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Concentrations of hc1 measured in the lower stratosphere in 1993 by the ALIAS instrument on the ER-2 aircraft reveal that only 40% of inorganic chlorine (CL sub y, inferred from in situ measurements of organic chlorinated source gases) is present as HC1, significantly lower than model predictions.
Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.
Chemical pretreatments are used to produce usable water by treating a water source with a chemical pretreatment that contains a hexavalent chromium and an acid to generate a treated water source, wherein the concentration of sulfate compounds in the acid is negligible, and wherein the treated water source remains substantially free of precipitates after the addition of the chemical pretreatment. Other methods include reducing the pH in urine to be distilled for potable water extraction by pretreating the urine before distillation with a pretreatment solution comprising one or more acid sources selected from a group consisting of phosphoric acid, hydrochloric acid, and nitric acid, wherein the urine remains substantially precipitate free after the addition of the pretreatment solution. Another method described comprises a process for reducing precipitation in urine to be processed for water extraction by mixing the urine with a pretreatment solution comprising hexavalent chromium compound and phosphoric acid.
Friction and wear behavior of Fe and Ni sliding on aluminum oxide in aerated sulfuric acid and hydrochloric acid were investigated. The results show that the concentration of acid is an important factor in controlling the metal loss caused by wear corrosion processes in the acids. At very dilute acid concentration (10 to the -4 N), Fe behaves differently from Ni. Fe develops a soft, friable deposit, while Ni develops no corrosion layer. The formation and removal of the corrosion deposit on Fe resulted in high metal loss and coefficient of friction, as compared to the relatively low metal loss and coefficient of friction observed for Ni. At slightly higher acid concentration (10 to the -3 and 10 to the -2 N), no corrosion products were produced on both Fe and Ni. Wear of Fe and Ni was generally at a minimum. At higher acid concentration (10 to the -1 N and above), loss of Fe and Ni increased as the acid concentration increased. In sulfuric acid the maximum loss of both Fe and Ni was at 7.5 N (30%) concentration, and the metal losses of both Fe and Ni dropped markedly at 15 N (50%) and above. In hydrochloric acid, however, the Fe loss continued to increase with the increase of acid concentration, and the maximum Fe loss occurred in the most concentrated acid (12.1 N, 37%). There were variations in loss with Ni from specimen to specimen examined in hydrochloric acids (10 to the -1 N and above). The coefficient of friction for Ni increased slightly with an increase in acid concentration up to 10 to the -2 N. When corrosion started to dominate in the wear-corrosion process, the coefficient of friction decreased in both sulfuric and hydrochloric acids at 10 to the -1 N and above.
Friction and wear behavior of Fe and Ni sliding on aluminum oxide in aerated sulfuric acid and hydrochloric acid were investigated. The results show that the concentration of acid is an important factor in controlling the metal loss caused by wear corrosion processes in the acids. At very dilute acid concentration (10 to the -4 N), Fe behaves differently from Ni. Fe develops a soft, friable deposit, while Ni develops no corrosion layer. The formation and removal of the corrosion deposit on Fe resulted in high metal loss and coefficient of friction, as compared to the relatively low metal loss and coefficient of friction observed for Ni. At slightly higher acid concentration (10 to the -3 and 10 to the -2 N), no corrosion products were produced on both Fe and Ni. Wear of Fe and Ni was generally at a minimum. At higher acid concentration (10 to the -1 N and above), loss of Fe and Ni increased as the acid concentration increased. In sulfuric acid the maximum loss of both Fe and Ni was at 7.5 N (30 percent) concentration, and the metal losses of both Fe and Ni dropped markedly at 15 N (50 percent) and above. In hydrochloric acid, however, the Fe loss continued to increase with the increase of acid concentration, and the maximum Fe loss occurred in the most concentrated acid (12.1 N, 37 percent). There were variations in loss with Ni from specimen to specimen examined in hydrochloric acids (10 to the -1 N and above). The coefficient of friction for Ni increased slightly with an increase in acid concentration up to 10 to the -2 N. When corrosion started to dominate in the wear-corrosion process, the coefficient of friction decreased in both sulfuric and hydrochloric acids at 10 to the -1 N and above.
