized as the support. This material was synthesized by using AlCl3 to modify the surface of mesoporous silica. This support was found to have no activity for hexane isomerization alone. However, when Pt nanoparticles were supported on the material, the activity and isomer selectivity in hexane reforming was increased several orders of magnitude as compared to the same nanoparticles supported on unmodified mesoporous silica. This dissertation builds on the existing knowledge of known concepts in catalysis science such as structure sensitive reactions, the metal-support interaction, and acid-base chemistry. The results show how small changes in the active sites of a catalyst can create large changes in the catalytic chemistry. This research demonstrates how careful material control, characterization and reaction study can help to elucidate the molecular level components necessary to design efficient catalysts.
Musselwhite, Nathan↗
Synthesis and Characterization of Mixed-Conducting Corrosion Resistant Oxide Supports
An extensive search and evaluation of electrochemically stable catalyst supports (including metal oxides like RuO2-SiO2, RuO2-TiO2, and ITO was perfomed during the 4 years of the project. The suports were also catalyzed by deposition of Pt and tested for its performance and electrochemical stability in RDE and fuel cell experiments. For testing the electrochemical stability and fuel cell performance of the catalysts and supports, we have employed the protocols in use at the Department of Energy and Nissan Technological Center North America (NTCNA). The use of such procedures allows a precise and reproducible estimation of the performance and stability of the materials and permits comparisons among laboratories and DOE funded projects. RuO2-SiO2 catalyst supports showed no loss in surface area during start-stop stability tests that were performed by cycling the electrode potential between 0 V to 1.8 V for 1000 cycles. Catalyzed support (40% Pt/RuO2-SiO2; 1:1 mole ratio) were tested in a PEFC, resulting in a current density of 750 mA/cm2 at 0.6 Volts, and a maximum power density of 570 mW/cm2. Measurements were conducted at 80 ºC with 75% relative humidity of the inlet gases (H2/O2); Pt loadings were 0.4 mg/cm2 at the cathode and 0.2 mg/cm2 at the anode. Start-stop stability tests for support and catalyzed support performed in RDE and PEFC set-ups have confirmed RuO2-TiO2 support stability. The beginning of life performance was exactly equal to end of life performance (in an MEA that has been subjected to severe start-stop cycling for 10,000 start/stop cycles between 1 V to 1.5 V). This result was in sharp contrast to baseline Pt/C catalyst that showed significant performance deterioration after accelerated stability tests. The Pt/TRO showed minimal loss in performance upon exposure to start-stop cycles. The loss in cell voltage at 1 A/cm2 at 100% RH was almost 700 mV for Pt/C whereas it was only ca. 15 mV for Pt/TRO. 40% RH data (of inlet gases) revealed a similar trend in terms of stability – exceptional stability for Pt/TRO as opposed to very poor stability for Pt/HSAC. These observations were attributed to the much higher stability of the TRO support compared to Carbon. The carbon dioxide concentration in the cathode exit stream during the accelerated degradation test with Pt/TRO (start-stop protocol) was extremely low (between 3 to 10 ppm of CO2). In contrast, the CO2 emission levels from a conventional Pt/C catalyst were found to be approx. 200 ppm. This observation was a clear indicator that the main source of carbon being oxidized to carbon dioxide in an MEA was the carbon catalyst support, and not the gas diffusion layer or the graphite flow fields. Indium tin oxide (ITO) was also evaluated as a catalyst support for PEFCs. Pt/ITO was very stable under start-up/shutdown accelerated degradation protocol (RDE tests in perchloric acid). The ECSA change was less than 4% over 10,000 cycles. The load cycling accelerated protocol (from 0.6 to 0.95 V vs. RHE) resulted in a loss of approximately 34% of the initial ECSA after 10,000 cycles. However, fuel cell testing resulted in a very low performing catalyst. XPS spectroscopy was employed to investigate the changes in the catalysts occuring during fuel cell operation. It was observed a shift of In 3d5/2 and In 3d3/2 peaks towards higher binding energies. This can be explained by the formation of hydroxides