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At least 721 records · Page 40

Soluble Graphene Nanosheets from Recycled Graphite of Spent Lithium Ion Batteries

Soluble graphene nanosheets are fabricated from recycled graphite of spent lithium ion batteries through a modified Hammers process followed by deoxygenation with NaOH–KOH eutectic. Ultrasonic exfoliation in N-methyl-pyrrolidone indicates the loosened graphene layers in recycled graphite are prone to exfoliation. Reduction of the exfoliated graphene oxide sheets was conducted in molten NaOH–KOH eutectic at different temperatures. The results show that molten NaOH–KOH effectively eliminates the unsaturated oxygen-containing moieties from the exfoliated graphene oxide sheets while creating more hydroxyl functional groups. Higher temperature treatment is more prone to remove hydroxyls while producing the shrinkage on the surface of graphene sheets. Graphene sheet with a good solubility is produced when the graphene oxide is heat-treated at 220 °C for 10 h. After reduction, the graphene oxide sheets exhibit excellent dispersibility or solubility in water, ethanol and other polar solvents, therefore being highly desirable for solution processing of graphene materials. Such study not only identifies a high-quality stockpile to prepare soluble graphene but also paves a feasible alternative of graphite recycling from spent lithium batteries.

36 MATERIALS SCIENCE↗

Fiber Laser Welding–Brazing Characteristics of Dissimilar Metals AZ31B Mg Alloys to Copper with Mg-Based Filler

Fiber laser welding–brazing of 1-mm-thick AZ31B Mg alloys to 1.5-mm-thick copper (T2) with Mg-based filler was performed in a lap configuration. The weld appearance, interfacial microstructure and mechanical properties were investigated with different heat inputs. The results indicated that processing windows for optimizing appropriate welding parameters were relatively narrow in this case. Visually acceptable joints with certain strength were achieved at appropriate welding parameters. The maximum tensile-shear fracture load of laser-welded-brazed Mg/Cu joint could reach 1730 N at the laser power of 1200 W, representing 64.1% joint efficiency relative to AZ31Mg base metal. The eutectic structure (α-Mg + Mg{sub 2}Cu) and Mg-Cu intermetallic compound was observed at the Mg/Cu interface, and Mg-Al-Cu ternary intermetallic compound were identified between intermetallics and eutectic structure at high heat input. All the joints fractured at the Mg-Cu interface. However, the fracture mode was found to differ. For laser power of 1200 W, the surface was characterized by tearing edge, while that with poor joint strength was almost dominated by smooth surface or flat tear pattern.

36 MATERIALS SCIENCE↗

Development of Graphene Nanoplatelet-Reinforced AZ91 Magnesium Alloy by Solidification Processing

It is a challenging task to effectively incorporate graphene nanoplatelets (GNPs) which have recently emerged as potential reinforcement for strengthening metals into magnesium-based matrices by conventional solidification processes due to their large surface areas and poor wettability. A solidification processing which combines mechanical stirring and ultrasonic dispersion of reinforcements in liquid matrix was employed to develop AZ91 magnesium alloy matrix composites reinforced with 0.25 and 0.5 wt.% GNPs. The microstructural studies conducted with scanning and transmission electron microscopes revealed that fairly uniform distribution and dispersion of GNPs through the matrix were achieved due to effective combination of mechanical and ultrasonic stirring. The GNPs embedded into the magnesium matrix led to significant enhancement in the hardness, tensile strength and ductility of the composites compared to those of unreinforced AZ91 alloy. The strength enhancement was predominantly attributed to the grain refinement by the GNP addition and dislocation generation strengthening due to the coefficient of thermal expansion mismatch between the matrix and reinforcement. The improved ductility was attributed to the refinement of β eutectics by transforming from lamellar to the divorced eutectics due to the GNP additions. In addition, the strengthening efficiency of the composite with 0.25 wt.% GNP was found to be higher than those of the composite with 0.5 wt.% GNP as the agglomeration tendency of GNPs is increased with increasing GNP content. These results were compared with those of the GNP-reinforced magnesium composites reported in the literature, indicating the potential of the process introduced in this study in terms of fabricating light and high-performance metal matrix composites.

