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Focused ion beam tomography dataset of Alloy 617 after corrosion in a eutectic mixture of sodium chloride and magnesium chloride at 700 degrees Celsius for 1000 hours.
The utility of molten chloride salts in concentrating solar power (CSP) is dependent on the ability to maintain low corrosive impurities. Without proper purification, the corrosion rates of containment alloys exceed the industry standard of corrosion—under 20 μm/year. An extensive body of literature focuses on the initial purification stage of molten chloride salts. However, occurrences such as maintenance, leaks, and so forth expose the salt to the atmosphere and reintroduce impurities. Therefore, it is critical to develop a purification strategy that can control impurity levels during CSP plant operation. Here we present the design and fabrication of a purification vessel to continuously remove impurities out of flowing molten salt.
To achieve DOE 2030 SunShot targets that reduce the cost of liquid-based solar by an additional 40% to 70% beyond 2018 costs, a more reliable, highly manufacturable flow valve, capable of achieving operational temperatures of >700°C is required [1]. This paper investigates the development of an innovative high-temperature chloride molten salt valve, with operation up to 750°C. This valve is intended to be employed within Gen 3 CSP liquid-based thermal energy storage (TES) systems as well as Gen 4 modular salt reactor (MSR) technologies. This work details the general design and flow testing of a bellows-seal flow control valve (FCV). This design includes an integrated closed-loop thermal control system to ensure robust design for freeze-thaw cycles. The self-contained thermal management STM system, is unique in the salt valve industry since it is an integrated solution to provide a consistent, repeatable alternative to typical heat tracing. Additionally, the design includes the employment of a novel heat pipe valve stem to facilitate enhanced passive thermal management into the valve assembly. This valve stem heat pipe is designed to facilitate natural circulation within the bonnet to ensure robust operation, during both nominal and transient thermal operation. The valve body and trim will be designed using SS316H, consistent with Flowserve Corporation’s existing product base and is code qualified but will utilize clad material for materials corrosion, manufacturing cost reduction and compatibility to ensure design flexibility. A test campaign was performed in this investigation utilizing a novel 750°C ternary chloride (20%NaCl/40%MgCl2/40%KCl by mol. wt. %) molten salt flow loop. A discussion about the design and installation of the valves within this test bed is provided for this investigation. Valve test results from this study assessed Cv curves as well as multiple actuator cycles, under varying thermodynamic and operational mode conditions, which would be characteristic within a commercial molten salt facility. The results indicate nominal operation for the baseline design, though improved performance and reliability is expected with the full designed FCV.
Thermodynamics of electrochemical cells consisting of Li with lithium chloride or bromide and thallium amalgam with thallium chloride or bromide in propylene carbonate
Hyperfiltration of sodium chloride and urea was studied with porous glass membranes in closed-end capillary form, to determine the effect of pressure, temperature, and concentration variations, and lifetime rejection and flux characteristics. Rejection data for sodium chloride were consistent with the functioning of the porous glass as a low-capacity ion-exchange membrane.
Examination of the observational basis for Kuiper's (1969) conclusion that the upper cloud layers of Venus are composed of dihydrated ferrous chloride particles. Using new spectrophotometric observations of Venus, it is found that there is no strong evidence for the Fe(2+) electronic band near 1 micron as deduced by Kuiper from the photometry of Venus by Irvine et al. (1968). Evidence for an absorption band on Venus near 0.5 micron is found to be valid, but nondefinitive in terms of the identification of ferrous iron. An absorption band near 0.39 micron appearing in the Venus photometric data of Irvine et al. (1968) is judged to be unreliable as an indicator of chemical composition, because of time-dependent variations in the violet and ultraviolet clouds and spectrum of Venus. In conclusion, it is found that the evidence for dihydrated ferrous chloride in the atmosphere of Venus is inconclusive.