or oxy-hydroxides in the surface of the catalyst. O1s spectrum for Pt/ITO catalyst after being operated in the fuel cell, also confirmed the formation of significant amounts of surface hydroxides (12 to 16%). The presence of surface hydroxides in the catalyst increased the electrode resistivity affecting fuel cell performance. NTCNA performed a detailed analysis of transport phenomena (reactants and products to/from the Pt active sites) in both commercial catalyst and Pt/RTO (in order to have a better understanding at the basic level). The proton resistance (Rionomer) in Pt/C and Pt/RTO cathode catalyst layers were 150 and 12 mΩ-cm2, respectively. Pt/RTO catalyst layer has about an order or magnitude lower proton transfer resistance than Pt/C catalyst layer. Since the ionomer/support ratio that was used in formulating the ink for both catalysts was the same (0.9), it is expected that the volumetric coverage of ionomer of both catalysts will be significantly different due to the disparity in the surface areas (Pt/C had ~ 800 m2/g, while Pt/RTO had ~ 50 m2/g). The differences in the ionomer volumetric coverage and the ionomer film thickness may explain the significantly higher proton conductivity in the Pt/RTO catalyst layer when compared to Pt/HSAC. It is therefore very important to optimize the ionomer loadings when synthesizing new catalyst supports (and never rely on values for carbon-based commercial catalysts). Finally, NTCNA has elaborated a cost model for non-carbon support materials considering their durability benefits. Material costs for production of Pt/ RuO2-TiO2 electrodes were compared to Pt/C. RuO2-TiO2 support was more expensive than carbon but the total material cost was still dominated by platinum cost. Though ruthenium is considered a precious metal, its cost is far less than platinum. It should also be noted that ruthenium only makes up 38% of the mass of the support, while the rest is inexpensive TiO2. After considering the durability advantages of Pt/RTO, cost model showed that even with almost double the Pt loading (0.35 vs 0.18 mgPt/cm2), Pt/RTO ($22.7/kWnet) is only slightly more expensive than Pt/C ($21.9/kWnet).
08 HYDROGEN↗
Spinel oxides as coke-resistant supports for NiO-based oxygen carriers in chemical looping combustion of methane
Due to their high activity for methane conversion under a cyclic redox scheme, supported nickel oxides are among the most extensively investigated oxygen carrier materials for chemical looping combustion (CLC) and reforming (CLR) of methane. However, coke formation remains as a key challenge for Ni-containing oxygen carriers. The current study investigates the effect of reducible, spinel-structured supports to enhance coke resistance of NiO-based oxygen carriers. It was hypothesized that reducible supports capable of continued yet slow lattice oxygen donation in the presence of methane can actively retard coke formation on the surface of the oxygen carriers. To evaluate such effects, NiFe 2 O 4 , MgFe 2 O 4 , and BaFe 2 O 4 are investigated as coke-resistant, reducible supports for NiO using mass spectrometry (MS) and thermogravimetric analysis (TGA) during chemical looping cycles. All three reducible supports were capable of continuous oxygen donation over an extended period of time (>40 min) without signs of coke formation. Further, when used as supports for NiO, the resulting oxygen carriers showed no sign of carbon deposition under typical methane CLC environments. In comparison, NiO supported on inert MgAl 2 O 4 exhibited significant coke formation after only 2.5 min. Moreover, NiO supported on NiFe 2 O 4 and BaFe 2 O 4 exhibited faster redox activity and higher oxygen carrying capacity when compared to the inert MgAl 2 O 4 -supported NiO. Detailed investigation of the reduction behavior of NiFe 2 O 4 -supported NiO revealed extensive solid-state reactions and Ni/Fe exchanges among the support, NiO, and newly formed phases. Specifically, initial weight loss in NiFe 2 O 4 -supported NiO was associated with reduction of the oxygen carrier to metallic Ni and Fe 3 O 4 phases. Subsequent coke inhibition was attributed to the slow reduction of Fe 3 O 4 and FeO phases. Multi-cyclic redox studies indicated that NiFe 2 O 4 -supported NiO gradually lost its redox activity. In comparison, both MgFe 2 O 4 - and BaFe 2 O 4 -supported NiO exhibited satisfactory redox stability, activity, and coke resistance.
