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At least 253 records · Page 14

Morphology engineering of iridium electrodes via modifying titanium substrates with controllable pillar structures for highly efficient oxygen evolution reaction

Nowadays, Ti is the well-chosen anode substrate material for proton exchange membrane electrolyzer cells (PEMECs) and modifications of the substrate surfaces are essential for the fabrication of highly efficient electrodes. Herein, we introduce the morphology engineering of Ir/Ti electrodes with different acid treatments of hydrochloric acid (HCl) and oxalic acid (OA), and the comparative benefits of these two acid treatment methods are studied from the aspects of their impacts on the morphology, interfacial contact resistance (ICR), and oxygen evolution reaction (OER) performances of resultant electrodes. Notably, compared to the flat surface from OA treatment, Ti substrates with the pillar structure could be successfully achieved via HCl etching. Further, the HCl and the oxalic acid (OA) treatments would reduce the interfacial contact resistance (ICR) to 15.2% and 5.5% of the pristine Ti substrate at 1.38 MPa, respectively. By iridium electrodeposition on Ti substrates, Ir/Ti electrodes with different catalyst loadings are fabricated. With similar low-loadings of about 0.05 mgIr cm –2 , an Ir/Ti electrode with HCl treated substrate exhibits a lower overpotential of ~283 mV at 10 mA cm –2 current density than 305 mV from OA treatment, due to the boosted reaction areas from HCl treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen-Bonding Surfaces for Ice Mitigation

Ice formation on aircraft, either on the ground or in-flight, is a major safety issue. While ground icing events occur predominantly during the winter months, in-flight icing can happen anytime during the year. The latter is more problematic since it could result in increased drag and loss of lift. Under a Phase I ARMD NARI Seedling Activity, coated aluminum surfaces possessing hydrogen-bonding groups were under investigation for mitigating ice formation. Hydroxyl and methyl terminated dimethylethoxysilanes were prepared via known chemistries and characterized by spectroscopic methods. These materials were subsequently used to coat aluminum surfaces. Surface compositions were based on pure hydroxyl and methyl terminated species as well as mixtures of the two. Coated surfaces were characterized by contact angle goniometry. Receding water contact angle data suggested several potential surfaces that may exhibit reduced ice adhesion. Qualitative icing experiments performed under representative environmental temperatures using supercooled distilled water delivered via spray coating were inconclusive. Molecular modeling studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition. Chain mobility resulted from the creation of "pockets" of increased free volume for longer chains to occupy.

Smith, Joseph G., Jr.↗

Adhesion of a bimetallic interface

The Hohenberg-Kohn and Kohn-Sham formalisms are used to examine binding (binding energy as a function of separation) for combinations of the simple metals Al(111), Zn(0001), Mg(0001), and Na(110) in contact. Similar metal contacts between Al, Zn, Mg, and Na are examined self-consistently in an ab initio calculation using the Kohn-Sham formalism. Crystallinity is included using the Aschroft pseudopotential via first order perturbation theory for the electron-ion interaction; and the ion-ion interaction is included exactly via a lattice sum. Binding energy was determined both in the local-density approximation and including gradient corrections to the exchange and correlation energy. Binding was found in all cases. In dissimilar metal contacts, interfacial bonding was greater than that in the weaker material predicting the possibility of metallic transfer. The nonzero position of the energy minimum in like metal contacts is explained in terms of consistency between the Ashcroft pseudopotential and the bulk charge density. Good agreement with experimental surface energies is obtained in the self-consistent calculation when nonlocal terms are included.

Ferrante, J.↗

UO 2 solubility and chemical interactions in molten LiCl-Li 2 O

Here, this study investigated the solubility of UO 2 in LiCl-2 wt% Li 2 O at 650 °C with O 2 partial pressures up to 114 torr. Experiments were run in which UO 2 powder was contacted with the molten salt for up to 120 h. Salt samples were taken and analyzed for U and corrosion product concentration using inductively coupled plasma mass spectrometry and for Li 2 O concentration using titration. The highest measured U concentration in the salt was 0.06 wt%, and O 2 partial pressure was observed to have little to no effect on the solubility. Increasing O 2 partial pressure did increase the concentration of corrosion products in the salt. The concentration of Li 2 O in the molten salt progressively decreased with time in contact with UO 2 . This can be explained by the formation of Li 2 UO 4 via reaction of UO 2 with Li 2 O.