36 MATERIALS SCIENCE↗

Microstructure and Mechanical Properties of Three-Layer TIG-Welded 2219 Aluminum Alloys with Dissimilar Heat Treatments

2219-C10S and 2219-CYS aluminum alloys are 2219 aluminum alloys with different heat treatment processes, and they have been widely used in the aerospace industry. In the present study, 2219-C10S and 2219-CYS aluminum alloys were butt-welded by three-layer tungsten inert gas arc welding (with the welding center of the third layer shifted toward the CYS side), and the microstructure characteristics and mechanical properties of the welded joint were investigated. The lamellar θ′ phases, the bulk or rod θ phases, and the coarse rod-shaped or pancake-shaped Al-Cu-Fe-Mn phases coexisted in the two aluminum alloys. The Cu content of the α-Al matrix and the distribution of eutectic structures of different welding layers in the weld zone (WZ) were varied, implying that the segregation degrees of the Cu element were different due to the different welding thermal cycles in different welding layers. The microhardness values of the CYS side were much higher than those of the C10S side in each region on both sides of the joint. The tensile test deformation was concentrated mainly in the regions of WZ and the over aged zone (OAZ), where the microhardness values were relatively low. The main deformation concentrated region was transferred from the CYS side to the C10S side with the increase in the tensile load during the tensile test. The fracture behavior of the tensile test showed that the macroscopic crack initiated near the front weld toe had gone through the crack blunt region, the shear fracture region of the partially melted zone (PMZ), and the shear fracture region of OAZ. Meanwhile, the fracture characteristics gradually evolved from brittle to ductile. The concentrated stress and the dense eutectic structure in the region near the front weld toe of the C10S side contributed to the fracture of the joint. The shift of the welding center of the third layer to the CYS side resulted in two effects: (i) the microhardness values from the middle layer to the top layer in the PMZ of the CYS side were the most significantly increased and (ii) the distance between the front weld toe and the fusion line of the CYS side was significantly larger.

36 MATERIALS SCIENCE↗

Effects of In Situ Intermetallics on the Microstructural Array and Saline Corrosion Performance of Cast Al/WCp Composites

Al-matrix composites, ex situ reinforced with WC nanoparticles and in situ reinforced with Al{sub 3}(Ti,W), Al{sub 12}W, Al{sub 5}W and Al{sub 4}W, have been fabricated by casting assisted by K{sub 2}TiF{sub 6} wetting agent addition and mechanical stirring. A satisfactory particle incorporation and distribution accompanied by a high reactivity have been attained. The presence, topography, chemical composition of all included phases and their occurrence as clusters or single particles are clarified and justified. Al{sub 12}W is the predominant aluminide phase at WC ≤ 1.5 vol.%. Al{sub 4}W (primarily) and Al{sub 5}W (secondarily) are the predominant aluminide phases at WC ≥ 2.0 vol.%. WC nanoparticles have acted as heterogeneous nucleation sites to Al{sub 3}Ti particles. Reverse polarization tests in 3.5 wt.% NaCl show that the governing form of corrosion is intergranular corrosion of Al around Al{sub 3}FeSi{sub 2} eutectic, fine plates. The corrosion steps/mechanisms are identified. Clusters of aluminides and carbide nanoparticles, as well as intergranular WC nano-dispersoids and their Al-matrix have remained corrosion-free. The role of the aluminides combined with WC remaining nano-cores as inhibitors of the eutectic Al{sub 3}FeSi{sub 2} cathodic activity is highlighted.