03 NATURAL GAS↗
Packaging and Transportation Support at LANL CTMA 2012
Operations Support Packaging and Transportation (OS-PT) supports LANL in various functions. Some highlights of the past year have been with the work relating to environmental remediation, type B packaging, non-DOT compliant transfers, and special permit training. The TA-21 remediation project was part of the ARRA funding that LANL received. The $212 million in funding was used to demolish 24 buildings at TA-21, excavate the lab's oldest waste disposal site, and install 16 groundwater monitoring wells. The project was completed ahead of schedule and under budget. More than 300 tons of metal was recycled and all the soil excavated from MDA-B was replaced with clean fill. OS-PT supported this projected by transporting more than 7 million pounds of waste to TA-54 Area G with an addendum to their TSD. Because of the public access on the transfer route, Los Alamos County restricted the transfer to happen from 2:00 AM to 4:00 AM. OS-PT conducted 8 transfers in support of this project. Some concerns included the contaminated trailers at receipt facilities when transferring filled Super Sacks. Future Super Sacks were over packed into new IP-2 Super Sacks before shipping. OS-PT is also supporting the remediation of TA-54 Area G. LANL has an agreement with the State of New Mexico to remove all TRU waste currently stored above ground from at Area G. OS-PT supports this initiative with transfers of TRU waste under LANL's TSD and support of TRU shipments to WIPP. Another project supported by our organization is gas cylinder/dewar recycling and remediation. We are focusing on reducing risk associated with unneeded gasses at LANL. To minimized excessive ordering, to save money and time, and to minimize hazards OS-PT is supporting a gas recycling program. This program will allow programmatic organization across LANL to share unused/unneeded gasses. Instead of old dewars being disposed of, OS-PT has began identifying these dewars and sending them for refurbishment. To date, this effort has saved LANL $450K and estimated saving for future efforts will be more than $1.5 million. Some Projects that are happening here at LANL are offsite source recovery, weapon component transfers, and isotope science production. There are specific packages that help support these projects for the shipment of related materials. OS-PT provides support to these packages to ensure they are and will be available to continue this support. The Areva 435-B Overpack will help the Offsite Source Recovery Project recover high activity gamma sources from various locations across the globe. The Safety Analysis for Packaging is scheduled for initial completion June of 2012. The DPP-1 package is designed to replace the Model FL, which was designed by Rocky Flats and began service in 1990. LANL has collaborated on package design with LLNL, Pantex, Y-12, and KCP. LANL is supporting LLNL on component fixture development. Testing to 10 CFR 71 is to be completed in the Fall of 2012 and scheduled for NA-174 approval in 2014. The SAFESHIELD package helps supports LANL's Isotope production projects. This package can transfer highly irradiated materials from LANL's accelerator to material processing facilities. LANL worked to renew the SAFESHEILD's Certification for 5 more years.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Oxidative dehydrogenation of isobutane over vanadia catalysts supported by titania nanoshapes
Support plays a complex role in catalysis by supported metal oxides and the exact support effect still remains elusive. One of the approaches to gain fundamental insights into the support effect is to utilize model support systems. In this study, we employed for the first time titania nanoshapes as the model supports and investigated how the variation of surface structure of the support (titania, TiO 2 ) impacts the catalysis of supported oxide (vanadia, VO x ). TiO 2 truncated rhombi, spheres and rods were synthesized via hydrothermal method and characterized with XRD and TEM. These TiO 2 nanoshapes represent different mixtures of surface facets including [1 0 1], [0 1 0] and [0 0 1] and were used to support vanadia. The structure of supported VO x species was characterized in detail with in situ Raman spectroscopy as a function of loading on the three TiO 2 nanoshapes. Oxidative dehydrogenation (ODH) of isobutane to isobutene was used as a model reaction to test how the support shape influences the activity, selectivity and activation energy of the surface VO x species. It was shown that the shape of TiO 2 support does not pose evident effect on either the structure of surface VO x species or the catalytic performance of surface VO x species in isobutane ODH reaction. Finally, this insignificant support shape effect was ascribed to the small difference in the surface oxygen vacancy formation energy among the different TiO 2 surfaces and the multi-faceting nature of the TiO 2 nanoshapes.
