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At least 19 records

Coprecipitation of Fe/Cr Hydroxides with Organics: Roles of Organic Properties in Composition and Stability of the Coprecipitates

Iron hydroxides are important scavengers for dissolved chromium (Cr) via coprecipitation processes; however, the influences of organic matter (OM) on Cr sequestration in Fe/ Cr-OM ternary systems and the stability of the coprecipitates are not well understood. Here, Fe/Cr-OM coprecipitation was conducted at pH 3, and Cr hydroxide was undersaturated. Acetic acid (HAc), poly(acrylic acid) (PAA), and Suwannee River natural organic matter (SRNOM) were selected as model OMs, which showed different complexation capabilities with Fe/Cr ions and Fe/Cr hydroxide particles. HAc had no significant effect on the coprecipitation, as the monodentate carboxyl ligand in HAc did not favor complexation with dissolved Fe/Cr ions or Fe/Cr hydroxide nanoparticles. Contrarily, PAA and SRNOM with polydentate carboxyl ligand had strong complexation with Fe/Cr ions and Fe/Cr hydroxide nanoparticles, leading to significant amounts of PAA/SRNOM sequestered in the coprecipitates, which caused the structural disorder and fast aggregation of the coprecipitates. In comparison with that of PAA, preferential complexation of Cr ions with SRNOM resulted in higher Cr/Fe ratios in the coprecipitates. This study advances the fundamental understanding of Fe/Cr-OM coprecipitation and mechanisms controlling the composition and stability of the coprecipitates, which is essential for successful Cr remediation and removal in both natural and engineered settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coprecipitation of Fe/Cr Hydroxides at Organic–Water Interfaces: Functional Group Richness and (De)protonation Control Amounts and Compositions of Coprecipitates

Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO 2 through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pK(a) values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) >> BSA(-NH 2 )) and composition (Cr/Fe molar ratio: on BSA(-NH2) >> HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH 2 were positively charged at acidic pH because of the high pK(a) value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH 2 coatings promoted the formation of Cr(OH) 3 . Finally, this study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selenium interaction with iron minerals: Quantitative comparison of sorption and coprecipitation impacts on mobility

Given the significance of selenium (Se) as a micronutrient, the radioactive nature of some of its isotopes, and its affinity to iron (Fe) minerals, extensive research has been conducted on the sorption mechanisms between Se and these minerals. Here, in this study, we employ sorption data sourced from the L-SCIE database and coprecipitation data from available literature to achieve the following objectives: i) establish coherence between adsorption and coprecipitation processes, ii) quantitatively evaluate the importance of these processes in nuclear waste repository science, and iii) propose a forward-looking approach for integrating coprecipitation into reactive transport models. Our findings indicate that a correlation between Se adsorption and coprecipitation can be established using the λ formalism. The comparable log(λ Se(IV) /λ Se(VI) ) ratios derived from adsorption and coprecipitation experiments suggest that these processes can be quantitatively compared and evaluated using our numerical approach. Across all iron oxide phases examined, coprecipitation leads to significantly greater immobilization of Se compared to adsorption. Specifically, for hydrous ferric oxide, hematite, and goethite, coprecipitation is predicted to result in 100–1000 times more Se immobilization compared to adsorption, irrespective of the Se oxidation state (Se(IV) or Se(VI)); notably stronger immobilization potential via coprecipitation was observed for magnetite. The modeling approach and quantitative analysis presented herein clearly highlight the importance of including coprecipitation processes when simulating Se (and other elements) transport, particularly under conditions where mineral compositions are transient or evolving with time. Neglecting coprecipitation in models is likely to lead to significant overestimates of migration.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Phase field modeling of shearing processes of a dual-lobed γ"|γ'|γ" coprecipitate

