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The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Parthasarathy, Arvind↗

Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

Parthasarathy, Arvind↗

The metal to metal interface and its effect on adhesion and friction

The nature of the interface, adhesion and friction properties of noble metals, platinum metals, Group IV (B) metals and transition metals were considered. The surface chemical activity of the noble and platinum metals is shown to effect metal to metal interfaces as does a valance bonding in the transition metals. With the Group IV (B) metals the degree of metallic nature of the elements is shown to effect interfacial behavior. The effect of surface segregation of alloy constituents such as silicon in iron and its influence on the metal to metal interface is discussed. In addition the effect of alloy constituents on changes in bulk properties such as transformations in tin are shown to effect interfacial adhesion and friction behavior.

Buckley, D. H.↗

The metal to metal interface and its effect on adhesion and friction

The paper considers the interface between two bulk metals and the effect of this interface on adhesive bonding, resistance to tangential displacements, friction and the interfacial transport from one surface to another. Using Auger emission spectroscopy, field ion microscopy, and low energy electron diffraction techniques, the influence of surface orientation, lattice registry, crystal lattice structure and defects, metal surface chemistry and alloying on the characteristics of the interface was studied for noble, platinum, transition, and Group 4B metals. With dissimilar metals in contact, epitaxial transfer of the cohesively weaker to the cohesively stronger metal has been observed. Surface chemical activity of the noble and platinum metals is shown to affect interfacial behavior as does a valence bonding in the transition metals, and the degree of metallic nature in the Group 4B elements. Alloying elements, e.g., Si and Fe, can alter interfacial behavior by segregation to the surface of metals or by altering bulk properties such as crystal transformation kinetics.

Buckley, D. H.↗

Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

Srinivasan, Supramaniam↗

ATS-F radiant cooler contamination test in a hydrazine thruster exhaust

A test was conducted under simulated space conditions to determine the potential thermal degradation of the ATS-F radiant cooler from any contaminants generated by a 0.44-N(0.1-lbf) hydrazine thruster. The radiant cooler, a 0.44-N(0.1-lbf)hydrazine engine, and an aluminum plate simulating the satellite interface were assembled to simulate their flight configuration. The cooler was provided with platinum sensors for measuring temperature, and its surfaces were instrumented with six quartz crystal microbalance units (QCM) to measure contaminant mass deposits. The complete assembly was tested in the molecular sink vacuum facility (Molsink) at the Jet Propulsion Laboratory. This was the first time that a radiant cooler and a hydrazine engine were tested together in a very-high-vacuum space simulator, and this test was the first successful measurement of detectable deposits from hydrazine rocket engine plumes in a high vacuum. The engine was subjected to an accelerated duty cycle of 1 pulse/min, and after 2-hr of operation, the QCMs began to shift in frequency. The tests continued for several days and, although there was considerable activity in the QCMs, the cooler never experienced thermal degradation.

Chirivella, J. E.↗

Advanced spacecraft fuel cell systems.

The specific goals of the system selected for development are 10,000 hours of operation with refurbishment, 20 lb/kW at a sustained power of 7 kW, and 21 kW peaking capability for durations of two hours. The system is designed to operate on low pressure, propulsion grade hydrogen and oxygen. Product water is removed by a passive water removal method that employs a porous hydrophobic membrane as a part of the water transport plate. Aspects of system component testing are discussed together with advanced materials to be used. It was found that the initial performance of a cell with a gold catalyzed cathode is superior to a cell with platinum catalyst. The problem of a certain inability to maintain the desired gas-electrolyte-catalyst interface is the main source of difficulty with the gold-based catalysts.

Thaller, L. H.↗

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗

Adhesion and friction of thin metal films

Sliding friction experiments were conducted in vacuum with thin films of titanium, chromium, iron, and platinum sputter deposited on quartz or mica substrates. A single crystal hemispherically tipped gold slider was used in contact with the films at loads of 1.0 to 30.0 and at a sliding velocity of 0.7 mm/min at 23 C. Test results indicate that the friction coefficient is dependent on the adhesion of two interfaces, that between the film and its substrate and the slider and the film. There exists a relationship between the percent d bond character of metals in bulk and in thin film form and the friction coefficient. Oxygen can increase adhesive bonding of a metal film (platinum) to a substrate.

