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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Secondary structure and dynamics study of the intrinsically disordered silica-mineralizing peptide P 5 S 3 during silicic acid condensation and silica decondensation

The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P5S3, a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains five protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated ortho silicic acid P5S3 strongly enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO2) at globally undersaturated concentrations. The secondary structure of P5S3 during these different functions was studied by circular dichroism (CD), complemented by nuclear magnetic resonance (NMR) studies of the peptide in the absence of silicate. The NMR studies of dual-labeled (13C, 15N) P5S3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5 to 9.5, the CD data verified the disordered secondary structure but also suggested the presence of some polyproline II character in the absence of silicic acid. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P5S3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. Consequently, the secondary structural changes observed for P5S3 correlate with the presence of oli-gomeric/polymeric silicic acid, presumably due to P5S3-silicic acid interactions. These interactions appear, at least in part, ionic in nature since dodecylsulfate micelles, which are negatively charged, cause similar conformational shifts to P5S3 in the absence of silica while ß-D-dodecyl maltoside micelles, which are neutral, do not. Thus, P5S3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid. Moreover, the dynamics of these pro-cesses may be indirectly monitored by following structural changes to P5S3 with CD spectroscopy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H{sub 2}SO{sub 4}-CuSO{sub 4} Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy

The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H{sub 2}SO{sub 4}-CuSO{sub 4} electrolyte were investigated by a direct observation method that combined the techniques of optical microscopy and channel flow double electrode. Linear sweep voltammetry of the anodes showed that the dissolution of Cu transited from the charge transfer-controlled reaction to the mass transfer-controlled reaction, followed by the passivation of the electrodes. The direct observation of the pure Cu anode revealed that Cu particles were generated on the surface and the particles fell away during passivation. On the other hand, a slime layer of Ag particles that adhered to the surface was generated during the dissolution of the Cu-5 wt pct Ag anode. The Cu-5 wt pct Ag anode was passivated with a lower current density than the pure Cu anode, which suggested that the morphology and adhesive characteristics of the slime on the anode affected the passivation. The direct observation method described herein is useful for understanding reactions on electrodes that undergo drastic changes in their surface morphology. Information obtained from this method can help with the development of new processes for the effective utilization of limited natural resources and energy, such as the recycling of Cu by electrorefining.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermo-chemical Fluid Flow Simulation in Hot-Dip Galvanizing: The Evaluation of Dross Build-Up Formation

This paper presents a new computational framework to investigate the driving force for the formation of intermetallic dross particles in the zinc bath and dross build-up on the bath hardware. This is a major problem in continuous hot-dip galvanizing lines. The Computational Fluid Dynamics (CFD) model calculates the turbulent thermo-chemical flow conditions within the liquid melt. A detailed modeling of the steel strip–liquid interface enhances this approach, by means of a conjugated heat transfer calculation and a spatially resolved, temperature- and concentration-dependent iron dissolution and aluminum uptake. The heart of the computational framework is a thermodynamic model, which assesses the driving force for the formation or dissolution of dross particles in the bath and dross build-up on stationary and rotating equipment. The simulation results are validated with temperature and species depth profile measurements. The applicability of the CFD model is shown by investigating the locally resolved aluminum uptake and iron dissolution at the steel-strip surface, and the multi-physics conditions in the region near the roll. The novel approach of evaluating the thermodynamic driving force enables the assessment of the formation of dross build-up at the roll surface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (α ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effect of retarders on the early hydration of calcium-sulpho-aluminate (CSA) type cements

The retardation of calcium-sulpho-aluminate (CSA) type cements by three common retarders—sodium gluconate, sodium–potassium tartrate and borax is investigated at a 2% addition rate. Each of the retarders has a different effect on the early-age hydrate assemblage, as shown by quantitative X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and pore solution analysis. Regardless of the retarder used, the hydration starts with mainly the dissolution of ready soluble (calcium) alkali sulphates and ye'elimite, followed by the formation of ettringite and aluminium hydroxide, whereby the specific clinker mineral dissolution as well as ettringite-forming reaction is delayed in different ways depending on the retarder used. The results showed that the retardation is mainly caused by preventing hydrates formation in the case of tartrate and gluconate. Contrary, borax retards the hydration by preventing to a certain extent the dissolution of ye'elimite and lowers the initial pH. Furthermore, the morphology of ettringite is altered depending on the type of the retarder used.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modelling of the sulfuric acid attack on different types of cementitious materials