36 MATERIALS SCIENCE↗

Refill Friction Stir Spot Welding Dissimilar Al/Mg Alloys

Dissimilar Al/Mg alloys were joined by refill friction stir spot welding (RFSSW) in this work. The effect of sleeve plunge depth on microstructure and mechanical properties of the joints was studied. The results showed that sound joint can be obtained at sleeve plunge depth of 2.4 mm. Intermetallic compounds (IMCs) layer, formed by the liquid eutectic phase, were observed at both the sleeve-affected zone and joint center. The IMC at the pin-affected zone was thicker than that at the sleeve-affected zone because of its flow characteristic. Less liquid eutectic phase formed during RFSSW when joint using Mg as the upper sheet because the oxide layer on the Al sheet was hard to break, resulting to thinner IMC layer. The maximum load of 3.6 kN was obtained at 2.6 mm when the Al alloys served as the upper sheet, and the maximum failure of 3.6 kN was also obtained at 2.4 mm when the Mg alloys served as the upper sheet. The RFSSW joint presented shear fracture mode. The XRD patterns showed that the IMC of Al{sub 3}Mg{sub 2} and Al{sub 12}Mg{sub 17} formed inside the joint.

36 MATERIALS SCIENCE↗

Combining solution-, precipitation- and load-transfer strengthening in a cast Al-Ce-Mn- Sc -Zr alloy

Here, a cast Al-9Ce-0.75Mn-0.18Sc-0.12Zr (wt%) alloy is designed to combine three strengthening phases: (i) micron-scale Al 11 Ce 3 platelets formed during eutectic solidification, (ii) nano-scale L1 2 -Al 3 (Sc,Zr) precipitates formed during aging, and (iii) Mn in solid solution in the α-Al matrix. Microstructural analyses by SEM, TEM, and atom-probe tomography reveal that Mn remains in solid solution in the as-cast alloy, providing solution strengthening with no influence on the eutectic Al-Al 11 Ce 3 microstructure, which provides precipitation- and load-transfer strengthening. During long-term over-aging at 400 °C, Mn-rich precipitates grow at the Al-Al 11 Ce 3 interface, with no effect on the microhardness. However, after short aging at 350 °C, a high number density of fine L1 2 -Al 3 (Sc,Zr) nanoprecipitates form in the Al matrix (with a coarser size at the Al-Al 11 Ce 3 interface), providing precipitation strengthening. The synergistic combination of the three strengthening mechanisms (solution, precipitation, and load transfer) in our Al-Ce-Mn-Sc-Zr alloy results in higher microhardness after aging at 350 and 400 °C, and higher creep resistance at 300 °C, as compared to alloys with two strengthening mechanisms: an Al-10Ce-0.93Mn control alloy (without precipitation strengthening from Sc and Zr), Al-Ce-Sc-Zr (without solution strengthening from Mn), and Al-Mn-Zr-Er (without load-transfer strengthening from Ce). Furthermore, these dual-strengthened alloys are more creep resistant than alloys with a single strengthening mechanism (Al-Ce, Al-Mn, and Al-Sc-Zr), confirming that the three mechanisms can be combined in pairs or all together.

36 MATERIALS SCIENCE↗

Solute- and solvent-based electromotive force cells for activity measurements of electroactive species in molten salts

A novel combination of solute- and solvent-based electrodes was used to determine the activities of NdCl 3 and GdCl 3 in molten LiCI-KCI eutectic using electromotive force measurements across a broad concentration range of dissolved electroactive species. First, an electrochemical cell using solute-based electrodes was used to define the relative activity of each species as a function of concentration and the concentration region in which Henry's law was applicable. Next, the electromotive force between a solute-based electrode with a known NdCl 3 or GdCl 3 concentration and a solvent-based electrode with a known electromotive force was measured. The solvent-based electrode potential was converted to the Lithium Eutectic Electrode (LEE) potential, which allowed the activity of dissolved NdCl 3 and GdCl 3 to be calculated at the concentrations measured using the solute-based electrodes. The described two-cell method uses electromotive force measurements to accurately determine the activity of electroactive species over a wide concentration range and provides a simple approach to closing the knowledge gap of thermochemical properties of molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental studies on metallic fuel relocation in a single-pin core structure of a sodium-cooled fast reactor