36 MATERIALS SCIENCE↗

Mechanisms of Al3+ dimerization in alkaline solutions

The molecular speciation of aluminum (Al3+) in alkaline solutions is fundamental to its precipitation chemistry within a number of industrial applications that include ore renement and industrial processing of Al wastes. Under these conditions, Al3+ is predominantly Al(OH) {4 , while at high [Al] dimeric species also known to form. To date, the mechanism of dimer formation remains unclear and it is likely infuenced by complex ion ion interactions. In the present work, we investigate the role of ion pairing and a suite of potential dimerization pathways using a three-pronged approach that consists of density functional theory-based molecular dynamics (DFTMD), static DFT calculations (sDFT) and semi-empirical density functional tight binding molecular dynamics (SEMD). Specic cation eects imparted by the background electrolyte cations Na+, Li+ and K+ have been examined. Our simulations predict that when the Al species are ion paired with either cation the formation of the oxo-bridged Al2O(OH) 2{6 is favored with respect to the dihydroxo-bridged Al2(OH) 2{8 , in agreement with previousspectroscopic work. The formation of both dimers rst proceeds by bridging of two monomeric units via one hydroxo ligand, leading to a labile Al2(OH) 2{8 isomer. The eect of contact ion pairing of Li+ and K+ on the dimerization energetics is distinctly more favorable than that of Na+, which may have an impact on further ligomerization.

Pouvreau, Maxime↗

Parameterizing Convective Organization Effects With a Moisture-PDF Approach in Climate Models: Concept and a Regional Case Simulation

We propose a parameterization scheme of convective organization effects based on a moisture-distribution approach, which can reflect aggregation of convective cells within a model grid as well as the interaction between convection and spatial heterogeneity in free-troposphere moisture. With this concept, convective cells in an aggregated state are surrounded by air that is moister than the grid-mean condition, which provides a “shielding” effect favorable for deeper convective updrafts. Such effects are represented quantitatively via utilizing a schematic diagram about the geometric interpretation of convective cluster, dry area, and their contact area, in which both the convective cluster size and dry area fraction increase during the development of convection. Our sensitivity analyses indicate that the new scheme performs well in capturing the mean precipitation features. Excluding the convective organization effects in the model leads to a considerable reduction in the simulated precipitation magnitude. Notably, there exists an inverse relationship between background mean moisture condition and sub-grid moisture variability for a given rain rate, suggesting that with a high spatial heterogeneity in free-troposphere moisture, convection can still develop and maintain its strength under relatively dry background conditions, consistent with the convection-permitting model simulation. Overall, our new parameterization of convective organization effects can successfully reproduce the relationship between precipitation and sub-grid moisture variability, which is a missing element in traditional convection parameterization schemes but important for the simulations of precipitation variability at various scales in climate models.

54 ENVIRONMENTAL SCIENCES↗

Combination Thermal Barrier And Wear Coatings For Engines

Thermal-barrier layers covered with self-lubricating surface layers. Zirconia thermal-barrier coat applied to surface of combustion chamber in engine by plasma-arc spraying. Then PS-200 plasma-arc sprayed onto zirconia. Self-lubricating coat prevents sliding contact between thermal barrier and piston ring, effectively preventing both wear and production of additional heat via friction. Other combinations of thermal-barrier and self-lubricating, wear-resistant coating materials used as long as two materials adhere to each other, applied by use of similar or compatible processes, have similar coefficients of thermal expansion, sufficiently strong at high temperatures, and affordable.