A chemical-reactive transport model is used to simulate the sulfuric acid attack of cement pastes based on ordinary Portland cement (CEM I), blended Portland cements (CEM III, CEM IV, and CEM V), and calcium aluminate cement (CAC). This model accounts for the dissolution of cement hydrates (portlandite, C-S-H, hydrogarnet), and the precipitation of deterioration products (ettringite and gypsum). Moreover, diffusion of the aqueous species in the pore space of the material is considered. With this model, the hydrate contents, the porosity, and the deterioration phase contents throughout a sulfuric acid attack are determined. Two indicators are defined to predict the service life of the cementitious materials: the deterioration depth and the dissolved calcium content. These two indicators show that calcium aluminate cement has a better resistance to sulfuric acid attack than that of Portland cements. This better resistance is mainly due to the partial dissolution of CAC hydrate as opposed to the total dissolutions of CH and C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Synchrotron X-ray nanotomographic and spectromicroscopic study of the tricalcium aluminate hydration in the presence of gypsum

The rheology of modern Portland cement (PC) concrete critically depends on the correct dosage of gypsum (calcium sulfate hydrate) to control the hydration of the most reactive phase - tricalcium aluminate (C{sub 3}A). The underlying physio-chemical mechanism, however, remains unsolved mainly due to the lack of high-spatial-resolved and chemistry-sensitive characterization of the C{sub 3}A dissolution frontier. Here, we fill this gap by integrating synchrotron-radiation based crystallographic, photon-energy-dependent spectroscopic and high-resolution morphological studies of the C{sub 3}A hydration product layer. We propose that ettringite (6CaO·Al{sub 2}O{sub 3}·SO{sub 3}·32H{sub 2}O) is the only hydration product after the initial reaction period and before complete gypsum dissolution. We quantify the 2D and 3D morphology of the ettringite network, e.g. the packing density of ettringite at various surface locations and the surface dissolution heterogeneity. Our results show no trace of a rate-controlling diffusion barrier. We expect our work to have significant impact on modeling the kinetics and morphological evolution of PC hydration.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion of 316 L stainless steel under the natural circulation of molten NaCl-MgCl 2 salt

The corrosion behavior of 316 L stainless steel (SS) was studied via the natural circulation of molten eutectic NaCl-MgCl 2 salt through a microloop. The post-corrosion tested 316 L SS microloop sections were characterized with microscopy techniques to determine the microstructural and microchemical changes that occurred at the alloy/salt interface. It was found that 316 L SS showed heterogeneous dissolution at the hot-leg, whereas deposition of corrosion products occurred at the cold-leg. For the first time, experimentally obtained molten salt flow-induced corrosion of 316 L SS results were combined with computational thermodynamic-kinetic models to validate the dissolution and deposition in terms of elemental compositional changes at the alloy/salt interface. The thermodynamic-kinetic modeling predicted that the heterogeneous dissolution of Cr and Fe from the hot-leg section of 316 L SS persisted throughout the salt circulation. The model also estimated that, despite Cr deposition starting earlier than Fe, the total redeposition of Fe is expected to be significantly greater than that of Cr over the circulation of salt. Furthermore, the modeling accurately predicted the subsurface enrichment of Mo which is attributed to the reduced Cr activity and the relatively higher diffusion rate of Mo within the alloy matrix. Here, the agreement between modeling and experimental results confirms that Fe chlorides dissolve at the hot-leg and subsequently deposit at the cold-leg due to activity changes driven by the thermal gradient. By contrast, Cr was not detected in the cold-leg deposits, which is attributed to its weaker temperature dependence on activity, limiting its redeposition under these conditions.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Mastering the synergy between Na 3 V 2 (PO 4 ) 2 F 3 electrode and electrolyte: A must for Na-ion cells

Sodium-ion batteries are emerging as suitable energy storage devices for special applications such as high-power devices with the advantages of being cheaper and more sustainable than the Li-ion equivalents. The sodium ion cells consisting of polyanionic Na 3 V 2 (PO 4 ) 2 F 3 - hard carbon electrodes exhibit high power rate capabilities but limited cycle life, especially at high temperatures. To circumvent this drawback we herein conducted in-depth analyses of the origins of structural degradations occurring in Na 3 V 2 (PO 4 ) 2 F 3 electrodes upon long cycling. Vanadium dissolution with associated parasitic reactions is identified as one of the major reasons for cell failure. Its amount varies depending on the electrolyte, with NaTFSI-based electrolyte showing the least vanadium dissolution as the TFSI - anion decomposes without producing acidic impurities, in contrast to the NaPF 6 -based electrolyte. The dissolved vanadium species undergoes oxidation and reduction processes at the Na 3 V 2 (PO 4 ) 2 F 3 and HC electrodes, respectively, with the electrochemical signature of these processes being used as a fingerprint to identify state of health of the 18650 cells. Here, having found that surface reactivity is the primary cause of vanadium dissolution we provide methods to mitigate it by combining surface coating and optimized electrolyte formulation.

