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At least 91 records · Page 5

Study of metal corrosion using ac impedance techniques in the STS launch environment

AC impedance measurements were performed to investigate the corrosion resistance of 19 alloys under conditions similar to the STS launch environment. The alloys were: Zirconium 702, Hastelloy C-22, Inconel 625, Hastelloy C-276, Hastelloy C-4, Inconel 600, 7Mo + N, Ferralium 255, Inco Alloy G-3, 20Cb-3, SS 904L, Inconel 825, SS 304LN, SS 316L, SS 317L, ES 2205, SS 304L, Hastelloy B-2, and Monel 400. AC impedance data were gathered for each alloy after one hour immersion time in each of the following three electrolyte solutions: 3.55 percent NaCl, 3.55 percent NaCl-0.1N HCl, and 3.55 percent NaCl-1.0N HCl. The data were analyzed qualitatively using the Nyquist plot and quantitatively using the Bode plot. Polarization resistance, Rp, values were obtained using the Bode plot. Zirconium 702 was the most corrosion resistant alloy in the three electrolytes. The ordering of the other alloys according the their resistance to corrosion varied as the concentration of hydrochloric acid in the electrolyte increased. The corrosion resistance of Zirconium 702 and Ferralium 255 increased as the concentration of hydrochloric acid in the electrolyte increased. The corrosion resistance of the other 17 alloys decreased as the concentration of the hyrdochloric acid in the electrolyte increased.

Calle, Luz M.↗

KOH concentration effect on the cycle life of nickel-hydrogen cells. 4: Results of failure analyse

Effects of KOH concentrations on failure modes and mechanisms of nickel-hydrogen cells were studied using long cycled boiler plate cells containing electrolytes of various KOH concentrations ranging 21 to 36 percent. Life of these cells were up to 40,000 cycles in an accelerated low earth orbit (LEO) cycle regime at 80 percent depth of discharge. An interim life test results were reported earlier in J. Power Sources, 22, 213-220, 1988. The results of final life test, end-of-life cell performance, and teardown analyses are discussed. These teardown analyses included visual observations, measurements of nickel electrode capacity in an electrolyte-flooded cell, dimensional changes of cell components, SEM studies on cell cross section, BET surface area and pore volume distribution in cycled nickel electrodes, and chemical analyses. Cycle life of a nickel-hydrogen cell was improved tremendously as KOH concentration was decreased from 36 to 31 percent and from 31 to 26 percent while effect of further concentration decrease was complicated as described in our earlier report. Failure mode of high concentration (31 to 36 percent) cells was gradual capacity decrease, while that of low concentration (21 to 26 percent) cells was mainly formation of a soft short. Long cycled (25,000 to 40,000 cycles) nickel electrodes were expanded more than 50 percent of the initial value, but no correlation was found between this expansion and measured capacity. All electrodes cycled in low concentration (21 to 26 percent) cells had higher capacity than those cycled in high concentration (31 to 36 percent) cells.

Lim, H. S.↗

Changes in total plasma content of electrolytes and proteins with maximal exercise.

To determine to what extent the increases in concentration of plasma proteins and electrolytes with short maximal work were a result of hemoconcentration, the changes in plasma volume and total content of the plasma constituents were simultaneously evaluated. The results obtained from six human subjects indicated that in comparison to preexercise values there was a net decrease in total content of plasma protein, sodium, and chloride in the first 2 min of the postexercise period, due primarily to a significant loss (13-15%) of plasma fluid. The total plasma potassium content was increased immediately after exercise but was significantly below the preexercise plasma content after 2 min of recovery.