Weingart, Mike↗

NASA's Electronic Procurement System and the Impact on Small Business

Three workshops, held in Lancaster, Orange County and Compton, were produced by the Los Angeles Regional Technology Alliance (LARTA) and NASA Far West Technology Transfer Center (FWRTTC). The workshops were held on December 12, 1997, February 5, 1998, and March 30, 1998, respectively. The purpose behind these workshops was to spread information regarding NASA procurement opportunities to small businesses in the region. This was accomplished by inviting economic and business development organizations to the three workshops, presenting NASA procurement resources to them, and asking them to distribute this information to the small businesses in their communities. With the assistance of LARTA, marketing and publicity in the form of direct mail, telemarketing, and promotion via a web site was implemented to publicize the workshops. These methods were remarkably effective because they enabled the workshops to attain its full capacity. Further publicity was provided by Wendy Reed of Valley Focus Magazine, an Antelope Valley Magazine aimed at business people. Her article entitled, "Doing Business with the Government" recapped the Lancaster workshop that she had attended and made references to several presentations. In the article, she discussed selling to the government via electronic commerce, and specifically mentioned Robert Medina, the NASA Dryden Small Business Specialist, as a contact person for those interested in pursuing procurement opportunities. The feedback provided by the participants is illustrated by the enclosed graphs and charts. These figures represent the number of participants who have frequented web sites presented at workshops, specifically the NASA procurement resources, and how extensive information dissemination was. Input from participants was favorable and encouraged more NASA Dryden workshops directly to the small business communities. There was an overwhelming response to the benefit of the NASA procurement opportunities presented at the workshops. Ninety-nine percent of participants who responded to surveys expressed that the NASA procurement information was beneficial. By the fifth month after the start of the workshops, NASA procurement resource inquiries peaked at 100%. Also during this time, 100% of respondents to a survey mentioned that they had passed along information from workshops to other small businesses or organizations that could benefit from it. These results indicate successful implementation of the Dryden Workshops. The objective of spreading NASA procurement opportunities throughout small businesses in the region was achieved through the three workshops. In conclusion, we recommend that further NASA procurement workshops be funded to continue the education and outreach that has been started. We also feel that in addition to targeting economic development service providers, Dryden procurement should also be provided directly to small business communities.

Dozier, Ken↗

Design and Fabrication of a 5-kWe Free-Piston Stirling Power Conversion System

Progress in the design and fabrication of a 5-kWe free-piston Stirling power conversion system is described. A scaled-down version of the successful 12.5-kWe Component Test Power Converter (CTPC) developed under NAS3-25463, this single cylinder prototype incorporates cost effective and readily available materials (steel versus beryllium) and components (a commercial linear alternator). The design consists of a displacer suspended on internally pumped gas bearings and a power piston/alternator supported on flexures. Non-contacting clearance seals are used between internal volumes. Heat to and from the prototype is supplied via pumped liquid loops passing through shell and tube heat exchangers. The control system incorporates several novel ideas such as a pulse start capability and a piston stroke set point control strategy that provides the ability to throttle the engine to match the required output power. It also ensures stable response to various disturbances such as electrical load variations while providing useful data regarding the position of both power piston and displacer. All design and analysis activities are complete and fabrication is underway. Prototype test is planned for summer 2008 at Foster-Miller to characterize the dynamics and steady-state operation of the prototype and determine maximum power output and system efficiency. Further tests will then be performed at Auburn University to determine start-up and shutdown characteristics and assess transient response to temperature and load variations.

Chapman, Peter A.↗

Making Superconducting Welds between Superconducting Wires

A technique for making superconducting joints between wires made of dissimilar superconducting metals has been devised. The technique is especially suitable for fabrication of superconducting circuits needed to support persistent electric currents in electromagnets in diverse cryogenic applications. Examples of such electromagnets include those in nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) systems and in superconducting quantum interference devices (SQUIDs). Sometimes, it is desirable to fabricate different parts of a persistent-current-supporting superconducting loop from different metals. For example, a sensory coil in a SQUID might be made of Pb, a Pb/Sn alloy, or a Cu wire plated with Pb/Sn, while the connections to the sensory coil might be made via Nb or Nb/Ti wires. Conventional wire-bonding techniques, including resistance spot welding and pressed contact, are not workable because of large differences between the hardnesses and melting temperatures of the different metals. The present technique is not subject to this limitation. The present technique involves the use (1) of a cheap, miniature, easy-to-operate, capacitor-discharging welding apparatus that has an Nb or Nb/Ti tip and operates with a continuous local flow of gaseous helium and (2) preparation of a joint in a special spark-discharge welding geometry. In a typical application, a piece of Nb foil about 25 m thick is rolled to form a tube, into which is inserted a wire that one seeks to weld to the tube (see figure). The tube can be slightly crimped for mechanical stability. Then a spark weld is made by use of the aforementioned apparatus with energy and time settings chosen to melt a small section of the niobium foil. The energy setting corresponds to the setting of a voltage to which the capacitor is charged. In an experiment, the technique was used to weld an Nb foil to a copper wire coated with a Pb/Sn soft solder, which is superconducting. The joint was evaluated as part of a persistent-current circuit having an inductance of 1 mH. A current was induced in a loop, and no attenuation of the current after a time interval 1,000 s was discernible in a measurement having a fractional accuracy of 10(exp -4): This observation supports the conclusion that the weld had an electrical resistance <10(exp -10) omega.