The Ni-based superalloy IN718 is one of the most widely used commercial alloy in the aerospace industry since its development in 1960s. The excellent mechanical properties have been attributed in a great deal to strengthening by coherent γ' and γ" precipitates. The deformation mechanisms of these two phases have been well studied individually. Recent experimental characterization has shown coprecipitates of these two phases in a variety of morphologies and it was argued that these coprecipitates may lead to improved strengthening as compared to their monolithic counterparts. However, the deformation mechanisms of these coprecipitates are still not well understood. In this study, we performed microscopic phase field simulations, with generalized-stacking-fault (GSF) energy surfaces from ab initio calculations as inputs, to systematically study the shearing processes of a periodical array of dual-lobed coprecipitates as well as monolithic precipitates. We found that the coupling between the γ' and γ" phases in the coprecipitates forces dislocations to take high energy shearing pathways in both phases that would not occur if they were in monolithic forms. The coupling also creates stacking fault configurations in the coprecipitates that require high stress to form. Thus, the presence of coprecipitates in general should increase the resistance to dislocation shearing and lead to higher strength levels. Various fault configurations observed during the shearing process are documented as a reference for future comparison with experimental observations. The link between stacking fault shearing and microtwinning is also discussed. Here, the mechanisms analyzed in this study deepens our understanding of coprecipitation effects on alloy strength and may form a cornerstone for multi-precipitate strengthened alloy design strategies.

36 MATERIALS SCIENCE↗

Creep Behavior of Compact γ′-γ″ Coprecipitation Strengthened IN718-Variant Superalloy

The development of high-temperature heavy-duty turbine disk materials is critical for improving the overall efficiency of combined cycle power plants. An alloy development strategy to this end involves superalloys strengthened by ‘compact’ γ′-γ″ coprecipitates. Compact morphology of coprecipitates consists of a cuboidal γ′ precipitate such that γ″ discs coat its six {001} faces. The present work is an attempt to investigate the microstructure and creep behavior of a fully aged alloy exhibiting compact coprecipitates. We conducted heat treatments, detailed microstructural characterization, and creep testing at 1200 °F (649 °C) on an IN718-variant alloy. Our results indicate that aged IN718-27 samples exhibit a relatively uniform distribution of compact coprecipitates, irrespective of the cooling rate. However, the alloy ruptured at low strains during creep tests at 1200 °F (649 °C). At 100 ksi (689 MPa) load, the alloy fails around 0.1% strain, and 75 ksi (517 MPa) loading causes rupture at 0.3% strain. We also report extensive intergranular failure in all the tested samples, which is attributed to cracking along grain boundary precipitates. The results suggest that while the compact coprecipitates are indeed thermally stable during thermomechanical processing, the microstructure of the alloy needs to be optimized for better creep strength and rupture life.

36 MATERIALS SCIENCE↗

Development of High-Performance Ni-base Alloys for Gas Turbine Wheels Using a Coprecipitation Approach (Final Technical Report)

In this project, a synergistic approach involving experiments informed by modelling was used to develop γ'/γ'' coprecipitation-strengthened Ni-base superalloys for land-based gas turbine wheels. In thick sections of such turbine wheels, the slow cooling rate normally observed, as well as variations in cooling rate could potentially result in drastically inhomogeneous and coarsened microstructure. Thus, ten alloy compositions were selected based on coprecipitation and sluggish γ’ growth and coarsening during three iterations of alloy development, assisted by extensive CALPHAD modeling. Phase equilibrium calculations, informed by the characterization of early alloys, were successful in predicting suitable aging treatments to obtain bimodal coprecipitate distribution in several alloys. These aging treatments were applied to the subsequent round of alloys and the resulting microstructures were characterized in detail. Two different cooling rates were used during each of these heat treatments to simulate the range of cooling rates observed in a thick section forging. The microstructures were used to calibrate a multi-phase field model (MPF), which was used to study the formation mechanisms of various coprecipitate morphologies observed in the experiments. Following this, the most promising alloys in each round were selected and studied using high temperature tensile and creep tests. Considering that a slower cooling rate would lead to a strength debit, while a faster cooling rate might lead to a decline in creep rupture life of a full-scale wheel, tensile tests were carried out for slower cooled samples, while creep tests were carried out for faster cooled samples. The deformation microstructures were then characterized using advanced characterization techniques such as Diffraction Contrast-Scanning Transmission Electron Microscopy (DC-STEM) and Electron Channeling Contrast Imaging (ECCI). Further, a mean-field creep model was developed and calibrated using these experimental findings to predict long-term creep behavior of these coprecipitation-strengthened alloys.