Van Beaumont, W.↗

Li-Ion Batteries for Space Applications: High Specific Energy and Wide-Operating Temperature

Compared to the conventional Ni-Co oxides (with or without AI additions), the NMC (1/3:1/3:1/3) cathode provides marginal improvement in specific capacity. However, some of the formulations based on the solid solutions of layered Li2Mn03 and LiM02 (M = Mn0.5Ni0.5} have shown capacities as high as 250 mAh/g, combined with high cell voltages (4.5 V) and with the likelihood of enhanced thermal stability. Multi-component electrolytes with low EC-proportions and selected co-solvents provide significant improvement in the low temperature performance, down to -60 C, combined with the non-flammable attribute from the co-solvents. The NMC cathode shows good compatibility with the carbonate-based low temperature electrolytes. Impressive performances have been realized at low temperatures of <= 30 C. Electrolytes with high salt concentration and high EC content fare well at room temperatures, while the formulations with low EC content and low salt concentration are preferred at low temperatures. DPA studies reveal increased SEI growth on the electrodes, especially anode, upon irradiation. Performance of low temperature electrolytes in prototype cells corroborate the findings from laboratory cells.

storage↗

Effect of KOH concentration and anions on the performance of Ni-H2 battery positive plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galavanostatic charging; and discharging in a flooded electrolyte cell. Three different concentrations of KOH (40 percent, 31 percent, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate or silicate were investigated. The end of charge voltage at C/10 charge and at 10 C showed the following order: 40 percent KOH is greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOE. The middischarge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without the added contaminants and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH where the capacity declined after 1000 cycles at 80 percent DOD. At the end of cycling the plate tested in the presence of sulfate and silicate experienced measurable weight loss as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the second oxidation peak that corresponds to the formation of a different phase of oxidized Ni has a lower peak current at -5 C compared to 25 C and oxygen evolution occurs a higher potential at -5 C. The reduction peak (discharge reaction) is more polarized at 25 C compared to -5 C. The presence of silicate alters the potentials only marginally. The implications of these results in plate treatment and low temperature operation are discussed.

Vaidyanathan, H.↗

Effect of KOH Concentration and Anions on the Performance of a Ni-H2 Battery Positive Plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galvanostatic charging and discharging in a flooded electrolyte cell. Three different concentrations of potassium hydroxide (KOH) (40, 31, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate, or silicate were investigated. The end-of-charge voltage at C/10 charge and at 10 degrees C showed the following order: 40 percent KOH greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOH. The mid discharge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without added contaminants, and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH, where the capacity declined after 1,000 cycles at 80 percent depth of discharge (DOD). At the end of cycling, all the plates tested experienced a weight loss, except in the case of 31 percent KOH, as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the cathodic peak potentials are less polarized in the presence and absence of silicate at -5 degrees C compared to 25 degrees C indicating a slightly higher voltage during discharge in a Ni-H2 battery. Futhermore, the features of the current-potential profile were practically unchanged in the presence of silicate.

Vaidyanathan, Hari↗

KOH concentration effect on the cycle life of nickel-hydrogen cells. Part 4: Results of failure analyses

KOH concentration effects on cycle life of a Ni/H2 cell have been studied by carrying out a cycle life test of ten Ni/H2 boiler plate cells which contain electrolytes of various KOH concentrations. Failure analyses of these cells were carried out after completion of the life test which accumulated up to 40,000 cycles at an 80 percent depth of discharge over a period of 3.7 years. These failure analyses included studies on changes of electrical characteristics of test cells and component analyses after disassembly of the cell. The component analyses included visual inspections, dimensional changes, capacity measurements of nickel electrodes, scanning electron microscopy, BET surface area measurements, and chemical analyses. Results have indicated that failure mode and change in the nickel electrode varied as the concentration was varied, especially, when the concentration was changed from 31 percent or higher to 26 percent or lower.

Lim, H. S.↗

KOH concentration effect on the cycle life of nickel-hydrogen cells. IV - Results of failure analysis

Potassium hydroxide concentration effects on the cycle life of a Ni/H2 cell have been studied by carrying out a cycle life test on ten Ni/H2 boiler plate cells which contain electrolytes of various KOH concentrations. Failure analyses of these cells were carried out after completion of the life test, which accumulated up to 40,000 cycles at an 80-percent depth of discharge over a period of 3.7 years. These failure analyses included studies on changes of electrical characteristics of test cells, and component analyses after disassembly of the cell. The component analyses included visual inspections, dimensional changes, capacity measurements of nickel electrodes, scanning electron microscopy, surface area measurements, and chemical analyses. Results have indicated that failure mode and change in the nickel electrode varied as the concentration was varied, especially when the concentration was changed from 31 percent or higher to 26 percent or lower.