Buckley, D. H.↗

Orbital transfer rocket engine technology: Advanced engine study

An advanced LOX/LH2 engine study for the use of NASA and vehicle prime contractors in developing concepts for manned missions to the Moon, Mars, and Phobos is documented. Parametric design data was obtained at five engine thrusts from 7.5K lbf to 50K lbf. Also, a separate task evaluated engine throttling over a 20:1 range and operation at a mixture ratio of 12 plus or minus 1 versus the 6 plus or minus 1 nominal. Cost data was also generated for DDT&E, first unit production, and factors in other life cycle costs. The major limitation of the study was lack of contact with vehicle prime contractors to resolve the issues in vehicle/engine interfaces. The baseline Aerojet dual propellant expander cycle was shown capable of meeting all performance requirements with an expected long operational life due to the high thermal margins. The basic engine design readily accommodated the 20:1 throttling requirement and operation up to a mixture ratio of 10 without change. By using platinum for baffled injector construction the increased thermal margin allowed operation up to mixture ratio 13. An initial engine modeling with an Aerojet transient simulation code (named MLETS) indicates stable engine operation with the baseline control system. A throttle ratio of 4 to 5 seconds from 10 percent to 100 percent thrust is also predicted. Performance predictions are 483.1 sec at 7.5K lbf, 487.3 sec at 20K lbf, and 485.2 sec at 50K lbf with a mixture ratio of 6 and an area ratio of 1200. Engine envelopes varied from 120 in. length/53 in. exit diameter at 7.5K lbf to 305 in. length/136 in. exit diameter at 50 K lbf. Packaging will be an important consideration. Continued work is recommended to include more vehicle prime contractor/engine contractor joint assessment of the interface issues.

Hayden, Warren R.↗

Two dimensional, transient catalytic combustion of CO-air on platinum

The light off transient of catalytic combustion of lean CO-air mixtures in a platinum coated channel of a honeycomb monolith is studied with a model that resolves transient radial and axial gradients in both the gas and the solid. For the conditions studied it is concluded that: the initial heat release occurs near the entrance at the gas-solid interface and is controlled by heterogeneous reactions; large spatial and temporal temperature gradients occur in the solid near the entrance controlled mostly by the availability of fuel; the temperature of the solid near the entrance achieves almost its steady state value before significant heating of the back; heterogeneous reactions and the gas heated up front and flowing downstream heat the back of the solid; the overall transient time is controlled by the thermal inertia of the solid and by forced convection; radiation significantly influences both transient and steady state particularly near the entrance; the oxidation of CO occurs mostly on the catalyst and becomes diffusion controlled soon into the transient.

Sinha, N.↗

Electrochemical performance investigations on the hydrogen depolarized CO2 concentrator

An extensive investigation of anode and cathode polarization in complete cells and half cells was conducted to determine the factors affecting HDC electrode polarization and the nature of this polarization. Matrix-electrolyte-electrode interactions and cell electrolyte composition were also investigated. The electrodes were found to have normal performance capabilities. The HDC anode polarization characteristics were correlated with a theoretical kinetic analysis; and, except for some quantitative details, a rather complete understanding of the causes for HDC electrode polarization was formulated. One of the important finding resulting from the kinetic analysis was that platinum appears to catalyze the decomposition of carbonic acid to carbon dioxide and water. It was concluded that the abnormal voltage performance of the One Man ARS HDC cells was caused by insufficient cell electrolyte volume under normal operating conditions due to deficiencies in the reservoir to cell interfacing.

Aylward, J. R.↗

Effect of barrier height on friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals

Friction experiments were conducted for the semiconductors silicon and gallium arsenide in contact with pure metals. Polycrystalline titanium, tantalum, nickel, palladium, and platinum were made to contact a single crystal silicon (111) surface. Indium, nickel, copper, and silver were made to contact a single crystal gallium arsenide (100) surface. Sliding was conducted both in room air and in a vacuum of 10 to the minus 9th power torr. The friction of semiconductors in contact with metals depended on a Schottky barrier height formed at the metal semiconductor interface. Metals with a higher barrier height on semiconductors gave lower friction. The effect of the barrier height on friction behavior for argon sputtered cleaned surfaces in vacuum was more specific than that for the surfaces containing films in room air. With a silicon surface sliding on titanium, many silicon particles back transferred. In contrast, a large quantity of indium transferred to the gallium arsenide surface.