25 ENERGY STORAGE↗
DOE OSTI2018

Recycling Glass Fiber Thermoplastic Composites from Wind Turbine Blades

We report that thermoplastic resin systems have long been discussed for use in large-scale composite parts but have yet to be exploited by the energy industry. The use of these resins versus their thermosetting counterparts can potentially introduce cost savings due to non-heated tooling, shorter manufacturing cycle times, and recovery of raw materials from the retired part. Because composite parts have high embedded energy, recovery of their constituent materials can provide substantial economic benefit. This study determines the feasibility of recycling composite wind turbine blade components that are fabricated with glass fiber reinforced Elium (R) thermoplastic resin. Several experiments are conducted to tabulate important material properties that are relevant to recycling, including thermal degradation, grinding, and dissolution of the polymer matrix to recover the constituent materials. Dissolution, which is a process unique to thermoplastic matrices, allows recovery of both the polymer matrix and full-length glass fibers, which maintain their stiffness (190 N/(mm g)) and strength (160 N/g) through the recovery process. Injection molded regrind material is stiffer (12 GPa compared to 10 GPa) and stronger (150 MPa compared to 84 MPa) than virgin material that had shorter fibers. An economic analysis of the technical data shows that recycling thermoplastic-glass fiber composites via dissolution into their constituent parts is commercially feasible under certain conditions. This analysis concludes that 50% of the glass fiber must be recovered and resold for a price of $0.28/kg. Furthermore, 90% of the resin must be recovered and resold at a price of $2.50/kg.

17 WIND ENERGY↗
DOE OSTI2014

Origin of the solid solution in the LiInSe{sub 2}–In{sub 2}Se{sub 3} system

Techniques of bulk and local analyses were used to characterize the melt-grown single crystals of LiInSe{sub 2}, where yellow matrix coexists together with extended red areas distributed irregularly. Bulk chemical analysis showed that the average stoichiometry of yellow matrix is close to ideal 1:1:2, but red areas are enriched with In{sub 2}Se{sub 3}. An excess In{sub 2}Se{sub 3} is incorporated coherently into the crystal lattice of LiInSe{sub 2}, forming the substitution solid solution with the general formula (Li{sub 1−3x}In{sub x}⎕{sub 2})InSe{sub 2} and changing the color from yellow to red. The test crystals with the 50–55% content of In{sub 2}Se{sub 3} were found by the X-ray analysis to be single phase. The differential dissolution technique, measuring the spatial variation of the composition with high resolution, demonstrated that the single phase crystals in the LiInSe{sub 2}–In{sub 2}Se{sub 3} system might be grown only in a very narrow range close to stoichiometric. Being supersaturated, the heterovalent solid solution phases decompose in the course of cooling, and the concentration micro-heterogeneity occurs in the matrix as the coherent (or incoherent) inclusions of two different types, practically pure selenides of lithium and indium. The origin and scale of the micro-heterogeneity determining the physical properties of LiInSe{sub 2} are discussed as a starting point for the development of physicochemical foundations for growing high quality optical crystals. - Graphical abstract: Differential dissolution technique applied for detection of dispersive precipitates in as-grown LiInSe{sub 2} single crystals: kinetic curves of the phase dissolution: F is the main phase Li{sub 0.96}In{sub 1.01}Se{sub 2} (98.9%), secondary minor phases Li{sub 2}Se (0.1%), In{sub 2}Se{sub 3} (0.9%). - Highlights: • Phase purity of crystals Li{sub 1−3x}In{sub 1+x}Se{sub 2} was examined by a new stoichiographic method. • Breakup of the metastable solid solution with temperature drop was detected. • Dispersive precipitates Li–Se and In–Se of low content result from the breakup. • A crucial role of the precipitates in optical properties of the crystals is shown. • Conditions are given how to grow stoichiometric and single-phase crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis of hexagonal wurtzite Cu{sub 2}ZnSnS{sub 4} prisms by an ultrasound-assisted microwave solvothermal method