Lim, H. S.↗

Electrodeposition of Metals in Microgravity Conditions

Metal electrodeposition may introduce various morphological variations depending on the electrolytic conditions including cell configurations. For liquid electrolytes, a precise study of these deposits may be complicated by convective motion due to buoyancy. Zero-gravity (0-G) condition provided by drop shaft or parabolic flight gives a straightforward mean to avoid this effect: we present here 0-G electrodeposition experiments, which we compare to ground experiments (1-G). Two electrochemical systems were studied by laser interferometry, allowing to measure the concentration variations in the electrolyte: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. For copper, concentration variations were in good agreement with theory. For lithium, an apparent induction time was observed for the concentration evolution at 1-G: due to this induction time and to the low diffusion coefficient in ionic liquid, the concentration variations were hardly measurable in the parabolic flight 0-G periods of 20 seconds.

Nishikawa, K.↗

The value of the 4-day headdown bedrest model for screening countermeasures

In order to evaluate the benefits of periodic exposure to the +G(z) vector as a countermeasure to the physiological responses to minus 6 degree head down bedrest (HDT), we considered a two-tiered approach: (a) to use 4 days HDT as a quick and inexpensive means of screening countermeasures, (b) to use a 60 day HDT to validate the most promising candidates. The approach and results of a 4 day study are described here. Methods: Nine males were admitted to our Human Research Facility for one ambulatory control day followed by 4 days HDT and were released on the next day after completion of a peak oxygen consumption test (VO(sub 2 peak)). A battery of tests was selected and standardized to evaluate the known early effects of HDT on plasma volume, early bone markers, orthostatic tolerance, physical performance, and fluid and electrolytes and their hormone regulation. Fluid sodium (Na) and potassium (K) intake and output in the urine were monitored throughout. Plasma volume was determined with a modified Evans Blue method and orthostatic tolerance with a 60 degree head-up tilt test for 30 minutes - both of which were determined on the ambulatory control day and on day 4 of HDT. Immediately after completion of the tilt test subjects were returned to the minus 6 degree position until the next morning when a VO(sub 2 peak) (horizontal ergometer) was done. This was compared to a similar control test determined on 2 separate occasions before subject admission. Results: Four hours after going HDT produced significant decreases (p less than 0.05) in the circulating concentration of fluid and electrolyte regulating hormones. Plasma volume, orthostatic tolerance and VO(sub 2 peak) changed significantly after 4 days HDT. There was also the expected natriuresis on day 1 of HDT but no significant diuresis. The consistency of the pre-bedrest VO(sub 2 peak) tilt tests and plasma volumes was remarkable. Conclusions: The 4 day HDT model seems highly promising for screening a variety of countermeasures alone and in combination before validating their benefits in extended bedrest or flight experiments.

Vernikos, J.↗

Cycle life of nickel-hydrogen cells. II - Accelerated cycle life test

A cycle life test of nickel-hydrogen (Ni/H2) cells containing electrolytes of various KOH concentrations and a sintered-type nickel electrode were carried out at 23 C using a 45-min accelerated low earth orbit (LEO) cycle regime at 80 percent depth of discharge. Ten cells containing 21 to 36 percent KOH were tested. Since this accelerated test regime accelerated the cycle life roughly twice as fast as a typical LEO regime, the present results indicate that the cells with 26 percent KOH may last over 5 years in an 80 percent depth-of-discharge cycling in an LEO regime. Cells with lower KOH concentrations (21 to 23.5 percent) also showed longer cycle life than those with KOH concentrations of 31 percent or higher, although the life was shorter than those with 26 percent KOH.