Anhydrous tin (2) chloride (SnCl2) is prepared by radiolysis with high energy electrons of a tin (4) chloride (SnCl4) solution in heptane. The SnCl4 is reduced to insoluble SNCl2. The energy yield, G(SnCl2), molecules of SnCl2, produced per 100 eV, increases with SnCl4 concentration from 1.6 at 0.15 M SnCl4 to 3.1 at 3.0 M SnCl4. Other parameters such as temperature total dose and beam current have little influence on G(SnCl2). The method may be used to prepare other metal halides if the higher valence, more covalent metal halide is soluble in aliphatic hydrocarbons and the lower more ionic metal halide is insoluble. The reaction mechanism is discussed; the radiolysis of both heptane and SnCl4 is involved. At high SnCl4 concentration G(SnCl2) appears to be limited by the yield of SnC13 radicals.
The conditions in which hydrochloric acid aerosol is predicted by the interaction of hydrogen chloride gas with the water vapor in humid air are analyzed. The liquid gas phase equilibrium for the HCL-H2O system is expressed in terms of relative humidity and hydrogen chloride concentration as parts per million, units commonly used in pollution studies. Presented are the concentration (wt %) of HC1 in the aerosol and the concentration of aerosol (ppm) predicted.
The failure of a central force model for sodium chloride is discussed. It is noted that it does not closely satisfy the Cauchy conditions at low temperatures, and that it fails the central force requirement of the Love condition. The available shock data for sodium chloride and its analysis is examined, and two reasons why the Hugoniot transformation pressure is likely to be less than 231 kbar are discussed. The important (but unjustified) theoretical assumptions made in converting Hugoniot to isothermal data is discussed; it is noted that serious error can enter for very large pressures for a given material and that at such high pressures the isothermal data should thus be considered only semiquantitative even if the Hugoniot data itself is accurate. An alternate method of estimating the isothermal transformation pressure from the Hugoniot transformation pressure is used. This method is based on the temperature derivative of the transformation pressure. On this basis it is concluded that an upper bound for the isothermal transformation of NaCl (to a CsCl-type structure) at room temperature is 257 kbar; it is noted that the actual value may be considerably less than this.
Hydrogen chloride (HCl) and aluminum oxide (Al2O3) are major exhaust products of solid rocket motors (SRM). Samples of calcination-produced alumina were exposed to continuously flowing mixtures of gaseous HCl/H2O in nitrogen. Transient sorption rates, as well as maximum sorptive capacities, were found to be largely controlled by specific surface area for samples of alpha, theta, and gamma alumina. Sorption rates for small samples were characterized linearly with an empirical relationship that accounted for specific area and logarithmic time. Chemisorption occurred on all aluminas studied and appeared to form from the sorption of about a 2/5 HCl-to-H2O mole ratio. The chemisorbed phase was predominantly water soluble, yielding chloride/aluminum III ion mole ratios of about 3.3/1 suggestive of dissolved surface chlorides and/or oxychlorides. Isopiestic experiments in hydrochloric acid indicated that dissolution of alumina led to an increase in water-vapor pressure. Dissolution in aqueous SRM acid aerosol droplets, therefore, might be expected to promote evaporation.
Sliding friction experiments were conducted with an iron rider on a copper disk and a copper rider on an iron disk. The sputter cleaned iron and copper disk surfaces were saturated with oxygen, methyl mercaptan, and methyl chloride at atmospheric pressure. Auger emission spectroscopy was used to monitor the surfaces. Lower friction was obtained in all experiments with the copper rider sliding on the iron disk than when the couple was reversed. For both iron and copper disks, methyl mercaptan gave the best surface coverage and was most effective in reducing friction. For both iron and copper disks, methyl chloride was the least effective in reducing friction. With sliding, copper transferred to iron and iron to copper.
Two different topics which only relate in that they are pertinent to lithium thionyl chloride battery safety are discussed. The first topic is a hazards analysis of a system (risk assessment), a formal approach that is used in nuclear engineering, predicting oil spills, etc. It is a formalized approach for obtaining assessment of the degree of risk associated with the use of any particular system. The second topic is a small piece of chemistry related to the explosions that can occur with lithium thionyl chloride systems. After the two topics are presented, a discussion is generated among the Workshop participants.