Wurtzite Cu{sub 2}ZnSnS{sub 4} (CZTS) hexagonal prisms were synthesized by a simple ultrasound-microwave solvothermal method. The product was characterized by XRD, FESEM, EDS, TEM, Raman and UV–vis spectrometer. The hexagonal prisms were 0.5–2 μm wide and 5–12 μm long. The PVP played an important role in the formation of the CZTS hexagonal prisms. In addition, the ultrasound-assisted microwave process was helpful for synthesis of wurtzite rather than kesterite phase CZTS. A nucleation–dissolution–recrystallization mechanism was also proposed to explain the growth of the CZTS hexagonal prisms. - Graphical abstract: Wurtzite Cu{sub 2}ZnSnS{sub 4} hexagonal prisms were synthesized by ultrasound-microwave solvothermal method. The ultrasound-assisted microwave process and PVP were useful to the growth of CZTS. A nucleation–dissolution–recrystallization growth mechanism was also proposed. - Highlights: • Wurtzite Cu{sub 2}ZnSnS{sub 4} was prepared by ultrasound-assisted microwave solvothermal method. • The wurtzite CZTS hexagonal prisms are demonstrated a band gap of 1.49 eV. • Synergistic effect of ultrasound and microwave is helpful to prepare Wurtzite CZTS. • PVP plays an important role in the formation of the CZTS hexagonal prisms. • Nucleation–dissolution–recrystallization growth mechanism of the CZTS was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Microstructural evolution and growth behavior of intermetallic compounds at the liquid Al/solid Fe interface by synchrotron X-ray radiography

Highlights: • A layered and tongue-like η phase was in-situ observed by synchrotron radiation X-ray radiography. • The coalescence of η phase bottom resulted in dissolution, further increasing the growth rate. • The θ phase growth behavior with different morphologies during cooling was analyzed. - Abstract: The growth of Inter-Metallic Compounds (IMCs) with dissolution was investigated on the liquid Al/solid Fe interconnection by using synchrotron radiation real-time imaging technology. At the initial stage of holding at 850 °C, a layer of the η-Fe{sub 2}Al{sub 5} phase formed at the interface, and tongue-like η grew into α-Fe. The tongue-like η phase had a stronger (001) texture than the layered phase. The coalescence of tongue-like η started at the bottom, followed by the dissolution of IMCs, which leads to a further increase in its growth rate. During solidification stage, the dotted, needle-like and flake θ-FeAl{sub 3} phases were sequentially formed.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Determining the biomass fraction of mixed waste fuels: A comparison of existing industry and {sup 14}C-based methodologies

Highlights: • Compares industry standard and {sup 14}C methods for determining bioenergy content of MSW. • Differences quantified through study at an operational energy from waste plant. • Manual sort and selective dissolution are unreliable measures of feedstock bioenergy. • {sup 14}C methods (esp. AMS) improve precision and reliability of bioenergy determination. • Implications for electricity generators and regulators for award of bio-incentives. - Abstract: {sup 14}C analysis of flue gas by accelerator mass spectrometry (AMS) and liquid scintillation counting (LSC) were used to determine the biomass fraction of mixed waste at an operational energy-from-waste (EfW) plant. Results were converted to bioenergy (% total) using mathematical algorithms and assessed against existing industry methodologies which involve manual sorting and selective dissolution (SD) of feedstock. Simultaneous determinations using flue gas showed excellent agreement: 44.8 ± 2.7% for AMS and 44.6 ± 12.3% for LSC. Comparable bioenergy results were obtained using a feedstock manual sort procedure (41.4%), whilst a procedure based on selective dissolution of representative waste material is reported as 75.5% (no errors quoted). {sup 14}C techniques present significant advantages in data acquisition, precision and reliability for both electricity generator and industry regulator.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2015

Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes

Highlights: • Research showed the origin of DIC in the groundwater around a reclaimed landfill. • Carbon isotope was used to evaluate the contributions of carbon from different sources. • The leachate-contaminated water was isotopically distinct from the natural groundwater. • DIC in the natural groundwater comes from organic matter and dissolution of carbonates. • In the contaminated water, DIC comes from organic matter in the aquifer and landfill. - Abstract: Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ{sup 13}C{sub DIC}) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ{sup 13}C{sub DIC} values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4–54% of the DIC pool is derived from organic matter degradation and 96–46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20–53% of the DIC is derived from organic matter degradation of natural origin and 80–47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO{sub 2} (P CO{sub 2}) was generally above the atmospheric, hence atmospheric CO{sub 2} as a source of carbon in DIC pool was negligible in the aquifer. P CO{sub 2} values in the aquifer in Otwock were always one to two orders of magnitude above the atmospheric P CO{sub 2}, and thus CO{sub 2} escaped directly into the vadose zone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Delamination mechanism study of large size waste printed circuit boards by using dimethylacetamide