Lim, H. S.↗

Raman spectral observation of a new phase observed in nickel electrodes cycled to failure

A ‘new phase’ is reported in nickel electrodes from Ni/H2 boilerplate cells which were cycled to failure in electrolyte of variable KOH concentration (21–36%). Raman spectra clearly show the presence of this phase, and these spectra have been used to estimate the amounts present on these electrodes. Ten of twelve electrodes examined contain this new phase. The cycle life at higher KOH concentrations (31 and 36%) was greatly reduced, and nickel electrodes from these cells exhibited extensive amounts of this new phase. The presence of this ‘new phase’ correlates with cell failure defined by low end of discharge voltages. It is proposed that the lowered capacity and failure of these electrodes was caused by loss of active mass and formation of a phase with reduced electrochemical activity. These results indicate that formation of this new phase is accelerated at higher KOH concentrations.

Patricia L Loyselle↗

Raman Spectral Observation of a "New Phase" Observed in Nickel Electrodes Cycled to Failure

A "new phase" is reported in nickel electrodes from Ni/H boilerplate cells which were cycled to failure in electrolyte of variable kOH concentration. Raman spectra clearly show the presence of this phase, and these spectra have been used to quantify the amounts present in these electrodes (in the volume sampled by the laser beam) Raman spectroscopy has been found to be capable of differentiating the various phases which can be present in nickel .This differentiation is possible because of the structural variation observed for these phases. Ten of twelve electrodes examined contain at least some of this new phase. The presence of this "new phase" correlates with cell failure, and it is proposed that the presence of this phase may play a role in early electrode failure.

Loyselle, P. L.↗

Flow Visualization of Low Prandtl Number Fluids using Electrochemical Measurements

It is well established that residual flows exist in contained liquid metal processes. In 1-g processing, buoyancy forces often drive these flows and their magnitudes can be substantial. It is also known that residual flows can exist during microgravity processing, and although greatly reduced in magnitude, they can influence the properties of the processed materials. Unfortunately, there are very few techniques to visualize flows in opaque, high temperature liquid metals, and those available are not easily adapted to flight investigation. In this study, a novel technique is developed that uses liquid tin as the model fluid and solid-state electrochemical cells constructed from Yttria-Stabilized Zirconia (YSZ) to establish and measure dissolved oxygen boundary conditions. The melt serves as a common electrode for each of the electrochemical cells in this design, while independent reference electrodes are maintained at the outside surfaces of the electrolyte. By constructing isolated electrochemical cells at various locations along the container walls, oxygen is introduced or extracted by imposing a known electrical potential or passing a given current between the melt and the reference electrode. This programmed titration then establishes a known oxygen concentration boundary condition at the selected electrolyte-melt interface. Using the other cells, the concentration of oxygen at the electrolyte-melt interface is also monitored by measuring the open-circuit potentials developed between the melt and reference electrodes. Thus the electrochemical cells serve to both establish boundary conditions for the passive tracer and sense its path. Rayleigh-Benard convection was used to validate the electrochemical approach to flow visualization. Thus, a numerical characterization of the second critical Rayleigh numbers in liquid tin was conducted for a variety of Cartesian aspect ratios. The extremely low Prandtl number of tin represents the lowest value studied numerically. Additionally, flow field oscillations are visualized and the effect of tilt on convecting systems is quantified. Experimental studies of the effect of convection in liquid tin are presented. Three geometries are studied: (1) double electrochemical cell with vertical concentration gradients; (2) double cell with horizontal concentration gradients; and (3) multiple cells with vertical temperature gradients. The first critical Rayleigh number transition is detected with geometry (1) and it is concluded that current measurements are not as affected by convection as EMF measurements. The system is compared with numerical simulations in geometry (2), and oscillating convection is detected with geometry (3).