Concentrations of gas phase hydrofluoric acid and hydrochloric acid have been determined in the upper stratosphere from near-infrared solar spectra recorded in the course of balloon flights from Palestine, Texas, in October 1978 and in September 1979. The average mixing ratios for HF deduced respectively from these flights are (4.8 plus or minus .3) x 10 to the -10th ppv above 30.3km and (6.2 plus or minus .5) x 10 to the -10th ppv above 36.8km. This observed difference is ascribed to an increase in the HF concentration out to at least 37km. The HCl mixing ratios deduced from the 1978 flight yield (4.5 plus or minus .6) x 10 to the -10th ppv at 21.7km, (7.5 plus or minus .7) x 10 to the -10th ppv at 27.5 km and (2.1 plus or minus .4) x 10 to the -9th ppv above 30.5km. Observations in 1979 imply an average HCl mixing ratio above 36.8km of (2.4 plus or minus .4) x 10 to the -9th ppv. Our data do not indicate a measurable temporal trend of the HCl concentration above 30km.
Nitric acid and hydrochloric acid vapors may condense in the winter polar stratospheres. Nitric acid clouds, unlike water ice clouds, would form at the temperatures at which polar stratospheric clouds (PSCs) are observed and would have optical depths of the magnitude observed suggesting that HNO3 is a dominant component of PSCs. ClO, N2O5 and ClNO3 may react on cloud particle surfaces yielding additional HNO3, HCl, and HOCL. In the vicinity of PSCs these reactions could deplete the stratosphere of photochemically active NO(x) species. The sedimentation of PSCs may remove these materials from the stratosphere. The loss of vapor phase NO(x) might allow halogen-based chemistry to create the ozone hole.
We present a re‐examination of mass spectral data obtained from the Pioneer Venus Large Probe Neutral Mass Spectrometer. Our interpretations of differing trace chemical species are suggestive of redox disequilibria in Venus' middle clouds. Assignments to the data (at 51.3 km) include phosphine, hydrogen sulfide, nitrous acid, nitric acid, carbon monoxide, hydrochloric acid, hydrogen cyanide, ethane, and potentially ammonia, chlorous acid, and several tentative PxOy species. All parent ions were predicated upon assignment of corresponding fragmentation products, isotopologues, and atomic species. The data reveal parent ions at varying oxidation states, implying the presence of reducing power in the clouds, and illuminating the potential for chemistries yet to be discovered. When considering the hypothetical habitability of Venus' clouds, the assignments reveal a potential signature of anaerobic phosphorus metabolism (phosphine), an electron donor for anoxygenic photosynthesis (nitrite), and major constituents of the nitrogen cycle (nitrate, nitrite, ammonia, and N2).
Mature valencia orange trees were sprayed with hydrochloric acid solutions (pH 7.8, 2.0, 1.0, and 0.5) in the field at the full bloom stage and at one month after fruit set. Potted valencia orange and dwarf citrus trees, four species of plants native to Merritt Island, and four agronomic species were exposed to various pH levels of simulated acid rain under controlled conditions. The acid rain was generated from dilutions of hydrochloric acid solutions or by passing water through an exhaust generated by burning solid rocket fuel. The plants were injured severely at pH levels below 1.0, but showed only slight injury at pH levels of 2.0 and above. Threshold injury levels were between 2.0 and 3.0 pH. The sensitivity of the different plant species to acid solutions was similar. Foliar injury symptoms were representative of acid rain including necrosis of young tissue, isolated necrotic spots or patches, and leaf abscission. Mature valencia orange trees sprayed with concentrations of 1.0 pH and 0.5 pH in the field had reduced fruit yields for two harvests after the treatment. All experimental trees were back to full productivity by the third harvest after treatment.