Penanen, Konstantin I.↗

The Training Process of the Organization Development and Training Office

The Organization Development and Training Office provides training and development opportunities to employees at NASA Glenn Research Center, as a division of the Office of Human Resources and Workforce Planning. Center-wide required trainings, new employee trainings, workshops and career development programs are organized by the OD&TO staff. They also arrange all academic, non-academic, headquarters, fellowship and learning center sponsored courses. They also service organizations wishing to work more effectively by facilitating teambuilding exercises. Equal Opportunity programs and upward mobility programs such as the STEP and GO programs for administrative staff. In working with my mentor I am very involved with Cuyahoga Community College classes, mandatory supervisory training and administrative staff workshops. My largest tasks are in the secretarial training category. The Supporting Organizations And Relationships workshop for administrative personnel, commonly known as SOAR, began last year and continued this summer with follow-up workshops. Months before a workshop or class is brought to Glenn, a need has to be realized. In this case, administrative staff did not feel they had an opportunity to receive relevant training and develop skills through teambuilding, networking and communication. A Statement of work is then created as several companies are contacted about providing the training. After the company best suited to meet the target group s needs is selected, the course is announced with an outline of all pertinent information. A reservation for a facility is made and applications or nominations, depending on the announcement s guidelines, are received from interested employees. Confirmations are sent to participants and final preparations are made but there are still several concluding steps. A training office staff member also assists the facilitator with setting up the facility and introducing the class. After the class, participants evaluations are read and summarized to determine the effectiveness of the class and instructor. In addition to the SOAR workshops, I have several projects and daily tasks to complete. Coding training applications, which require me to be familiar with Glenn s budgetary allocations and policies on training, is an ongoing process. It also requires verifying information reported by an employee via her C-478 form, more commonly known as the training application. I am also the point of contact for the Cuyahoga Community College Advising Sessions held here at NASA Glenn which involves coordinating counselors visits with employees schedules. Two databases had to be created. The first database holds information on administrative staff, and the other tracks supervisors training histories. Through these assignments I gained experience in Microsoft Access 2002 and spreadsheet creation, communicating with co-workers, and successfully facilitating a training to serve specific purposes. With trainings and evaluations to assessment them, the Organization Development and Training Office can assure a quality product and continued customer satisfaction.

Johnson, Melissa S.↗

Earth to Moon Transfers - Direct vs Via Libration Points (L1, L2)

Recommend Direct Remote Ocean Area impact disposal for caseswithout hazardous (e.g., radioactive) material on LTV kickstage Controlled Earth contact. Relatively small disposal AV. Avoids close encounter with Moon. Trajectories can be very sensitive to initial conditions (at disposalmaneuver).V to correct for errors is small. Recommend Heliocentric Orbit disposal for cases with hazardousmaterial on LTV kickstage. No Earth or Lunar disposal issues (e.g.. impact location, debris footprint,litter). Relatively low disposal AV cost. Further study required to determine possibility of re-contact with Earth.