Highlights: • Dimethylacetamide (DMA) dissolved the epoxy resin of printed circuit boards (WPCB). • PCBs of 1, 4, 9 and 16 cm{sup 2} were delaminated in 150, 180, 300 and 420 min, respectively. • Peaks of epoxy resin and DMA were evident in the NMR spectra. • Shift in C=O, OH peaks of DMA & resin, respectively was registered w.r.t. time. • Hydrogen bonding between C=O of DMA and OH of resin results in the dissolution. - Abstract: Present work investigates the recycling of waste printed circuit boards (PCBs) by cracking of its multi-layered structure by using dimethylacetamide (DMA). The study shows that cracking and separation of layers of PCBs increases as the temperature increases; and decreases as the surface area of PCBs increases. After separation of layers, the used solvent was analyzed by proton and carbon nuclear magnetic resonance spectroscopy (NMR) to understand the dissolution phenomenon of resin. Further, NMR and Fourier transform infrared spectroscopy analysis of DMA sample after 1 h, 2 h, 3 h, 4 h and 8 h of reaction with PCBs at 433 K and PCB:DMA ratio (wt/vol) of 3:10 has been carried out to investigate the mechanism of dissolution of resin. These studies revealed that hydroxyl group of PCBs polymeric chain participates in hydrogen bonding with parent carbonyl group of DMA molecule that results in the solvation of resin. Possible chemical reaction based on the above finding has been discussed. Using this technique, separation of the metallic fraction without application of any energy intensive mechanical pre-processing is possible.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Phase Transformation Mechanism of Amorphous Calcium Phosphate to Hydroxyapatite Investigated by Liquid-Cell Transmission Electron Microscopy

Crystallization via phase transformation of a metastable precursor is a ubiquitous and effective strategy used by living systems to direct the growth of crystalline nanomaterials with remarkable functional properties. However, determining the exact process by which transformation occurs at the nanoscale is a difficult challenge. In this work, the recrystallization process of amorphous calcium phosphate (ACP) to hydroxyapatite (HAP) is explored by liquid-cell transmission electron microscopy. The effect of confinement in the liquid-cell is found to increase the size of ACP nanoparticles. In the presence of Mg 2+ , these large ACP nanoparticles transform to HAP by first dissolving from the interior to create a hollow structure, after which HAP forms preferentially on the surface and then subsequently in the bulk solution. We propose that the preferential dissolution within ACP particles is due to a change in the structure and/or chemistry of the ACP surface, likely associated with dehydration before crystallization of HAP. These results imply an important role of the confined environment of the liquid-cell in regulating the size of ACP particles, which then affects the surface structure and the detailed dissolution–recrystallization pathway. Moreover, we stress the key role of Mg 2+ in controlling HAP formation by stabilizing ACP via reduction in ACP solubility. This work provides a better understanding of the roles of additives and confinement during the phase transformation of ACP to HAP through dissolution and recrystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Recovery of Oxidized Actinides, Np(VI), Pu(VI), and Am(VI), from Cocrystallized Uranyl Nitrate Hexahydrate: A Single Technology Approach to Used Nuclear Fuel Recycling

In this work, the utility of recovering cocrystallized Np, Pu, and Am from a uranyl nitrate hexahydrate crystalline phase has been examined. Progressive dissolution studies were carried out on samples of either Np(VI), Pu(VI), or Am(VI) cocrystallized with uranyl nitrate hexahydrate, resulting in a linear relationship between the amount of actinides dissolved as a function of volume of HNO 3 added, which indicates homogeneous distribution of the transuranic species throughout the crystalline solid. The ratio of the concentration of U to the heavier actinides was maintained over the entire dissolution and mimicked that of the starting cocrystallization solution. A series of five crystallization–dissolution–recrystallization cycles of uranyl nitrate hexahydrate from nitric acid have been achieved in the presence of Am(VI), where the behavior of Am(VI) followed that of U(VI) for each step of all five cycles. Negligible reduction of Am(VI) to Am(III) was observed between each recrystallization cycle. These results indicate the utility of a group hexavalent actinide cocrystallization approach toward used nuclear fuel recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