Experiments dropping molten uranium into test sections of single fuel pin geometry filled with sodium were conducted to investigate relocation behavior of metallic fuel in the core structures of sodium-cooled fast reactors during a hypothetical core disruptive accident. Metallic uranium was used as a fuel material and HT-9M was used as a fuel cladding material in the experiment in order to accurately mock-up the thermo-physical behavior of the relocation. The fuel cladding failed due to eutectic formation between the uranium and HT-9M for all experiments. The extent of the eutectic formation increased with increasing molten uranium temperature. Voids in the relocated fuel were observed for all experiments and were likely formed by sodium boiling in contact with the fuel. In one experiment, numerous fragments of the relocated fuel were found. In conclusion, it could be concluded that the injected metallic uranium fuel was fragmented and dispersed in the narrow coolant channel by sodium boiling

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Experimental studies on metallic fuel relocation in a pin bundle core structure of a sodium-cooled fast reactor

Understanding the relocation behavior of metallic fuel in severe accident scenarios is one of the most important factors in the safety assessment of sodium-cooled fast reactors (SFRs). In the present study, the relocation behavior of uranium metallic fuel was investigated by conducting metallic fuel relocation experiments using 19-pin bundle test sections in the Argonne's Metallic Uranium Safety Experiment (MUSE) facility. Post-test radiographic images were taken to characterize the uranium fuel relocation within the pin bundle test section. In addition, the pressure drop in the test sections was measured after the relocation experiments to evaluate the blockage of the sodium coolant channel. The pressure drop in the pin bundle test sections was also analytically calculated by varying the porosity and the pore size of the relocated fuel. The porosity and pore size of the relocated fuel in the pin bundle test sections were estimated by comparing those calculated pressure drop values with the measured pressure drop values from the pressure drop tests. In this work, the experimental results showed that the more formation of the eutectics could lead to more fuel dispersion and less blockage due to the lower freezing point of the eutectics.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Effect of ATF Cr-coated-Zircaloy on BWR In-vessel Accident Progression during a Station Blackout

The deposition of protective coatings on nuclear fuel cladding has been considered as a near-term Accident Tolerant Fuel (ATF) concept that will reduce the high-temperature oxidation rate and enhance accident tolerance of the cladding while providing additional benefits during normal and transient. In this study, the performance of the proposed ATF concept of Cr-coated-Zircaloy is assessed using a generic Boiling Water Reactor MELCOR plant model considering a Short-term Station Blackout (STSBO) scenario. Simulation results indicate that the use of Cr-coated-Zircaloy as cladding and canister material mitigates the core degradation process as compared to the traditional Zircaloy cladding and canister design. The onset of fuel degradation and collapse is delayed by over thirty minutes, and the extent of fuel degradation is reduced. Specifically, the gross in-vessel hydrogen generation decreased by almost a factor of three. Although the eutectic reaction between Cr-coating and Zircaloy could cause an early failure of the coating, the improvement in the delay of fuel degradation is still notable. In addition, a thicker coating is found helpful to obtain additional coping time and to decrease hydrogen generation. In addition to the eutectic formation that may compromise Cr-coated Zr, a different failure mode is identified for the Cr-coated-Zr when compared to Zircaloy; i.e., a complete melt of base material leads to component collapse before the coating is oxidized and consumed. These findings can help the industry focus on productive areas of research and development for accident-tolerant fuel concepts and enhancement of core safety margins.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Solvation Dynamics of Wet Ethaline: Water is the Magic Component

The past two decades witnessed the development of a new type of solvent system, named deep eutectic solvents, which have become increasingly investigated because they offer new and potentially favorable properties, such as wide tunability in electrochemical, mechanical, and transport properties. Deep eutectic solvent (DES) systems are composed of at least one main solvent and an additional component that is meant to interrupt the original solvent/solvent interactions, thereby introducing lower melting points relative to each individual component. Ethaline (a 1:2 mole% mixture of choline chloride and ethylene glycol) is one of the most promising DES systems. However, it is also known to be very hygroscopic, which is a constant concern because water absorption during the use of ethaline alters its properties. Within this work, we demonstrate that modest amounts of water addition (1-10%) to ethaline are of little concern for practical use and can even lead to performance improvements, such as accelerated relaxation and solvation. In contrast, very small amounts of <1% of water lead to additional slowing of the solvent response. Thus, we suggest that the attempt to dry ethaline below 1% moisture is rather counter-productive if one attempts to achieve effective solvation and charge transport properties from DESs. This study investigates the effect of water content on the diffusional relaxation dynamics of ethaline. A set of independent spectroscopic experiments and computational simulations are aimed to provide insight into the solvent response of the DES system using femtosecond time-resolved absorption spectroscopy (fs-TA), broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR) diffusometry and broadband relaxometry, and molecular dynamics simulations (MDS) on ethaline with 0, 0.1, 1, 10, and 28.5wt% added water. For dry ethaline, we identify choline chloride as the rate-limiting solvation component in ethaline. However, the role of the solvent components changes gradually as water is added. Further, we provide quantitative solvent relaxation rates using the different presented time-resolved spectroscopic techniques and find remarkable agreement between them. Based on the solvent relaxation rates and combined with MDS, we develop a molecular understanding of the individual solvent components and their interactions in dry and wet ethaline with varying amounts of water content.

