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Infrared reflectance spectra of Na2S with contaminant Na2CO3 - Effects of adsorbed H2O and CO2 and relation to studies of Io
A previously reported laboratory determination of the IR spectrum of Na2S is presently noted to have been incorrectly interpreted, due to the inadvertent contamination of the sample with Na2CO3. New Na2S spectra are presented, and the Na2CO3 spectrum is examined in order to demonstrate that this phase is the primary sample contaminant. Na2S is a candidate surface component on the Jupiter satellite, Io, in view of its apparent high IR brightness and spectral neutrality in the 1-5 micron range.
Materials Data on Na2CO3 by Materials Project
Na2CO3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a hexagonal planar geometry to six equivalent O2- atoms. All Na–O bond lengths are 2.65 Å. In the second Na1+ site, Na1+ is bonded to six equivalent O2- atoms to form face-sharing NaO6 octahedra. All Na–O bond lengths are 2.37 Å. C4+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. All C–O bond lengths are 1.30 Å. O2- is bonded in a 5-coordinate geometry to four Na1+ and one C4+ atom.
Materials Data on Na2CO3 by Materials Project
Na2CO3 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are three inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.60–2.71 Å. In the second Na1+ site, Na1+ is bonded to six O2- atoms to form face-sharing NaO6 octahedra. There are two shorter (2.35 Å) and four longer (2.37 Å) Na–O bond lengths. In the third Na1+ site, Na1+ is bonded to six O2- atoms to form face-sharing NaO6 octahedra. There are four shorter (2.33 Å) and two longer (2.45 Å) Na–O bond lengths. C4+ is bonded in a trigonal planar geometry to three O2- atoms. All C–O bond lengths are 1.30 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to five Na1+ and one C4+ atom. In the second O2- site, O2- is bonded in a 1-coordinate geometry to four Na1+ and one C4+ atom.
High-temperature molten salt thermal energy storage systems for solar applications
Experimental results of compatibility screening studies of 100 salt/containment/thermal conductivity enhancement (TCE) combinations for the high temperature solar thermal application range of 704 deg to 871 C (1300 to 1600 F) are presented. Nine candidate containment/HX alloy materials and two TCE materials were tested with six candidate solar thermal alkali and alkaline earth carbonate storage salts (both reagent and technical grade of each). Compatibility tests were conducted with salt encapsulated in approx. 6.0 inch x 1 inch welded containers of test material from 300 to 3000 hours. Compatibility evaluations were end application oriented, considering the potential 30 year lifetime requirement of solar thermal power plant components. Analyses were based on depth and nature of salt side corrosion of materials, containment alloy thermal aging effects, weld integrity in salt environment, air side containment oxidation, and chemical and physical analyses of the salt. A need for more reliable, and in some cases first time determined thermophysical and transport property data was also identified for molten carbonates in the 704 to 871 C temperature range. In particular, accurate melting point (mp) measurements were performed for Li2CO3 and Na2CO3 while melting point, heat of fusion, and specific heat determinations were conducted on 81.3 weight percent Na2CO3-18.7 weight percent K2CO3 and 52.2 weight percent BaCO3-47.8 weight percent Na2CO3 to support future TES system design and ultimate scale up of solar thermal energy storage (TES) subsystems.
Molten salt corrosion of SiC: Pitting mechanism
Thin films of Na2SO4 and Na2CO3 at 1000 C lead to severe pitting of sintered alpha-SiC. These pits are important as they cause a strength reduction in this material. The growth of product layers is related to pit formation for the Na2CO3 case. The early reaction stages involve repeated oxidation and dissolution to form sodium silicate. This results in severe grain boundary attack. After this a porous silica layer forms between the sodium silicate melt and the SiC. The pores in this layer appear to act as paths for the melt to reach the SiC and create larger pits.
Molten-salt corrosion of silicon nitride. I - Sodium carbonate. II - Sodium sulfate
An experimental study of the corrosion of Si3N4 under thin films of Na2CO3 at 1000 C has been conducted using both pure Si3N4 and Si3N4 with various additives. The reaction mechanism is shown to consist of: (1) the decomposition of Na2CO3 and the formation of Na2SiO3; (2) rapid oxidation; and (3) the formation of a protective silica layer below the silicate. In the second part, the corrosion mechanism of Si3N4 + Na2SO4/O2 at 1000 C was studied for both pure and additive-containing Si3N4. The reaction of Si3N4 + Na2SO4 was found to involve an initial period of slow weight loss (due to Na2SO4 vaporization and oxidation-dissolution) followed by further oxidation or the near termination of the reaction, depending on the Si3N4 additive.
Plutonium Retention by Crystalline Silicotitanate under Hyperalkaline Conditions Relevant to Tank-Side Cesium-Removal at the Hanford Site
Crystalline silicotitanate (CST) is used in Hanford’s Tank-Side Cesium-Removal (TSCR) process to selectively remove Cs-137 from highly caustic, nitrate-rich tank supernatants. Recent testing with actual waste samples suggests that CST can also retain measurable plutonium (Pu), which could affect radiological classification and disposal pathways for spent CST. To quantify this behavior, Pu partitioning to CST was studied under Hanford-relevant conditions using batch-contact experiments in a representative simulant (2 M NaNO3, 0.7 M NaOH). Isotherm data were measured and distribution ratios calculated, with Cs+ uptake used as benchmark. Under low-carbonate conditions, Pu was retained strongly by CST in systems initially contacted with either PuO2 nanoparticles (Pu(IV)) or aqueous Pu(VI), with distribution ratios of ~2,200–3,700 mL/g, generally exceeding those for Cs+ (~400–1,000 mL/g). Increasing carbonate concentration strongly reduced PuO2 nanoparticle retention; at [Na2CO3] = 1 M, distribution ratios decreased by up to one order of magnitude to roughly 100–300 mL/g. Electron microscopy suggests that Pu retention involves a combination of mechanisms such as PuO2 NP aggregation induced by CST leachate components, and association with CST bead surfaces.