36 MATERIALS SCIENCE↗
Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
Solid supports play an indispensable role in heterogeneous catalysis, as they can directly affect the catalytic activity and selectivity of supported catalysts. However, the specific roles of such supports remain to be demystified owing to the difficulties in obtaining precise structural information on supported catalysts. To understand the effects of MOF topology, pore environment, and metal identity of node supports on the catalytic activity, a Ni catalyst was supported on eight Zr- or Hf-MOFs based on 8-connected nodes: namely M-NU-1200, M-NU-1000, M-NU-1008, and M-NU-1010 (M = Zr, Hf). Single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the supported catalyst structures. To investigate the support effects on their activities, the supported Ni catalysts were evaluated by using ethylene hydrogenation as a model reaction. The results revealed that all Hf-based-MOF-supported Ni catalysts exhibited higher catalytic reactivity with TOF (turnover frequency) values at least double of those isostructural Zr counterparts. Additionally, MOFs with less congested metal anchoring sites, as a result of the topology and surrounding pore environment, yielded higher TOFs, suggesting the importance of supports in dictating both the catalyst accessibility and activity. Computational analysis complemented the experimental observations and provided insights into reaction barrier differences and their performance variation. Furthermore, this study demonstrates the essential role of the supports and provides a thought for selecting/designing suitable supports in heterogeneous catalysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Identifying the Catalytic Active Site for Propylene Metathesis by Supported ReO x Catalysts
A series of supported ReO x catalysts were investigated that allowed identifying the unique surface anchoring sites on oxide supports responsible for activating the surface ReO 4 sites for propylene metathesis (the catalytic active site). The catalysts were synthesized by incipient-wetness impregnation of aqueous HReO 4 onto the oxide supports (Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 and CeO 2 ), characterized under dehydrated and propylene metathesis reaction conditions with in situ spectroscopy (Raman, DRIFTS, UV-Vis and NAP-XPS), and chemically probed (CH 3 CH=CH 2 -TPSR, CH 2 =CH 2 /CH 3 CH=CHCH 3 titration and steady-state self-metathesis of propylene to ethylene and 2-butene). The initially calcined supported rhenia species anchor as isolated surface Re 7+ O 4 sites on the oxide supports by reacting with the surface hydroxyls (terminal S-OH, bridged S-OH-S and tricoordinated S 3 -OH) of the oxide supports. The specific oxide support was found to control the number of activated sites (Al 2 O 3 >> ZrO 2 > CeO 2 > TiO 2 > SiO 2 ) and propylene metathesis activity (Al 2 O 3 >> ZrO 2 >> TiO 2 ~ CeO 2 ~ SiO 2 ) revealing that the oxide support action is a potent ligand for the surface ReO x sites. The activation and specific activity of the surface ReO x sites depend on several factors (nature of surface hydroxyls (S 3 -OH > S-OH-S > S-OH), coordination of the oxide support surface cation (ZrO 7 , AlO 6 , CeO 4 ) and electronegativity of the oxide support cation (SiO 2 > Al 2 O 3 > TiO 2 > ZrO 2 > CeO 2 ). No relationships exist between olefin metathesis activity and acid strength of surface Lewis and Brønsted sites. Here, prior studies primarily focused on supported ReO x /Al 2 O 3 and the lack of examination of non-Al 2 O 3 supported rhenia catalysts precluded comparison between efficient and inefficient olefin metathesis catalysts, which prevented identifying the catalytic active site for olefin metathesis by supported ReO x catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Stakeholder Support for Wildlife Conservation Funding Policies