25 ENERGY STORAGE↗

Safeguards in Pyroprocessing: an Integrated Model Development and Measurement Data Analysis

Pyroprocessing is an electrochemical method based on the molten salt electrolyte, mainly the LiCl-KCl eutectic molten salt, to recycle the used nuclear fuel. For a conceptual design of commercial pyroprocessing facility, tons of special nuclear materials, namely U and Pu, may be involved, which could be used for non-peaceful purposes if they are diverted. Effective safeguards approaches have to be developed prior to the development and construction of a pyroprocessing facility. Present research focused on two main objectives, namely calculating the properties of nuclear species in LiCl-KCl molten salt and developing integrated model to safeguard a pyroprocessing facility. Understanding the characteristics of special nuclear materials in LiCl-KCl eutectic salt is extremely important to understand their behaviors in an electrorefiner. The model development for the separation processes in the pyroprocessing, including electrorefining, actinide drawdown, and rare earth drawdown benefits the understanding of material transport and separation performance of these processes under various conditions. The output signals, such as potential, current, and species concentration contribute to the material balance closure and provide safeguards signatures to detect the scenarios of diversion. U and Pu are the two main elements concerned in this study due to our interest in safeguards.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrolytes in Multiple-Phase Hydrogen Storage Reactions

Multiple-phase hydrogen storage materials such as metal alanates and borohydrides, and destabilized systems offer the possibility of high hydrogen storage capacity with favorable thermodynamics. However, the multiphase nature of these materials intrinsically limits the kinetics due to the required transport of species between phases, which are typically in dry powder form. To address this limitation, the influence of added electrolytes is explored. This approach is motivated by analogy with similar multiphase battery reactions that show reduced kinetic limitations while necessarily containing electrolytes. Previous experimental results showing improved kinetics for MgH2/Sn (using a LiBH4/KBH4 eutectic electrolyte) and NaAlH4 (using a diglyme electrolyte) are further analyzed in terms of this analogy. The results show that the analogy is useful and rate constants are increased. Importantly, the inclusion of an electrolyte also appears to alleviate the continuously decreasing rates with the extent of reaction, which is characteristic of many multiphase hydrides. Instead, reaction rates are approximately constant until near completion. Together, these effects can lead to >10× shorter overall reaction times. In addition, new results are presented for the hydrogenation of MgB2 using Li/K/CsI and Li/K/CsCl eutectic electrolytes, where >60% conversion to Mg(BH4)2 was demonstrated at 350 bar.

08 HYDROGEN↗

Fundamental Study of Uranium Dendrites Electrochemically Separated in Molten Salt with the Presence of Cerium