Crunkleton, D.↗

Electrochemical Impedance Spectroscopy of Alloys in a Simulated Space Shuttle Launch Environment

Corrosion studies began at NASA/Kennedy Space Center in 1966 during the Gemini/Apollo Programs with the evaluation of long-term protective coatings for the atmospheric protection of carbon steel. An outdoor exposure facility on the beach near the launch pad was established for this purpose at that time. The site has provided over 35 years of technical information on the evaluation of the long-term corrosion performance of many materials and coatings as well as on maintenance procedures. Results from these evaluations have helped NASA find new materials and processes that increase the safety and reliability of our flight hardware, launch structures, and ground support equipment. The launch environment at the Kennedy Space Center (KSC) is extremely corrosive due to the combination of ocean salt spray, heat, humidity, and sunlight. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pad were rendered even more severe by the acidic exhaust from the solid rocket boosters. Over the years, many materials have been evaluated for their corrosion performance under conditions similar to those found at the launch pads. These studies have typically included atmospheric exposure and evaluation with conventional electrochemical methods such as open circuit potential (OCP) measurements, polarization techniques, and electrochemical impedance spectroscopy (EIS). The atmosphere at the Space Shuttle launch site is aggressive to most metals and causes severe pitting in many of the common stainless steel alloys such as type 304L stainless steel (304L SS). A study was undertaken to find a more corrosion resistant material to replace the existing 304L SS tubing. This paper presents the results from atmospheric exposure as well as electrochemical measurements on the corrosion resistance of AL-6XN (UNS N08367) and 254-SMO (UNS S32154). Type 304L SS (UNS S30403) was used as a control. Conditions at the Space Shuttle launch pad were simulated by using a hydrochloric acid (HC1) and alumina (Al203) slurry rinse for the atmospheric exposure and an electrolyte consisting of 3.55% sodium chloride (NaC1) with increased concentrations of hydrochloric acid (HC1) for the electrochemical measurements. The results from both types of measurements revealed the superior corrosion performance of the higher-alloyed materials. Unlike 304L SS, 254-SMO and AL-6XN exhibited a significantly improved resistance to corrosion as the concentration of hydrochloric acid in he 3.55% NaCl electrolyte solution was increased.

Calle, L. M.↗

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗

A theory of electrophoresis of emulsion drops in aqueous two-phase polymer systems

An electrophoresis study has been carried out in an emulsion formed from an electrically neutral aqueous mixture of dextran and polyethylene glycol equilibrated at sufficient concentrations in the presence of electrolytes. Electrophoresis of a drop of one phase suspended in the other is observed, and the direction of the drop's motion is reversed when the disperse phase and the continuous phase are interchanged. In the presence of sulfate, phosphate, or citrate ions, an electrostatic potential difference of the order of a few mV exists between the two phases. The potential implied by the direction of the electrophoretic motion is opposite to the Donnan potential observed between the two phases. The mobility of an emulsion drop increases with the drop radius and depends on ion concentration. These results are explained in terms of a model postulating an electric dipole layer associated with a mixture of oriented polymer molecules at the surface of a drop, with a potential difference between the interiors of the two phases resulting from the unequal ion distribution.

Levine, S.↗

Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells

Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in three different mixtures of alkyl carbonates have been found well suited for use in rechargeable lithium-ion electrochemical cells at low temperatures. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells down to -60 C. This research at earlier stages was reported in numerous previous NASA Tech Briefs articles, the three most recent being "Ethyl Methyl Carbonate as a Cosolvent for Lithium-Ion Cells" (NPO-20605), Vol. 25, Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells No. 6 (June 2001), page 53; "Alkyl Pyrocarbonate Electrolyte Additives for Li-Ion Cells" (NPO-20775), Vol. 26, No. 5 (May 2002), page 37; and "Fluorinated Alkyl Carbonates as Cosolvents in Li-Ion Cells (NPO-21076), Vol. 26, No. 5 (May 2002), page 38. The present solvent mixtures, in terms of volume proportions of their ingredients, are 1 ethylene carbonate (EC) + 1 diethyl carbonate (DEC) + 1 dimethyl carbonate (DMC) + 3 ethyl methyl carbonate (EMC); 3EC + 3DMC + 14EMC; and 1EC + 1DEC + 1DMC + 4EMC. Relative to similar mixtures reported previously, the present mixtures, which contain smaller proportions of EC, have been found to afford better performance in experimental Li-ion cells at temperatures < -20 C.

Smart, Marshall↗