State wildlife management agencies in the United States have depended on a “user-pay” funding model for conservation efforts that relies on revenue from hunting license sales and a federal excise tax on firearms, ammunition, and archery equipment. Declines in hunting participation, however, jeopardize sustainability of the current funding model. Ensuring support among stakeholders for wildlife management and conservation may require expanding sources of funding and incorporating the perspectives and values of a diversifying constituency into decision making processes. We used a web-based survey of wildlife-associated recreationists in Michigan, USA to evaluate support for a range of conservation funding policies. Respondents self-identified primarily as hunters (n = 2,558) or wildlife watchers (n = 942). We used binary logistic regression to evaluate support for four conservation funding policy options: state sales tax, lottery proceeds, extractive industry revenue, and a user-based tax on outdoor gear (i.e., “backpack tax”). Determinants of support varied by type of policy and stakeholder characteristics. We found no statistically significant differences between hunters and wildlife watchers in their support for conservation funding policies when accounting for other variables such as wildlife value orientations, engagement in stewardship behaviors, age, and gender. The industry-based policy achieved the greatest level of approval, while the backpack tax had the lowest. Respondents were mixed in their support of the sales tax and lottery proceeds options. Cluster analysis revealed three homogenous groups related to conservation funding policies: “strong support,” “mixed/opposed,” and “anti-backpack tax.” Clusters differed in their support for conservation funding policies and on psychological and demographic variables. The “strong support” and “anti-backpack tax” groups differed in their levels of stewardship engagement, knowledge of conservation funding mechanisms, and support for the backpack tax option. The “mixed-opposed” group tended to be older, less educated, and less likely to be a member of a conservation organization. Results suggest support for conservation funding differs by policy type and social and psychological characteristics of stakeholders. Based on differences in policy support revealed in this study, we suggest a multi-tiered approach to funding conservation and building on support among wildlife stakeholders to mitigate the looming funding crisis for state wildlife agencies.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
A Lunar Surface System Supportability Technology Development Roadmap
This paper discusses the establishment of a Supportability Technology Development Roadmap as a guide for developing capabilities intended to allow NASA's Constellation program to enable a supportable, sustainable and affordable exploration of the Moon and Mars. Presented is a discussion of "supportability", in terms of space facility maintenance, repair and related logistics and a comparison of how lunar outpost supportability differs from the International Space Station. Supportability lessons learned from NASA and Department of Defense experience and their impact on a future lunar outpost is discussed. A supportability concept for future missions to the Moon and Mars that involves a transition from a highly logistics dependent to a logistically independent operation is discussed. Lunar outpost supportability capability needs are summarized and a supportability technology development strategy is established. The resulting Lunar Surface Systems Supportability Strategy defines general criteria that will be used to select technologies that will enable future flight crews to act effectively to respond to problems and exploit opportunities in a environment of extreme resource scarcity and isolation. This strategy also introduces the concept of exploiting flight hardware as a supportability resource. The technology roadmap involves development of three mutually supporting technology categories, Diagnostics Test & Verification, Maintenance & Repair, and Scavenging & Recycling. The technology roadmap establishes two distinct technology types, "Embedded" and "Process" technologies, with different implementation and thus different criteria and development approaches. The supportability technology roadmap addresses the technology readiness level, and estimated development schedule for technology groups that includes down-selection decision gates that correlate with the lunar program milestones. The resulting supportability technology roadmap is intended to develop a set of technologies with widest possible capability and utility with a minimum impact on crew time and training and remain within the time and cost constraints of the Constellation program