36 MATERIALS SCIENCE↗

Fate of arsenic during up to 4.5 years of aging of Fe III -As V coprecipitates at acidic pH: Effect of reaction media (Nitrate vs. Sulfate), Fe/As molar ratio, and pH

Iron-arsenate (Fe III -As V ) coprecipitate generated in acid mine drainage and hydrometallurgical practices is one of the potential sources of As contamination in the environment. However, the As behavior as well as the transformation process of the Fe III -As V coprecipitate is still not fully understood under acidic conditions. This work systematically studied the effect of reaction media (sulfate vs. nitrate), Fe/As molar ratios, and acidic pH values on the transformation rates, routes, and products of the Fe III -As V coprecipitates at different temperatures during up to 4.5 years of aging. X-ray diffraction (XRD), transmission electron spectroscopy (TEM), Raman spectroscopy, and extended X-ray absorption fine structure spectroscopy (EXAFS) results showed that the Fe III -As V coprecipitates with Fe/As = 2 transformed to scorodite at pH 4 in both sulfate and nitrate media with poorly crystalline ferric arsenate as precursor. In comparison, for the Fe/As = 4 samples, parascorodite and hematite were formed in sulfate and nitrate media, respectively. We note arsenic was released into the liquid phase during the aging process for the samples with Fe/As = 2 and 4. The aqueous As concentrations ([As] aq ) in sulfate media were larger than those in nitrate media for both the Fe/As = 2 and 4 samples. In addition, the transformation products were goethite and Na-jarosite at Fe/As = 8 and 16, pH 2.5 with the decrease of [As] aq . The results also indicated that 6-line ferrihydrite was a common intermediate for many Fe-As transformation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion–mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ~10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41–92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (~1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO 3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. Finally, these roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

54 ENVIRONMENTAL SCIENCES↗

Revisiting Selenium Interactions with Pyrite: From Adsorption to Coprecipitation

Interactions of selenium (Se), a trace element bio-essential at low concentrations but highly toxic at high concentrations, with the most abundant sulfide mineral in the Earth's crust, namely pyrite, was investigated over a wide range of time scales. At the nanosecond scale, selenate Se(VI)O 4 2– adsorption onto the net pyrite surface is shown by ab-initio computations to proceed via the formation of a chemical bond between an oxyanion oxygen atom and a surface Fe atom, weakening the other Se-O bonds and reducing Se atom oxidation state. At the hour-to-day scale, adsorption and coprecipitation of selenate Se(VI)O 4 2– and selenite, Se(IV)O 3 2– , were investigated through wet chemical batch experiments at various pH values at different sulfide concentrations. Selenium removal from solution is slower and weaker for selenate than for selenite. After 24h, only 10% of selenate, against 60% of selenite (up to 100% in the presence of sulfide), is removed by the pyrite surface. Independently of its original oxidation state, adsorbed Se is completely reduced to elemental trigonal selenium via adsorption, precipitation or coprecipitation, as shown by XANES spectroscopy. Here, our EXAFS results, compared to published data on Se-rich pyrite, show a Se to S substitution within the pyrite structure. The reductive coprecipitation mechanism of selenium with pyrite represents valuable new insights for improving our understanding of modern and ancient biogeochemical cycles involving Se. In addition, several industries can benefit from direct applications of our findings, such as water treatment, green technologies and sustainable mining.

Adsorption↗

Data for "Relative Reactivity and Bioavailability of Mercury Sorbed to or Coprecipitated with Aged Iron Sulfides"