In this study, uranium was electrochemically separated in the presence of cerium in eutectic LiCl-KCl at varying concentrations of cerium and varying overpotentials. Harvested dendrites were then examined and analyzed for their morphological features and elemental composition using various analytical techniques. Conclusions: Increasing the applied overpotential causes the dendrites to evolve from relatively simple and large platelet-like crystals (25 mV), to a grid-like network with crystals having jagged and smooth features (50 mV, 100 mV), and finally into a very chaotic and complex crystal morphology (200 mV) for all uranium-cerium compositions explored. Varying the uranium:cerium concentration ratio did not have much effect on the uranium dendrite morphologies. EDS results show that cerium is not co-deposited on the surface of the dendrite crystals, ICP-MS results do show a presence of cerium in the volumetric composition. This is likely due to salt occlusion during the dendrite formation. XRD has been performed on several samples at the 25 mV overpotential with 1 wt% U and 0 wt% Ce in the molten salt eutectic. These results indicate that there is not salt occlusion within the dendrites during electrochemical separation. Additionally, the uranium metal quickly oxidizes during preparation for XRD.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrochemical and Thermodynamic Properties of U in LiCl-KCl-UCl{sub 3} salt system

Pyro-processing technology has been considered and examined by several countries as a promising method for the recovery and recycle of uranium and actinide elements from used nuclear fuel. One of the key processes in pyro-processing is an electro-refiner (ER) where the metallic fission products are loaded into an anode basket and dissolved into lithium-potassium chloride (LiCl-KCl) eutectic salt at 773 K. Many researchers have been exploring the fundamental characterizations of U in LiCl-KCl system by using various electrochemical methods, resulting in several reported values of diffusion coefficient, apparent standard potential, and activity coefficient of U in the salt system. In addition, several researchers measured kinetic parameter of U (exchange current density, i{sub 0}) by using Tafel and linear polarization (LP) methods. Despite available data sets on this ternary salt system, there are discrepancies due to different experimental conditions, design, size of the cell, and measurement techniques. In addition, the i{sub 0} for U/U{sup 3+} reaction has only been measured since 2009; therefore, only few data sets are available to date although the i{sub 0} is critical for the development of dynamic ER model. The value of i{sub 0} is a kinetic characteristic in an ideal equilibrium state; therefore, it is very challenging to be measured by experiments. The authors have estimated the values of i{sub 0} via Tafel and linear polarization methods (LP); however, these methods are lack of maintaining electrode surface area during the measurements. In addition, some data are not following the trends from other literature studies due to its difficulties of the measurement. Therefore, further experimental determinations have to be accomplished to understand the i{sub 0} kinetics and the database for the i{sub 0} of U/U{sup 3+} couple in LiCl-KCl eutectic salt needs to be established systematically. In the present study, an experimental setup was designed and used in a consistent manner to build a meaningful database for U in LiCl-KCl system. LiCl-KCl-UCl{sub 3} salt was prepared at different concentrations and temperatures ranging from 0.5 wt% to 4 wt% and 723 K to 798 K, respectively. Then, CV, open circuit potential (OCP), and electrochemical impedance spectroscopy (EIS) were performed to understand the electrochemical, thermodynamic, and kinetic properties of U. Specially, i{sub 0} values have not been measured via EIS method; therefore, this study provides a good chance to confirm the i{sub 0} values with the new technique.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced Tensile and Tear Toughness Properties of Thin-Wall Vacuum-Assisted High-Pressure Die-Cast Aural-5 Alloy by Friction Stir Processing

Steadily rising demand for glider weight reduction has driven the development of vacuum-assisted high-pressure die-cast (HPDC) Al-alloys for automotive structural components. Aural-5 is a strontium-modified HPDC alloy utilizing manganese (Mn) to reduce die soldering, eliminating detrimental needle-shaped Fe-bearing ß-phase intermetallic and improving ductility. HPDC Aural-5 contains shrinkage porosity, dendrites with Al-Si eutectic colonies, externally solidified crystals (ESCs), shear-band structure, and large second-phase particulates. Porosity, ESCs and large second-phase particles work as crack initiation sites, negatively impacting tensile properties. In this study, friction stir processing (FSP) is employed for microstructural modification of a thin-walled HPDC Aural-5 by eliminating porosity and breaking down dendrites, second-phase particles, eutectic colonies, ESCs and shear-band structures to create wrought microstructure with homogenized particle distribution. Mechanical property characterization indicates ~30% and ~35% enhancement in yield strength and ductility and associated marked effects on ~69% improvement in tear toughness according to the ASTM B871 test.

Friction stir processing, Aural-5, Strength, Tear ↗