High-temperature molten salt thermal energy storage systems for solar applications
Alkali and alkaline earth carbonate latent-heat storage salts, metallic containment materials, and thermal conductivity enhancement materials were investigated to satisfy the high temperature (704 to 871 C) thermal energy storage requirements of advanced solar-thermal power generation concepts are described. Properties of the following six salts selected for compatibility studies are given: three pure carbonates, K2CO3, Li2CO3 and Na2CO3; two eutectic mixtures, BaCO3/Na2CO3 and K2CO3/NaCO3, and one off-eutectic mixture of Na2CO3/K2CO3.
Rheological study of clay-kaolin aqueous suspensions
Rheological characteristics of clay-kaolin aqueous suspensions were studied by a rotational viscometer to correlate their behavior with the properties of ceramic slips for casting containing quartz, feldspars, and other nonplastic materials. In particular, the effects of the different amounts of dry materials and deflocculant (mixture 1:1 of Na2CO3 and Na2SiO3) and of temperatures on the shear-time-dependent properties of suspensions were examined.
Deflocculation of clay suspensions using sodium polyacrylates
Rheological properties of elutriated kaolin suspensions deflocculated by Na polyacrylate (DAC 3 and DAC 4) were studied and compared to those deflocculated by the conventional Na2CO3 water and glass and imported Dispex N40. The deflocculating effect of Na polyacrylate was comparable to that of Dispex N40. The optimum amounts of Na polyacrylate were determined for suspensions based on 5-type kaolin. The Na polyacrylate can be successfully used for decreasing the water content of ceramic slips for casting and spray drying.
Mechanism of strength degradation for hot corrosion of alpha-SiC
Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000%. This hot corrosion attack reduced room temperature strengths by as much as 50%. Strength degradation was porportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is consistent with published values.
Hot corrosion of sintered alpha-SiC at 1000 C
The hot corrosion of sintered alpha-SiC by thin films of Na2SO4 and Na2CO3 was studied at 1000 C in controlled gas atmospheres. Under all conditions, corrosion led to 10 to 20 times the amount of SiO2 formed in pure oxidation after a 48-h exposure. In addition, small amounts of sodium silicate formed. Melts of Na2SO4/SO3 caused uniform pitting of the SiC substrate; Na2CO3/CO2 melts caused localized pitting and grain-boundary attack. In all cases, the protective SiO2 layer dissolved to form silicate, leading to corrosion. In the sulfate case, free carbon in the SiC promotes this process. In all cases the presence of liquid films is responsible for rapid transport rates and the subsequent rapid reaction.
Boron determination in steels by Inductively-Coupled Plasma spectometry (ICP)
The sample is treated with 5N H2SO4 followed by concentrated HNO3 and the diluted mixture is filtered. Soluble B is determined in the filtrate by Inductively-Coupled Plasma (ICP) spectrometry after addition HCl and extraction of Fe with ethyl-ether. The residue is fused with Na2CO3 and, after treatment with HCl, the insoluble B is determined by ICP spectrometry as before. The method permits determination of ppm amounts of B in steel.
Hot corrosion attack and strength degradation of SiC and Si(sub)3N(sub)4
Thin films of Na2SO4 and Na2CO3 molten salt deposits were used to corrode sintered SiC and Si3N4 at 1000 C. The resulting attack produced pitting and grain boundary etching resulting in strength decreases ranging from 15 to 50 percent. Corrosion pits were the predominant sources of fracture. The degree of strength decrease was found to be roughly correlated with the depth of the pit, as predicted from fracture toughness considerations. Gas evolution and bubble formation were key aspects of pit formation. Many of the observations of furnace exposures held true in a more realistic burner rig test.
Mechanism of strength degradation for hot corrosion of alpha-SiC
Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000 percent. This hot corrosion attack reduced room temperature strengths by as much as 50 percent. Strength degradation was proportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is cnsistent ith published values.
Corrosion pitting of SiC by molten salts
The corrosion of SiC by thin films of Na2CO3 and Na2SO4 at 1000 C is characterized by a severe pitting attack of the SiC substrate. A range of different Si and SiC substrates were examined to isolate the factors critical to pitting. Two types of pitting attack are identified: attack at structural discontinuities and a crater-like attack. The crater-like pits are correlated with bubble formation during oxidation of the SiC. It appears that bubbles create unprotected regions, which are susceptible to enhanced attack and, hence, pit formation.
Numerical simulation of solidification in a horizontal cylindrical annulus charged with an aqueous salt solution
A computational study of solidification of a binary Na2CO3 solution in a horizontal cylindrical annulus is performed using a continuum formulation with a control-volume based, finite-difference scheme. The initial conditions were selected to facilitate the study of counter thermal and solutal convection, accompanied by extensive mushy region growth. Numerical results are compared with experimental data with mixed success. Qualitative agreement is obtained for the overall solidification process and associated physical phenomena. However, the plume thickness calculated for the solutally-driven convective upflow is substantially smaller than the observed value. Evolution of double-diffusive layers is predicted, but over a time scale much smaller than that observed experimentally. Good agreement is obtained between predicted and measured results for solid growth, but the mushy region thickness is significantly overpredicted.