Mishina, H.↗

The friction behavior of semiconductors Si and GaAs in contact with pure metals

The friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals was studied. Five transition and two nontransition metals, titanium, tantalum, nickel, palladium, platinum, copper, and silver, slid on a single crystal silicon (111) surface. Four metals, indium, nickel, copper and silver, slid on a single crystal gallium arsenide (100) surface. Experiments were conducted in room air and in a vacuum of 10 to the minus 7th power N/sq cm (10 to the minus 9th power torr). The results indicate that the sliding of silicon on the transition metals exhibits relatively higher friction than for the nontransition metals in contact with silicon. There is a clear correlation between friction and Schottky barrier height formed at the metal silicon interface for the transition metals. Transition metals with a higher barrier height on silicon had a lower friction. The same effect of barrier height was found for the friction of gallium arsenide in contact with metals.

Mishina, H.↗

High Temperature Characteristics of Pt/TaSi2/Pt/W and Pt/Ti/W Diffusion Barrier Systems for Ohmic Contacts to 4H-SiC

The degradation of ohmic contacts to 4H-SiC pressure sensors over time at high temperature is primarily due to two failure mechanisms: migrating bond pad Au and atmospheric O toward the ohmic contact SiC interface and the inter-metallic mixing between diffusion barrier systems (DBS) and the underlying ohmic contact metallization. We investigated the effectiveness of Pt/TaSi2/Pt/W (DBS-A) and Pt/Ti/W (DBS-B) in preventing Au and O diffusion through the underlying binary Ti/W or alloyed W50:Ni50 ohmic contacts to 4H-SiC and the DBS ohmic contact intermixing at temperature up to 700 C.

Platinum↗

A Study of Nucleate Boiling with Forced Convection in Microgravity

The ultimate objective of basic studies of flow boiling in microgravity is to improve the understanding of the processes involved, as manifested by the ability to predict its behavior. This is not yet the case for boiling heat transfer even in earth gravity, despite the considerable research activity over the past 30 years. The elements that constitute the nucleate boiling process - nucleation, growth, motion, and collapse of the vapor bubbles (if the bulk liquid is subcooled) - are common to both pool and flow boiling. It is well known that the imposition of bulk liquid motion affects the vapor bubble behavior relative to pool boiling, but does not appear to significantly influence the heat transfer. Indeed, it has been recommended in the past that empirical correlations or experimental data of pool boiling be used for design purposes with forced convection nucleate boiling. It is anticipated that such will most certainly not be possible for boiling in microgravity, based on observations made with pool boiling in microgravity. In earth gravity buoyancy will act to remove the vapor bubbles from the vicinity of the heater surface regardless of how much the imposed bulk velocity is reduced, depending, of course, on the geometry of the system. Vapor bubbles have been observed to dramatically increase in size in pool boiling in microgravity, and the heat flux at which dryout took place was reduced considerably below what is generally termed the critical heat flux (CHF) in earth gravity, depending on the bulk liquid subcooling. However, at heat flux levels below dryout, the nucleate pool boiling process was enhanced considerably over that in earth gravity, in spite of the large vapor bubbles formed in microgravity and perhaps as a consequence. These large vapor bubbles tended to remain in the vicinity of the heater surface, and the enhanced heat transfer appeared to be associated with the presence of what variously has been referred to as a liquid microlayer between the bubble and the heater surface. The enhancement of the boiling process with low velocities in earth gravity for those orientations producing the formation of a liquid macrolayer described above, accompanied by "sliding" vapor bubbles, has been demonstrated. The enhancement was presented as a function of orientation, subcooling, and heated length, while a criterion for the heat transfer for mixed natural/forced convection nucleate boiling was given previously. A major unknown in the prediction and application of flow boiling heat transfer in microgravity is the upper limit of the heat flux for the onset of dryout (or critical heat flux - CHF), for given conditions of fluid-heater surfaces, including geometry, system pressure and bulk liquid subcooling. It is clearly understood that the behavior in microgravity will be no different than on earth with sufficiently high flow velocities, and would require no space experimentation. However, the boundary at which this takes place is still an unknown. Previous results of CHF measurements were presented for low velocity flow boiling at various orientations in earth gravity as a function of flow velocity and bulk liquid subcooling, along with preliminary measurements of bubble residence times on a flat heater surface. This showed promise as a parameter to be used in modeling the CHF, both in earth gravity and in microgravity. The objective of the work here is to draw attention to and show results of current modeling efforts for the CHF, with low velocities in earth gravity at different orientations and subcoolings. Many geometrical possibilities for a heater surface exist in flowing boiling, with boiling on the inner and outer surfaces of tubes perhaps being the most common. If the vapor bubble residence time on and departure size from the heater surface bear a relationship to the CHF, as results to be given indicate, it is important that visualization of and access to vapor bubble growth be conveniently available for research purposes. In addition, it is desirable to reduce the number of variables as much as possible in a fundamental study. These considerations dictated the use of a flat heater surface, which is rectangular in shape, 1.91 cm by 3.81 cm (0.75 x 1.5 inches), consisting either of a 400 Angstrom thick semi-transparent gold film sputtered on a quartz substrate which serves simultaneously as a heater and a resistance thermometer, or a copper substrate of the same size. The heater substrate is a disc which can be rotated so that the heated length in the flow direction can be changed from 1.91 to 3.81 cm (0.75 to 1.5 inches). The fluid is R-113, and the velocities can be varied between 0.5 cm/s and 60 cm/s. For a sufficiently low velocity the CHF can be modeled reasonably well at various orientations by the correlation for pool boiling corrected for the influence of bulk liquid subcooling, multiplied by the square root of q, the angle relative to horizontal. This arises from equating buoyancy and drag forces in the inverted positions where the vapor bubbles are held against the heater surface as they slide. A distortion of the measurements relative to pool boiling occurs as the flow velocity increases. In modeling this effect at different levels of subcooling it appeared appropriate to estimate the volumetric rate of vapor generation, using measurements of bubble frequency (or residence time), void fraction and average bubble boundary layer thickness. These were determined with the use of a platinum hot wire probe 0.025 mm in diameter by 1.3 mm long, applying a constant current to distinguish between contact with liquid or vapor. Two-dimensional spatial variations are obtained with a special mechanism to resolve displacements in increments of 0.025 mm. From such measurements it was determined that the fraction of the surface heat transfer resulting in evaporation varies inversely with the subcooling correction factor for the CHF. The measured inverse bubble residence time is normalized relative to that predicted for an infinite horizontal flat plate at the CHF, and is correlated well with the CHF normalized relative to that for pool boiling, for various orientation angles and subcooling levels. This correspondence is then combined with a normalizing factor for the energy flux leaving the heater surface at the CHF and the computed bubble radius at departure, determined from the balance between the outward velocity of the interface due to evaporation and the buoyance induced velocity of the center of mass of the bubble. The product of the CHF and the corresponding residence time was determined to be a constant for all orientations at a given bulk flow velocity and liquid subcooling, and must be determined empirically for each velocity and subcooling at present. It then becomes possible to predict the CHF for the different orientations, velocities, and subcoolings. These are compared with normalized measurements of the CHF for velocities ranging from 4 cm/s to 55 cm/s, subcoolings from 2.8 to 22.2 K, over orientations angles of 360 degrees.

