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Electrolyte film breakers made from polytetrafluoroethylene are installed in the reactant and water vapor removal outlets of each cell and sealed by elastomers. Use of these devices in the water vapor removal cavity outlets prevents loss of KOH solution through film migration during water removal.
Experiment with a rotating disk and ring apparatus showed no poisoning by cadmium in 8.5 M KOH, alone or with Cl(-) or CO3(=). Poisoning does not occur either in 0.1 M KOH supernatant at CdO, but a partially reversible poisoning results from .0001 M CdCl2 and traces of fatty acid are present. Evidence indicates that the catastrophic poisoning affects the four-electron O2 reduction more than it does the one-electron H3O(+) discharge.
A method to prevent zinc interference with the titration of OH- and CO3-2 ions in alkaline electrolytes with standard acid is presented. The Ba-EDTA complex was tested and shown to prevent zinc interference with acid-base titrations without introducing other types of interference. Theoretical considerations indicate that this method can be used to prevent interference by other metals.
A technique employing NaOH phase change material for large-scale thermal energy storage to 900 F (482 C) is described; the concept consists of 12-foot diameter by 60-foot long cylindrical steel shell with closely spaced internal tubes similar to a shell and tube heat exchanger. The NaOH heat storage medium fills the space between the tubes and outer shell. To charge the system, superheated steam flowing through the tubes melts and raises the temperature of NaOH; for discharge, pressurized water flows through the same tube bundle. A technique for system design and cost estimation is shown. General technical and economic properties of the storage unit integrated into a solar power plant are discussed.
A thermal storage system for use in solar power electricity generation was investigated analytically and experimentally. The thermal storage medium is principally anhydrous NaOH with 8% NaNO3 and 0.2% MnO2. Heat is charged into storage at 584 K and discharged from storage at 582 K by Therminol-66. Physical and thermophysical properties of the storage medium were measured. A mathematical simulation and computer program describing the operation of the system were developed. A 1/10 scale model of a system capable of storing and delivering 3.1 x 10 to the 6th power kJ of heat was designed, built, and tested. Tests included steady state charging, discharging, idling, and charge-discharge conditions simulating a solar daily cycle. Experimental data and computer-predicted results are correlated. A reference design including cost estimates of the full-size system was developed.
Three methods of in situ cross-linking polyvinyl alcohol films are presented. They are: (1) acetalization with a dialdehyde such as glutaraldehyde, (2) acetalization with aldehyde groups formed by selective oxidative cleaving of the few percent of 1,2 diol units present in polyvinyl alcohol, and (3) cross-linking by hydrogen abstraction by reaction with hydrogen atoms and hydroxyl radicals from irradiated water. For the third method, improvement in film conductivity in KOH solution at the expense of mechanical strength is obtained by the presence of polyacrylic acid in the polyvinyl alcohol films. Resistivities in 45 percent KOH are given for in situ cross-linked films prepared by each of the three methods.
The laboratory scale testing of a modified anhydrous NaOH latent heat storage concept for small solar thermal power systems such as total energy systems utilizing organic Rankine systems is discussed. A diagnostic test on the thermal energy storage module and an investigation of alternative heat transfer fluids and heat exchange concepts are specifically addressed. A previously developed computer simulation model is modified to predict the performance of the module in a solar total energy system environment. In addition, the computer model is expanded to investigate parametrically the incorporation of a second heat exchange inside the module which will vaporize and superheat the Rankine cycle power fluid.
An attempt is made to measure the sum of the elastic, rotational and vibrational scattering of electrons by KOH at low impact energies (5 to 20 eV) at angles from 10 to 120 deg. Energy loss spectra taken in the 0 to 18 eV range using an electron impact spectrometer are used to identify the species contributing to electric scattering. At temperatures between 300 and 500 C, only inelastic spectral features belonging to water are detected, while at temperatures from 500 to 800 C strong atomic K lines, indicative of molecular dissociation, and H2 energy loss features become prominent. No features attributable to KOH, the KOH dimer, O2 or potassium oxides were observed, due to the effects of the dissociation products, and it is concluded that another technique will have to be developed in order to measure electron scattering by KOH.
The various failure mechanisms were identified for the nickel electrode. The nickel sinter is involved in all these failure modes. The first one, chemical attack by carbonate, nitrate or other electrolyte components, involves corrosion of the nickel sinters. The second is the physical mode, which involves swelling of the electrode and physical shifting of the sinter in the electrodes. The third is the mechanical failure mode, and is due to fatigue or to the oxygen pressure that causes deformation or fracture of the sinter.
Conditioning is the initial cycling where cell capacity is usually unstable. The causes of the initial capacity build were examined. Gridless electrodes were fabricated to ensure mechanical homogeneity, so that a strain measured in one direction would be typical of a strain measured in the other directions. Plate hardness was also determined. These two parameters stabilize together.