A 3D networked, dense form of single-walled carbon nanotubes (SWNT) has been made through isotropic shrinking of a gel-like SWNT-water paste by very slow evaporation. Approximately 35 g of Raw HiPco nanotubes were cleaned by the method of soft baking (250 C for 15 hours in air saturated with water vapor) in a glass beaker followed by leaching with concentrated hydrochloric acid. Typically, one liter of concentrated hydrochloric acid was added to the soft-baked voluminous mass in the same large beaker, and allowed to digest at room temperature with stirring overnight. The acid-digested SWNT slurry was filtered through a large porcelain Buchner funnel under atmospheric pressure. The slurry was continuously flushed, while still in the funnel, with a very slow but steady stream of deionized water employing a peristaltic pump. This process, referred to as gwashing, h continued until the filtrate water dripping from the Buchner funnel was clear, colorless, and neutral to a pH paper. This took about 15 liters of water to flow through the slurry over a day. At this point, the water pump was stopped and the SWNT-water slurry was allowed to drain the excess water for about 10 hours. The resulting thick paste of SWNT-neutral water was transferred to a beaker. The beaker was covered with aluminum foil with few holes and allowed to dry very slowly in a hood at room temperature. In about eight weeks, the sample gradually dried isotropically to a cylindrical dense mass referred to as a carbon nanotube block (CNB). There was no carbonaceous matter sticking to any of the glass surface where the SWNT-water paste made contact. The approximate dimensions of the cylindrical SWNT block that weighed 28 g were 1.5 in. (.3.8 cm) in diameter and 1.25 in. (.3.2 cm) in height. The bottom portion of the cylinder that was in contact with the beaker surface was slightly wider, indicating some resistance to shrinking. The cylindrical mass also consisted of several pores. The cylindrical mass was very tough and could not be broken with a small hammer using considerable force. The mass of the solid could be polished over a fine grain emery paper or even a smooth, stainless steel surface indicative of alignment at finer levels.
It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.
The potential of shuttle operations to contribute to atmospheric pollution is investigated. Presented in this interim report are results of the study to date on rocket exhaust inventory, exhaust interactions, dispersion of the ground cloud, detection and measurement of hydrochloric acid and aluminum oxide, environmental effects of hydrochloric acid and aluminum oxide, stratospheric effects of shuttle effluents, and mesospheric and ionospheric effects of orbiter reentry. The results indicate space shuttle operation will not result in adverse environmental effects if appropriate launch constraints are met.
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.
Metal oxide containing polymers and particularly styrene, acrylic or protein polymers containing fine, magnetic iron oxide particles are formed by combining a NO.sub.2 -substituted polymer with an acid such as hydrochloric acid in the presence of metal, particularly iron particles. The iron is oxidized to fine, black Fe.sub.3 O.sub.4 particles which deposit selectively on the polymer particles. Nitrated polymers are formed by reacting functionally substituted, nitrated organic compounds such as trinitrobenzene sulfonate or dinitrofluoro benzene with a functionally coreactive polymer such as an amine modified acrylic polymer or a protein. Other transition metals such as cobalt can also be incorporated into polymers using this method.
In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines can be achieved using alternate pretreatment formulations under laboratory conditions. Additional testing and hazard assessments will be required to determine the feasibility of utilizing the proposed urine pretreatment formulations on ISS.
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.
The exhaust products of a solid rocket motor using as propellant 14% binder, 16% aluminum, and 70% (wt) ammonium perchlorate consist of hydrogen chloride, water, alumina, and other compounds. The equilibrium and some frozen compositions of the chemical species upon interaction with the atmosphere were computed. The conditions under which hydrogen chloride interacts with the water vapor in humid air to form an aerosol containing hydrochloric acid were computed for various weight ratios of air/exhaust products. These computations were also performed for the case of a combined SRM and hydrogen-oxygen rocket engine. Regimes of temperature and relative humidity where this aerosol is expected were identified. Within these regimes, the concentration of HCL in the aerosol and weight fraction of aerosol to gas phase were plotted. Hydrochloric acid aerosol formation was found to be particularly likely in cool humid weather.
A ball-on-plate (both consisting of hardened M-50 steel) sliding elastohydrodynamic contact was run with trimethylolpropane triheptanoate (TMPTH) with and without tricresyl phosphate (TCP). The contact area of the plate was optically profiled with a phase-locked interference microscope (PLIM) both before and after exposure to alcoholic hydrochloric acid. As scuffing was approached, the profile within the contact region changed more rapidly after the acid treatment; after scuffing, it assumed a constant high value. A metallurgical phase found in the scuff mark was apparently responsible for the high reactivity. The microscopic profile changes (sensitivity, + or - 3 nm (+ or - A) in depth) involved primarily the small asperities (radius, 3 microns); the larger ones were unaffected. Soaking the steel in TCP smoothed the fine structure of the surface profile but increased its reactivity toward alcoholic hydrochloric acid before sliding was started. Thus it would appear that PLIM examination could be used for screening potentially scuff-resistant materials.