Merte, Herman, Jr.↗

Thermodynamic Effect of Platinum Addition to beta-NiAl: An Initial Investigation

An initial investigation was conducted to determine the effect of platinum addition on the activities of aluminum and nickel in beta-NiAl(Pt) over the temperature range 1354 to 1692 K. These measurements were made with a multiple effusion-cell configured mass spectrometer (multi-cell KEMS). The results of this study show that Pt additions act to decreased alpha(Al) and increased the alpha(Ni) in beta-NiAl(Pt) for constant X(sub Ni)/X(sub Al) approx. = 1.13, while at constant X(sub Al) the affect of Pt on Al is greatly reduced. The measured partial enthalpies of mixing indicate Al-atoms have a strong self interaction while Ni- and Pt-atoms in have similar interactions with Al-atoms. Conversely the binding of Ni-atoms in beta-NiAl decreases with Pt addition independent of Al concentration. These initial results prove the technique can be applied to the Ni-Al-Pt system but more activity measurements are required to fully understand the thermodynamics of this system and how Pt additions improved the scaling behavior of nickel-based superalloys. In addition, with the choice of a suitable oxide material for the effusion-cell, the "closed" isothermal nature of the effusion-cell allows the direct investigation of an alloy-oxide equilibrium which resembles the "local-equilibrium" description of the metal-scale interface observed during high temperature oxidation. It is proposed that with an Al(l) + Al2O3(s) experimental reference state together with the route measurement of the relative partial-pressures of Al(g) and Al2O(g) allows the activities of O and Al2O3 to be determined along with the activities of Ni and Al. These measurements provide a direct method of investigating the thermodynamics of the metal-scale interface of a TGO-scale.

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