A loaded spherical aluminum oxider rider was made to slide, while in various solutions, on a flat iron or nickel surface reciprocate a distance of 1 cm. Time of experiments was 1 hr during which the rider passed over the rider passed over the center section of the track 540 times. Coefficients of friction were measured throughout the experiments. Wear was measured by scanning the track with a profilometer. Analysis of some of the wear tracks included use of the SEM (scanning electron microscrope) and XPS (X-ray photoelectron spectroscopy). Investigated were the effect of various concentractions of NaOH and of water. On iron, increasing NaOH concentration above 0.01 N caused the friction and wear to decrease. This decrease is accompanied by a decrease in surface concentration of ferric oxide (Fe2O3) while more complex iron-oxygen compounds, not clearly identified, also form. At low concentrations of NaOH, such as 0.01 N, where the friction is high, the wear track is badely torn up and the surface is broken. At high concentration, such as 10 N, where the friction is low, the wear track is smooth. The general conclusion is that NaOH forms a protective, low friction film on iron which is destroyed by wear at low concentrations but remains intact at high concentrations of NaOH. Nickel behaves differently than iron in that only a little NaOH gives a low coefficient of friction and a surface which, although roughened in the wear track, remains intact.
The reactions of carbon dioxide with various metals are discussed. The equations which govern the rates of CO2 removal from the atmosphere in spacecraft environmental control systems are discussed. Results from performance testing of various Space Shuttle environmental control systems are presented with the correlation of the equations to the performance given.
A loaded spherical aluminum oxider rider was made to slide, while in various solutions, on a flat iron or nickel surface reciprocate a distance of 1 cm. Time of experiments was 1 hr during which the rider passed over the center section of the track 540 times. Coeficients of friction were measured throughout the experiments. Wear was measured by scanning the track with a profilometer. Analysis of some of the wear tracks included use of the SEM (scanning electron microscope) and XPS (X-ray photoelectron spectroscopy). Investigated were the effect of various concentrations of NaOH and of water. On iron, increasing NaOH concentration above 0.01 N caused the friction and wear to decrease. This decrease is accompanied by a decrease in surface concentration of ferric oxide (Fe2O3) while more complex iron-oxygen compounds, not clearly identified, also form. At low concentrations of NaOH, such as 0.01 N, where the friction is high, the wear track is badly torn up and the surface is broken. At high concentration, such as 10 N, where the friction is low, the wear track is smooth. The general conclusion is that NaOH forms a protective, low friction film on iron which is destroyed by wear at low concentrations but remains intact at high conentrations of NaOH. Nickel behaves differently than iron in that only a little NaOH gives a low coefficient of friction and a surface which, although roughened in the wear track, remains intact. Previously announced in STAR as N83-10171
The influence of OH ion impurities on thermoluminescent sensitivity and supralinearity in LiF:Mg, Ti is analyzed. Available evidence is shown to be consistant with the presence of Ti-OH and Mg-OH complexes. The track interaction model is used to explain the data, with competing centers decreasing sensitivity and supralinearity at high concentrations.
Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished.
A possible origin of early hydrogen by UV-induced photoreduction of ferrous ions was investigated by measuring the rate of H2 formation from irradiated FeSO4 solutions as a function of pH and the range of UV sources. It was found that, in addition to the known reaction in acid solution which decreases in yield with increasing pH and requires far-UV light, there is an efficient reaction occurring between pH 6 and 9 which utilizes near-UV light (of a 200-W mercury arc lamp). This latter reaction is a linear function of both the concentration of Fe(2+) and the light intensity. These results support the suggestion of Braterman et al. (1983) that the near-UV-driven photooxidation of ferrous ions may be responsible for the origin of the banded iron formations on the early earth. The efficient photoreaction could also explain the source of reducing equivalents for CO2 reduction.
The vapor pressures of Ca(OH)2(g), Al(OH)3(g), and Si(OH)4(g) molecules in equilibrium with solid calcium-, aluminum, and silicon-oxides, respectively, were determined, and were used to derive the heats of formation and entropies of these species, which are expected to be abundant under the currently postulated physical conditions in the primordial solar nebula. These data, in conjunction with thermodynamic data from literature, were used to calculate the relative abundances of M, MO(x), and M(OH)n gas species and relative volatilities of Fe, Mg, Si, Ca, and Al for ranges of temperature, total pressure, and H/O abundance ratio corresponding to the plausible ranges of physical conditions in the solar nebula. The results are used to explain how Ca and Al could have evaporated from Ca,Al-rich inclusions in carbonaceous chondrites, while Si, Mg, and Fe condensed onto them during the preaccretion alteration of CAIs.
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