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At least 37 records · Page 2

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗

Stabilizing NMC 811 Li-Ion Battery Cathode through a Rapid Coprecipitation Process

Improving the capacity of LiNi x Mn y Co 1-x-y O 2 (NMC) by increasing the Ni content results in materials with poor cycling performance and reduced thermal stability. These problems can be alleviated by creating concentration gradients in the materials, but this requires more expensive batch processing. Herein, a simple process is described that can create a coating that penetrates into the precursor particles, creating unique gradients in the precursor material. The coated material demonstrates improved cycling performance and thermal stability as compared to uncoated materials. Additionally, rapid heating to simulate a thermal runaway event while observing these materials with X-rays gives a deeper understanding of how the coating affects the decomposition process.

25 ENERGY STORAGE↗

Coprecipitation of thermal lysine-rich proteinoids with polyribonucleotides

An experimental study was conducted to determine whether the precipitation of thermal proteinoids with homopolynucleotides can serve as a tool for studying the specificities between proteins and polynucleotides. Attention is given to exploring the best means of quantitation of the precipitate and the effect of varying the lysine content and the amount of Mg(2+) on the results. The formation of microparticles was monitored both by turbidity and by the mass of precipitate formed. Only under certain conditions was the turbidity a reliable indication of the amount of precipitate. Increasing concentration of Mg(2+) tended to displace proteinoid from the complex with polynucleotide. The results indicate that the interaction of thermal proteinoids with polynucleotides appears to be a suitable tool for studying specificities of interactions between proteins and nucleic acids.

Lacey, J. C., Jr.↗

The evaporation path of seawater and the coprecipitation of Br- and K+ with halite

Brines and salt were sampled at the Morton Bahamas solar salt production facility on Great Inagua Island in the Bahamas. The brines were analyzed by ion chromatography to define more precisely than heretofore the evaporation path of seawater to the end of the halite facies. At Inagua, calcium carbonate begins to precipitate at a brine concentration factor of 1.8 times that of seawater. Gypsum begins to precipitate at a brine concentration of 3.8 times seawater, and halite at a concentration factor of 10.6. Three of the most concentrated brines from Inagua (40 times seawater) were evaporated further in the laboratory. Magnesium sulfate first precipitated at brine concentrations about 70 times those of seawater, and potassium-bearing phases began to precipitate for these brines at concentrations greater than 90 times those of seawater. The distribution of coefficients of Br- and K+ between brines and halite were determined by combining analytical data for the Inagua brines with measurements of the Br- and K+ content of halites from Inagua and of halite which had precipitated from Inagua brines during storage. The observed average value of DBr- is 0.032, in good agreement with some of the previous measurements. The measured values of DK+ are highly variable (0.001 to 0.021); DK+ for halite precipitated early in the halite facies is in the vicinity of 0.015.

NASA Discipline Exobiology↗

Transformation of Ferrihydrite to Goethite and the Fate of Plutonium

Understanding the interactions between plutonium and iron (oxy)hydroxide minerals is necessary to gain a predictive understanding of plutonium environmental mobility and to evaluate long-term performance of nuclear waste repositories. We investigated the fate of plutonium during the formation of ferrihydrite and its subsequent transformation into goethite. Ferrihydrite was synthesized with varying quantities of Pu(IV) following either a sorption or coprecipitation process; the ferrihydrite was then aged hydrothermally to yield goethite. Additionally, the synthesized materials were characterized via extended X-ray absorption fine structure spectroscopy, transmission electron microscopy, and acid leaching to elucidate the nature of plutonium association with ferrihydrite and goethite. In samples prepared following the sorption method, plutonium was identified in two different forms: a PuO 2 precipitate and a surface-sorbed plutonium complex. For the samples prepared via coprecipitation, no PuO 2 formation occurs in the ferrihydrite precursor and in the goethite experiments where plutonium concentration is ≤1000 ppm (mg kg –1 ). In these coprecipitation products, plutonium is strongly bound to the minerals either via formation of an inner sphere complex, or via an incorporation process. In the coprecipitation experiments, PuO 2 formation only occurs at the highest plutonium concentration (3000 ppm), suggesting that during ferrihydrite transformation into goethite, part of the plutonium can be remobilized to form PuO 2 nanoparticles. Collectively, our results demonstrate that the nature of plutonium associated with the precursor ferrihydrite (adsorbed vs coprecipitated) will have a direct impact on the association of plutonium with its alteration product (goethite). Furthermore, the data illustrate that some properties of plutonium association with the precursor ferrihydrite are retained through the transformation into goethite. These findings show that plutonium strongly associates with iron (oxy)hydroxides formed through coprecipitation processes and in these materials, plutonium can be strongly retained by the iron minerals.