Condon, Gerald L.↗

Crane-Load Contact Sensor

An electronic instrument has been developed as a prototype of a portable crane-load contact sensor. Such a sensor could be helpful in an application in which the load rests on a base in a horizontal position determined by vertical alignment pins (see Figure 1). If the crane is not positioned to lift the load precisely vertically, then the load can be expected to swing once it has been lifted clear of the pins. If the load is especially heavy, large, and/or fragile, it could hurt workers and/or damage itself and nearby objects. By indicating whether the load remains in contact with the pins when it has been lifted a fraction of the length of the pins, the crane-load contact sensor helps the crane operator determine whether it is safe to lift the load clear of the pins: If there is contact, then the load is resting against the sides of the pins and, hence, it may not be safe to lift; if contact is occasionally broken, then the load is probably not resting against the pins, so it should be safe to lift. It is assumed that the load and base, or at least the pins and the surfaces of the alignment holes in the load, are electrically conductive, so the instrument can use electrical contact to indicate mechanical contact. However, DC resistance cannot be used as an indicator of contact for the following reasons: The load and the base are both electrically grounded through cables (the load is grounded through the lifting cable of the crane) to prevent discharge of static electricity. In other words, the DC resistance between the load and the pins is always low, as though they were always in direct contact. Therefore, instead of DC resistance, the instrument utilizes the AC electrical impedance between the pins and the load. The signal frequency used in the measurement is high enough (.1 MHz) that the impedance contributed by the cables and the electrical ground network of the building in which the crane and the base are situated is significantly greater than the contact impedance between the pins and the load. The instrument includes a signal generator and voltage-measuring circuitry, and is connected to the load and the base as shown in Figure 2. The output of the signal generator (typically having amplitude of the order of a volt) is applied to the load via a 50-resistor, and the voltage between the load and the pins is measured. When the load and the pins are not in contact, the impedance between them is relatively high, causing the measured voltage to exceed a threshold value. When the load and the pins are in contact, the impedance between them falls to a much lower value, causing the voltage to fall below the threshold value. The voltage-measuring circuitry turns on a red light-emitting diode (LED) to indicate the lower-voltage/ contact condition. Whenever the contact has been broken and the non-contact/higher-voltage condition has lasted for more than 2 ms, the voltage-measuring circuitry indicates this condition by blinking a green LED.

Youngquist, Robert↗

Contact formation in gallium arsenide solar cells

Gold and gold-based alloys, commonly used as solar cell contact materials, are known to react readily with gallium arsenide. Experiments were performed to identify the mechanisms involved in these GaAs-metal interactions. It is shown that the reaction of GaAs with gold takes place via a dissociative diffusion process. It is shown further that the GaAs-metal reaction rate is controlled to a very great extent by the condition of the free surface of the contact metal, an interesting example of which is the previously unexplained increase in the reaction rate that has been observed for samples annealed in a vacuum environment as compared to those annealed in a gaseous ambient. A number of other hard-to-explain observations, such as the low-temperature formation of voids in the gold lattice and crystallite growth on the gold surface, are explained by invoking this mechanism.

Weizer, Victor G.↗

Tuning the fluid wetting dynamics on gold microstructures using photoactive compounds

This work demonstrates how photoactive compounds can be used to tune the surface chemistry, surface free energy, and the wetting velocity of fluids on Spiropyran functionalized surfaces with different surface microstructures. Evidence of this photowetting effect is based on data showing: (1) the cyclic changes in the static, advancing, and receding contact angles $\theta$ CA for multiple UV$\rightleftarrows$vis photoswitching cycles with both smooth and microstructured surfaces and (2) the changes in the fluid wicking velocity (via UV$\rightleftarrows$vis photoswitching) on different Spiropyran functionalized hemiwicking surfaces. X-ray photoelectron spectroscopy is used to determine the efficiency of photoswitching caused by the quality of the Spiropyran functionalization. Reversible photoisomerization of Spiropyran generates a gradient in surface free energy, resulting in a similar change in contact angle ($\theta$ CA ) in the photoswitchable surfaces. In conclusion, by incorporating these changes into the Owens-Wendt and Van Oss surface energy models, the energy of smooth Au surfaces can also be predicted for both UV and visible light irradiations, where reversible contact angle variations of $\Delta$$\theta$ CA ≈ 5–10° are achieved with both water and water-ethanol mixtures due to the conversion of SP to merocyanine, which corresponds to a total free energy change of ~13% on the photoswitchable surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A conformal heat-drying direct ink writing 3D printing for high-performance lithium-ion batteries