Oeftering, Richard C.↗
A Lunar Surface System Supportability Technology Development Roadmap
This paper discusses the establishment of a Supportability Technology Development Roadmap as a guide for developing capabilities intended to allow NASA s Constellation program to enable a supportable, sustainable and affordable exploration of the Moon and Mars. Presented is a discussion of supportability, in terms of space facility maintenance, repair and related logistics and a comparison of how lunar outpost supportability differs from the International Space Station. Supportability lessons learned from NASA and Department of Defense experience and their impact on a future lunar outpost is discussed. A supportability concept for future missions to the Moon and Mars that involves a transition from a highly logistics dependent to a logistically independent operation is discussed. Lunar outpost supportability capability needs are summarized and a supportability technology development strategy is established. The resulting Lunar Surface Systems Supportability Strategy defines general criteria that will be used to select technologies that will enable future flight crews to act effectively to respond to problems and exploit opportunities in an environment of extreme resource scarcity and isolation. This strategy also introduces the concept of exploiting flight hardware as a supportability resource. The technology roadmap involves development of three mutually supporting technology categories, Diagnostics Test and Verification, Maintenance and Repair, and Scavenging and Recycling. The technology roadmap establishes two distinct technology types, "Embedded" and "Process" technologies, with different implementation and thus different criteria and development approaches. The supportability technology roadmap addresses the technology readiness level, and estimated development schedule for technology groups that includes down-selection decision gates that correlate with the lunar program milestones. The resulting supportability technology roadmap is intended to develop a set of technologies with widest possible capability and utility with a minimum impact on crew time and training and remain within the time and cost constraints of the Constellation program.
Oeftering, Richard C.↗
An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh 2 P
Here, the production of hydrocarbon fuels from biomass pyrolysis requires the development of effective deoxygenation catalysts, and insight into how the properties of the support influence performance is critical for catalyst design. In this report, nanoparticles of Ni and Rh 2 P were synthesized using solution-phase techniques and dispersed on high surface area supports. The supports included a relatively inert material (C), an acidic reducible metal-oxide (TiO 2 ), an acidic irreducible metal-oxide (Al 2 O 3 ), and a basic irreducible metal-oxide (MgO). The eight active phase/support combinations were investigated for the deoxygenation of guaiacol, a pyrolysis vapor model compound, under ex situ catalytic fast pyrolysis conditions (350 °C, 0.44 MPa H 2 ). Compared to the baseline performance of the C-supported catalysts, Ni/TiO 2 and Rh 2 P/TiO 2 exhibited higher guaiacol conversion and lower O : C ratios for C 5+ products, highlighting the enhanced activity and greater selectivity to deoxygenated products derived from the use of an acidic reducible metal-oxide support. The Al 2 O 3 -supported catalysts also exhibited higher conversion than the C-supported catalysts and promoted alkylation reactions, which improve carbon efficiency and increase the carbon number of the C 5+ products. However, Ni/Al 2 O 3 and Rh 2 P/Al 2 O 3 were less selective towards deoxygenated products than the C-supported catalysts. The MgO-supported catalyst exhibited lower conversion and decreased yield of deoxygenated products compared to the C-supported catalysts. The results reported here suggest that basic metal-oxide supports may inhibit deoxygenation of phenolics under CFP conditions. Contrastingly, support acidity and reducibility were demonstrated to promote conversion and selectivity to deoxygenated products, respectively.