54 ENVIRONMENTAL SCIENCES↗

Development of high T(sub c) (greater than 110 K) Bi, Tl, and Y-based materials as superconducting circuit elements

Experimental work has continued on the development and characterization of bulk and hot pressed powders and tapecast materials in the Bi-Sr-Ca-Cu-O and Tl-Ba-Ca-Cu-O systems. A process for producing warp-free, sintered, superconducting tapes of Bi composition Bi2Sr2Ca2Cu3O(x) with a mixed oxide process was established. This procedure required a triple calcination at 830 C for 24 hours and sintering at 845 C from 20 to 200 hours. Hot pressing the triple calcined powder at 845 C for 6 hours at 5000 psi yielded a dense material which on further heat treatment at 845 C for 24 hours exhibited a Tc of 108.2 K. A further improvement in the processing of the bismuth materials was achieved via a chemical coprecipitation process wherein the starting nitrate materials were coprecipitated with oxalic acid, thus yielding a more chemically homogeneous, more reactive powder. With the coprecipitated powders, only one calcine at 830 C for 12 hours and a final sinter at 845 C for 30 hours was sufficient to produce a bulk superconducting material with a Tc of 108.4 K. SAFIRE-type grounding links were successfully fabricated from sintered, tapecast, coprecipitated BSCCO 2223 powders. Compositional and processing investigations were continued on the Tl-based superconductors. Manganese and lithium additions and sintering temperature and time were examined to determine their influence on superconducting properties. It was found that lithium substitutions for copper enhance the transition temperatures while manganese additions produced deleterious effects on the superconducting properties. A suitable procedure for producing reproducible bulk and tapecast material of Tl composition Tl2Ba2Ca2Cu3O(x) was developed and used in fabricating uniform superconducting tapes. The highest transition temperature for Tl-based tapes was measured at 110.2 K. Thallium superconducting SAFIRE-type grounding links were fabricated from the tapes.

Haertling, Gene H.↗

Methods for preparing superalloy articles and related articles

A method for preparing an improved article including a nickel-based superalloy is presented. The method includes heat-treating a workpiece including a nickel-based superalloy at a temperature above the gamma-prime solvus temperature of the nickel-based superalloy and cooling the heat-treated workpiece with a cooling rate less than 50 degrees Fahrenheit/minute from the temperature above the gamma-prime solvus temperature of the nickel-based superalloy so as to obtain a cooled workpiece. The cooled workpiece includes a coprecipitate of a gamma-prime phase and a gamma-double-prime phase, wherein the gamma-prime phase of the coprecipitate has an average particle size less than 250 nanometers. An article having a minimum dimension greater than 6 inches is also presented. The article includes a material having a coprecipitate of a gamma-prime phase and a gamma-double-prime phase, wherein the gamma-prime phase of the coprecipitate has an average particle size less than 250 nanometers.

36 MATERIALS SCIENCE↗

Positive Role of Fluorine Impurity in Recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Materials

Lithium-ion battery (LIB) recycling is considered as an important component to enable industry sustainability. A massive number of LIBs in portable electronics, electric vehicles, and grid storage will eventually end up as wastes, leading to serious economic and environmental problems. Hence, tremendous efforts have been made to improve the hydrometallurgical recycling process because it is the most promising option for handling end-of-life LIBs owing to its wide applicability, low cost, and high productivity. Despite these advantages, some extra elements (Al, Fe, C, F, and so forth) remain as impurities in the removal process and are retained in the solution, which is a great challenge to obtain high-quality cathode materials. In this work, the impacts caused by fluorine impurity on the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode are intensively investigated via hydrometallurgical coprecipitation for the first time. Our results show that up to 1 at. % fluorine impurity brings a positive influence on the recovered material due to a higher Ni 2+ ratio on the surface of cathode particles. In addition, the presence of fluoride ions during coprecipitation could lead to the formation of holes in cathode particles, which improves the rate capability and cyclability dramatically. Compared to the virgin material, the capacity of the NCM622 material with 0.2 at. % fluorine impurity is boosted by ~8% (167.7 mA h/g) with a remarkable capacity retention of 98.0% after 100 cycles at 0.33 C. Besides, the cathode with 0.2 at. % fluorine impurity shows a far better rate performance, especially at high rates (~7% increased at 5 C) than that of virgin. Furthermore, these results convince that a low concentration of fluorine impurity is desirable in the hydrometallurgical recycling process. More importantly, this study offers implications in the design of high-performance NCM622 cathode materials via coprecipitation production with ion doping in the near future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