The potential for inorganic mercury (Hg) to be converted to methylmercury depends, in part, on the chemical form of Hg and its bioavailability to anaerobic microorganisms that can methylate Hg. In anaerobic settings, Hg can be associated with sulfide phases, including ferrous iron sulfide (FeS), which can sorb or coprecipitated with Hg. The objective of this study was to determine if the aging state of FeS alters the Hg coordination environment as well as the reactivity and bioavailability of sorbed and coprecipitated Hg species. FeS particles were synthesized with and without Hg2+ and aged in anaerobic conditions for multiple time frames spanning from 1 hour to 1 month. For FeS particles synthesized without Hg, Hg2+ was subsequently sorbed to the FeS for 1 day. Analysis of Hg speciation of these materials by X-ray absorption near edge spectroscopy revealed a predominance of 4-coodinate Hg-S species in the sorbed Hg-FeS solids and a mixture of 2- and 4-coordinate Hg-S in the coprecipitated Hg-FeS. The leaching potential of the Hg was assessed by exposing the particles to a solution of dissolved glutathione (a thiolate-based Hg chelator). As expected, the sorbed Hg-FeS released more soluble Hg compared to the co-precipitated Hg-FeS. However, when these particles were exposed to Desulfovibrio desulfuricans ND132 (a known Hg methylator), more Hg was methylated from the co-precipitated Hg-FeS than the sorbed Hg-FeS, consistent with expectations from the Hg-S coordination state and inconsistent with the selective leaching results. Overall, these results suggest that the bioavailability of particulate Hg cannot be easily discerned by leaching potential into bulk solution. Rather, bioavailability entails more subtle interactions at particle-cell interfaces and perhaps correlates with the local Hg-S coordination state in the particles. This data package contains data shown in the referenced publication, including all figures. Each figure is available in the respective *.csv file and a summary of all files are also included in the the xlsx file. Additional formatted data include X-ray diffraction data of the FeS solids are also available in a HPF format (Panalytical software), X-ray absorption spectroscopy data as *.prj files (Athena), and X-ray fluorescence data in its raw data form.

54 ENVIRONMENTAL SCIENCES↗

An acetate precursor process for BSCCO (2223) thin films and coprecipitated powders

Since the discovery of high temperature superconducting oxides much attention has been paid to finding better and useful ways to take advantage of the special properties exhibited by these materials. One such process is the development of thin films for engineering applications. Another such process is the coprecipitation route to producing superconducting powders. An acetate precursor process for use in thin film fabrication and a chemical coprecipitation route to Bismuth based superconducting materials has been developed. Data obtained from the thin film process were inconclusive to date and require more study. The chemical coprecipitation method of producing bulk material is a viable method, and is preferred over the previously used solid state route. This method of powder production appears to be an excellent route to producing thin section tape cast material and screen printed devices, as it requires less calcines than the oxide route to produce quality powders.

Haertling, Gene H.↗

Predicting Morphological Evolution during Coprecipitation of MnCO 3 Battery Cathode Precursors Using Multiscale Simulations Aided by Targeted Synthesis

The performance of lithium-ion batteries is intimately linked to both the structure and the morphology of the cathode material, which in turn is critically linked to the synthesis conditions. However, few studies focus on understanding synthesis, especially during the coprecipitation of metal oxide precursors, a process that largely determines the final morphology of the material. In this paper, we go beyond the typical equilibrium particle shape analysis conducted in the literature and incorporate kinetic aspects of morphology evolution. We perform these studies using controlled synthesis on a well-defined metal salt system (MnCO 3 ) combined with multiscale simulations and high-resolution microscopy. Results show that with increasing metal concentration, the particles transition from rhombohedral to cubic to spherical shapes. Computational analysis using density functional theory (DFT) reveals that rhombohedral shaped particles evolve under equilibrium conditions. Phase field techniques indicate that at higher metal concentrations, fast growth kinetics of the precipitates result in the transition to cubic and, subsequently, spherical shapes, accompanied by a decrease in particle size. This study, while limited to the one metal salt system, provides an approach to shed light on the synthesis process of mixed transition metal salts, gradient materials, and other cathode materials of interest to the battery community.

25 ENERGY STORAGE↗

Efficient separation and coprecipitation for simplified cathode recycling

Hydrometallurgical recycling of spent lithium-ion batteries is among the most promising recovery approaches. The current hydrometallurgical method for battery recycling faces challenges such as complex separation and precipitation processes, and environmental concerns from the use of caustic inorganic acid and hazardous hydrogen peroxide. Our proposed modified method, namely polyol-metallurgy, uses citric acid in ethylene glycol as dual-function green solution to overcome these obstacles. This bifunctional solution leaches valuable metal ions from cathode materials (e.g., LiCoO 2 ), and then acts as chelating agents to selectively precipitate cobalt through an esterification reaction, without the need for additional precipitation agents. The leaching efficiency of cobalt and lithium reaches 99.55% and 97.65%, respectively, and more than 96% of cobalt could be directly self-precipitated and recovered. Further, the unique characteristics of the dual-function solution also avoids impurities from Al foils and PVDF/carbon black films, enabling the simple separation process. Therefore, the process can be completed in one-pot system with efficient leaching, separation and coprecipitation, making it more efficient and feasible for operation than existing alternatives.