Sodium chloride is one of the primary contaminants that enter gas turbine engines and contribute, either directly or indirectly, to the hot corrosion degradation of hot-gas-path components. The paper surveys the results of laboratory experiments along with thermodynamic and mass transport calculations, intended for elucidating the behavior of sodium chloride in combustion environments. It is shown that besides being a source of sodium for the formation of corrosive liquid Na2SO4, the NaCl itself contributes in other indirect ways to the material degradation associated with the high-temperature environmental attack. In addition, the experimental results lend credence to the conceptual scheme presented schematically (behavior of NaCl in a turbine engine combustion gas environment) and resolve conflicting aspects of relevant NaCl misconceptions.
Electron capture gas chromatography techniques were used to obtain measurements of methyl chloride concentrations in the atmosphere, at latitudes ranging from about 65 N to 90 S. Most of the measurements were made over the Pacific Ocean. Average global concentrations within the boundary layer were found to be 815 plus or minus 25 pptv in 1977 and 755 plus or minus 37 pptv in 1978. Lower concentrations were observed above the boundary layer with average values of 629 plus or minus 23 pptv and 618 plus or minus 23 pptv in 1977 and 1978, respectively. Within 20 deg of the equator, the boundary layer concentrations were significantly higher than those above the boundary layer. The sources, the sinks, the budgets, and the latitudinal distributions of methyl chloride are discussed in the paper.
The effect of a high level of chloride content (800 ppm) in MON-1 propellant on the crack growth properties of seven materials was investigated. Sustained load tests were conducted at 49 C (120 F) temperature with thin gauge tensile specimens having a semi-elliptical surface flaw. Alloys included aluminum 1100, 3003, 5086 and 6061; corrosion resistant steel types A286 and 347; and titanium 6Al-4V. The configurations tested with precracked flaws exposed to MON-1 were: parent or base metal, center weld, and heat affected zone. It was concluded that this chloride level in MON-1 does not affect the stress corrosion, crack growth properties of these alloys after 1000 hour exposure duration under high stresses.
Case polarity design choices are discussed. Two examples of case-negative designs are presented. One battery is thionyl chloride limited and the other is lithium limited. The case-positive design is thionyl chloride limited. It is found that the case-positive/case-negative design consideration does not seem to have much bearing on storage. However, during low rate discharge, the case-negative cells show a steadily decreasing capacity as you go to lower and lower rates.
Partitioning of hydrogen chloride between the aerosol and gaseous phases in the first Space Shuttle exhaust cloud was experimentally investigated as the exhaust cloud was diluted with ambient air. Airborne measurements were obtained of gaseous hydrogen chloride (HCl), total HCl, relative humidity, and temperature to determine the conditions controlling HCl aerosol formation in the Shuttle exhaust cloud. Two segments of the cloud, each at a significantly different relative humidity, were monitored. Equilibrium predictions of HCl aerosol formation agreed with the measured HCl partitioning at the higher and lower relative humidity conditions, but do not agree at the aerosol formation threshold region. Measurements were taken in the Shuttle exhaust cloud from 8.6 min until 2 h and 8 min after launch. HCl concentrations ranged from 17.5 to 0.9 ppm and relative humidity from 86% to less than 10%.
The adsorption of hydrogen chloride and water vapors on five TiO2 powders in both the anatase and rutile crystalline forms was studied as a function of temperature, pressure, and outgas conditions. The adsorbents were characterized utilizing X-ray powder diffraction, scanning electron microscopy, surface area analysis, indicator method, microelectrophoresis, XPS, and infrared spectroscopy. It was found that both outgas temperature and adsorption temperature influenced the adsorption of water vapor on TiO2, while water vapor adsorption on TiO2 was completely reversible. It is argued that the number of hydroxyl groups present on the surface determines the adsorption capacity of water on the different titanium dioxides. It was found that heats of immersion in water were affected significantly by outgas temperature. Hydrogen chloride adsorption isotherms at 30 C measured on TiO2 after outgassing at 100-400 C showed that a part of the total HCl adsorbed was irreversibly adsorbed. The highest HCl adsorption capacity per unit area was exhibited by anatase, while pure rutile exhibited the lowest adsorption capacity.