High areal capacity electrodes hold great potential for high-energy density lithium-ion batteries (LIBs), but their poor electrochemical kinetics limit their power density. Here, in this study, high areal capacity 3D-structured LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathodes (4.3 mAh cm -2 ) are prepared via 3D printing with a manner of direct ink writing. The electrodes had an enlarged electrode–electrolyte contact area, shortened diffusion pathway, and reduced intercalation-induced stress, thereby delivering enhanced rate capability and cyclability in LIBs, which is 143.6 mAh g -1 at 3C and a 60.2 % capacity retention over 800 cycles at 1C. Moreover, at electrode level, the 3D-NMC exhibits an energy and power densities of 313.1 Wh kg -1 and 657.9 W kg -1 , respectively. Furthermore, the theoretical calculation suggests that reducing the gap width will be highly beneficial to the energy and power densities. This work establishes a milestone in understanding the cycling effect on the electrode local structure, including the void area and the LiNi 0.8 Mn 0.1 Co 0.1 O 2 region, which confirms the effectiveness of 3D printing for electrode preparation.

25 ENERGY STORAGE↗

Binding of Phosphate Species to Ca 2+ and Mg 2+ in Aqueous Solution

Phosphate derivatives and their interaction with metal cations are involved in many important biological phenomena, so an accurate characterization of the phosphate-metal interaction is necessary to properly understand the role of phosphate-metal contacts in mediating biological function. Herein, we improved the standard 12-6 Lennard-Jones (LJ) potential via the usage of the 12-6-4 LJ model, which incorporates ion-induced dipole interactions. Via parameter scanning, we fine-tuned the 12-6-4 LJ polarizability values to obtain accurate absolute binding free energies for the phosphate anions H 2 PO 4 – , HPO 4 2– , PO 4 3– coordinating with Ca 2+ and Mg 2+ . First, we modified the phosphate 12-6-4 LJ parameters to reproduce the solvation free energies of the series of phosphate anions using the thermodynamic integration (TI) method. Then, using the potential mean force (PMF) method, the polarizability of the metal-phosphate interaction was obtained. We show that the free energy profiles of phosphate ions coordinated to Ca 2+ and Mg 2+ generally show similar trends at longer metal–phosphate distances, while the absolute binding energy values increased with deprotonation. The resulting parameters demonstrate the flexibility of the 12-6-4 LJ-type nonbonded model and its usefulness in accurately describing cation–anion interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exchange-Mediated Transport in Battery Electrolytes: Ultrafast or Ultraslow?

Understanding the mechanisms of charge transport in batteries is important for the rational design of new electrolyte formulations. Persistent questions about ion transport mechanisms in battery electrolytes are often framed in terms of vehicular diffusion by persistent ion–solvent complexes versus structural diffusion through the breaking and reformation of ion–solvent contacts, i.e., solvent exchange events. Ultrafast two-dimensional (2D) IR spectroscopy can probe exchange processes directly via the evolution of the cross-peaks on picosecond time scales. However, vibrational energy transfer in the absence of solvent exchange gives rise to the same spectral signatures, hiding the desired processes. Here we employ 2D IR on solvent resonances of a mixture of acetonitrile isotopologues to differentiate chemical exchange and energy-transfer dynamics in a comprehensive series of Li + , Mg 2+ , Zn 2+ , Ca 2+ , and Ba 2+ bis(trifluoromethylsulfonyl)imide electrolytes from the dilute to the superconcentrated regime. No exchange phenomena occur within at least 100 ps, regardless of the ion identity, salt concentration, and presence of water. All of the observed spectral dynamics originate from the intermolecular energy transfer. These results place the lower experimental boundary on the ion–solvent residence times to several hundred picoseconds, much slower than previously suggested. With the help of MD simulations and conductivity measurements on the Li + and Zn 2+ systems, we discuss these results as a continuum of vehicular and structural modalities that vary with concentration and emphasize the importance of collective electrolyte motions to ion transport. These results hold broadly applicable to many battery-relevant ions and solvents.

25 ENERGY STORAGE↗