25 ENERGY STORAGE↗

(Fe, Cr)(OH) 3 Coprecipitation in Solution and on Soil: Roles of Surface Functional Groups and Solution pH

The simultaneous precipitation of (Fe, Cr)(OH) 3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO 2 and Al 2 O 3 . Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH) 3 accumulation on negatively charged SiO 2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH) 3 and surfaces. The elevated pH through protonation of Al 2 O 3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Here, due to ignorable NOM adsorption onto SiO 2 , the amounts of (Fe, Cr)(OH) 3 precipitates on bare/NOM-SiO 2 were similar; contrarily, attributed to favored NOM adsorption onto Al 2 O 3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH) 3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al 2 O 3 than bare-Al 2 O 3 . With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH) 3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH) 3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.

(Fe, Cr)(OH)3 distribution↗

Unveiling Morphology and Crystallinity Dynamics in Ni x Mn 1– x CO 3 Cathode Precursors through Batch-Mode Coprecipitation

This study delves into the synthesis and control of Ni x Mn 1–x CO 3 , a critical class of Mn-rich, Co-free precursors vital for cathode-oxide materials in energy storage and conversion technologies. Employing batch-mode coprecipitation, we systematically generated samples with varying Ni concentrations (x = 0, 0.1, 0.3, 0.5, 0.7, and 0.9) and conducted a comprehensive analysis of their compositions, crystallinities, transition-metal distributions, and particle morphologies through both experimental and computational methods. A significant variation in particle size and crystallinity was observed, contingent on the Ni content. Further, a pivotal transition emerged at Ni concentrations above x = ~0.5, transforming uniform morphologies, such as spherical, monodisperse, pseudo-single-crystalline particles, into bimodal, polycrystalline structures. Furthermore, the study highlights the role of Ni–ammonia complexes leading to Ni-deficient precipitates and underscores the importance of ammonia concentration in achieving precise Ni content control. This study unveils critical reaction conditions governing Mn-rich precursor properties that are vital for cathode-oxides, emphasizing the need for meticulous synthetic control and offering the potential for practical applications in advanced energy storage and conversion systems.

25 ENERGY STORAGE↗

Stability Enhancement in Na 0.67 Fe 0.2 Mn 0.8 O 2 Positive Electrodes via Spherical Coprecipitated Hydroxide Precursor Synthesis for Na-Ion Batteries

Mn/Fe-based layered transition metal oxides (LTMOs) are promising positive electrode materials for sodium-ion batteries (SIBs) due to their high abundance, low cost, and stable price fluctuations. At commercial scale, the fabrication of these materials commonly employs coprecipitation of hydroxide precursors, which allows for the scalable synthesis of uniform, dense particles with a tunable morphology. However, the common chelating agent (ammonia) forms unstable complexes with Fe 2+ ions, resulting in uncontrollable particle morphology and poor electrochemical properties. Here, in this study, three chelation strategies (no chelation, ammonia, oxalate) for Fe/Mn-based hydroxides are evaluated. It was found that oxalate chelation produced uniform, dense spherical hydroxide particles while particles via ammonia / no chelate routes exhibited no morphological control. The LTMOs synthesized from the oxalate-chelated hydroxide precursor formed uniform spherical particles, while the other two LTMOs showed greater variation in particle morphology. The oxalate-chelated LTMO electrode exhibited increased cycling stability due to reduced parasitic reactions with the electrolyte, as characterized by static leakage current measurements and electrochemical impedance spectroscopy.

25 ENERGY STORAGE↗

Improving the Thermal Stability of NMC 622 Li-Ion Battery Cathodes through Doping During Coprecipitation

Increasing the Ni content of LiNi x MnyCo 1-x-y O 2 (NMC) cathodes can increase the capacity, but additional stability is needed to improve safety and longevity characteristics. In order to achieve this improved stability, Mg and Zr were added during the coprecipitation to uniformly dope the final cathode material. These dopants reduced the capacity of the material to some extent, depending on the concentration and calcination temperature. However, these dopants can impart substantial stabilization. It was found that the degree of stabilization is strongly dependent on the calcination temperature of the material. In addition, we used synchrotron X-ray diffraction during thermal breakdown to better understand why the different dopants impact the thermal stability and confirm the stabilization effects of the dopants.

25 ENERGY STORAGE↗