09 BIOMASS FUELS↗
Articulating Support for Horizontal Resistive Exercise
A versatile mechanical device provides support for a user engaged in any of a variety of resistive exercises in a substantially horizontal orientation. The unique features and versatility of the device promise to be useful in bedrest studies, rehabilitation, and specialized strength training. The device affords a capability for selectively loading and unloading of portions of the user s body through its support mechanisms, so that specific parts of the body can be trained with little or no effect on other parts that may be disabled or in the process of recovery from injury. Thus, the device is ideal for rehabilitation exercise programs prescribed by physicians and physical therapists. The capability for selective loading and support also offers potential benefits to strength and conditioning trainers and athletes who wish to selectively strengthen selected parts. The principal innovative aspect of the device is that it supports the subject s weight while enabling the subject, lying substantially horizontally, to perform an exercise that closely approximates a full standing squat. The device includes mechanisms that support the subject in such a way that the hips are free to translate both horizontally and vertically and are free to rotate about the line connecting the hips. At the same time, the shoulders are free to translate horizontally while the upper back is free to rotate about the line connecting the shoulders. Among the mechanisms for hip motion and support is a counterbalance that offsets the weight of the subject as the subject s pelvis translates horizontally and vertically and rotates the pelvis about the line connecting the hips. The counterbalance is connected to a pelvic support system that allows these pelvic movements. The subject is also supported at the shoulder by a mechanism that can tilt to provide continuous support of the upper back while allowing the rotation required for arching the back as the pelvis is displaced. The shoulder support also affords a capability for horizontal motion, and acts as the point of attachment of a load that is provided for squat and heel-raise exercises. The device is compatible with any resistive-exercise machine that provides bilateral loading via a moving cable or other mechanical linkage. The hip-translation and shoulder-translation and -rotation degrees of freedom of the supports can be locked individually or in combination in order to support the subject as necessary for exercises other than the standing squat. If necessary, for such exercises, the load can be applied directly to the subject by use of various attachments. In addition to the aforementioned heel raise, such exercises include the upright row, leg press, curls, extension of the triceps, front raise, lateral raise, and rear raise.
Gundo, Daniel↗
Tuning Zr 6 Metal–Organic Framework (MOF) Nodes as Catalyst Supports: Site Densities and Electron-Donor Properties Influence Molecular Iridium Complexes as Ethylene Conversion Catalysts
The Zr 6 nodes of the metal–organic frameworks (MOFs) UiO-66 and UiO-67 are metal oxide clusters of atomic precision and can be used as catalyst supports. The bonding sites on these nodes—that is, hydrogen-bonded H 2 O/OH groups on UiO-67 and non-hydrogen-bonded terminal OH groups on UiO-66—were regulated by modulation of the MOF syntheses. Ir(C 2 H 4 ) 2 (C 5 H 7 O 2 ) complexes reacted with these sites to give site-isolated Ir(C 2 H 4 ) 2 complexes, each anchored to the node by two Ir–Onode bonds. The supported iridium complexes on these sites have been characterized by infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies and density functional theory calculations. The ethylene ligands on iridium are readily replaced by CO, and the ν CO frequencies of the resultant complexes and those of comparable complexes reported elsewhere show that the support electron-donor tendencies increase in the order HY zeolite << UiO-66 < UiO-67 (= NU-1000) < ZrO 2 < MgO. The sharpness of the IR ν CO bands shows that the degree of uniformity of the support bonding sites decreases in the order ZrO 2 ≈ UiO-67 ≈ NU-1000 < MgO < UiO-66 << HY zeolite. The reactivity of supported Ir(CO) 2 complexes with C2H4 to form Ir(C 2 H 4 )(CO) and Ir(C 2 H 4 ) 2 (CO) is influenced by the support electron-donor properties, with the reactivity increasing in the order MgO = ZrO 2 = NU-1000 (not reactive) < UiO-66 < UiO-67 << HY zeolite. Density functional theory calculations characterizing the complexes supported on NU-1000, UiO-66/67, and HY zeolite concur with the use of the calculated ν CO bands as indicators of electron-donor properties of the supported metal catalysts. Our calculations also show that the reactivity of the supported Ir(CO) 2 complexes with C 2 H 4 is correlated with the electron-donor properties of the iridium center. Lastly, the supported Ir(C 2 H 4 ) 2 samples are precatalysts for ethylene hydrogenation and ethylene dimerization, with the activity for each reaction increasing with increasing electron-withdrawing strength of the support.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