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Characterization of the Uranium-Bearing Products of the Ammonia Injection Remediation Method - 15707

Commissioned in 1943, the Hanford Site is the home of the world's first full-scale nuclear production facility. After more than 40 years of processing, improper discharge and failed storage tanks have resulted in the contamination of the Hanford vadose zone with radiologically contaminated waste. Remediation methods considered for the area include sequestration of the mobile uranium by injection of ammonia (NH{sub 3}) gas. Injection of this reactive gas increases the pore water pH, promoting the dissolution of soil minerals; a subsequent re-establishment of natural conditions is believed to result in the recrystallization of those soil minerals and the co-precipitation of uranium phases. Characterization of the precipitates formed when the ammonia (NH{sub 3}) injection method, proposed for the Hanford vadose zone, is applied to synthetic pore water on a laboratory scale. This involves: Identification of the uranium-bearing phases; A study of the effect of pore water constitution on the phases produced. Synthetic pore water solutions were prepared to mimic selected constituents of the pore water from the Hanford 200 Area: Varying constituent concentrations; Observations led to modifications to increase relative uranium content: 200 ppm → 500 ppm U; Substituted sodium silicate for silicic acid. Dried samples were analyzed by SEM-EDS and powder X-ray diffraction (XRD). A suspension in ethanol was prepared and analyzed by Transmission Electron Microscope (TEM) with Selective Area Electron Diffraction (SAED). Studied and applied geochemical modeling software (Visual Minteq and Geo-chemist's Workbench) for speciation and prediction of potential species formed. Discussion/Conclusions: - SEM-EDS Analysis: Scanning electron microscopy revealed areas of high average atomic weight which would be confirmed to be uranium-rich by energy dispersive spectroscopy analysis. The samples prepared with a more than two-fold increase in uranium concentration did not show the crystal-like forms spotted in the lower [U] samples. The samples prepared with silicic acid substituted in showed little to no uranium precipitation [not shown]. - Diffraction Analysis: Powder XRD analysis of the low [U] samples confirmed the presence of repeating crystalline patterns in the precipitate samples. Nitratine (NaNO{sub 3}) showed a massive presence, potentially obscuring significant peaks in the low [U] samples. Though it was not predicted, there was a tentative match for cejkaite (Na{sub 4}(UO{sub 2})(CO{sub 3}){sub 3}). Elevated uranium samples showed none of the needle-like crystalline shapes [diffraction data pending]. TEM - SAED confirmed the presence of a polycrystalline phase. Data analysis is complex but a comparison of average d-spacings with those of reference minerals could further support a match with cejkaite. - Geochemical Modeling: The system conditions were input into geochemical modeling software to predict the forms present throughout the reaction process. The model was used to demonstrate that the pH of the system could be increased using [NH{sub 4}{sup +}] in solution to better represent the system. Using the [NH{sub 4}{sup +}] increase, the changes in significant species with increasing pH were observed. Future Work: Repeat samples will be prepared and analyzed to bolster any potential identification. Promising samples will be submitted to the PNNL's EMSL facility, which is better equipped to perform the required analyses. An expanded study on the impact of carbonate (CO{sub 3}{sup 2-}) on the phases produced.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of biochar prepared from biogas digestate

Highlights: • Solid digestate (SD) is a potential feedstock for preparing biochars. • The optimal BET surface area of resulting biochar from SD is over 100 m{sup 2}/g. • The higher temperature leads to the increase in true density of resulting biochar, but exhibited a decreased higher heating value. • The SD-based biochar may be used as a biofertilizer due to the mesoporosity and the abundant in nutrient minerals. - Abstract: In the study, the biogas digestate was evaluated as a potential feedstock for preparing biochars at a broad temperature range of 300–900 °C. The physico-chemical and pore properties of the resulting biochars (denoted as SDBC, solid digestate biochar), including calorific value (higher heating value), surface area/pore volume/pore size distribution, true density, scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray powder diffraction (XRD), were studied. It was found that the higher heating values of the SDBC products were on a decreasing trend as pyrolysis temperature increased, but they indicated an increase in true density. The results are probably associated with the active pyrolysis of the lignocellulosic fragments and the calcination (or shrinkage) processes, thus resulting in the increased contents of aromatic carbon clusters and main mineral constituents remained. Based on the pore properties, pyrolysis temperature at around 800 °C seemed to be the optimal condition for producing SDBC, where its Brunauer-Emmet-Teller (BET) surface area (>100 m{sup 2}/g) largely increased as compared to that of the digestate feedstock (<1 m{sup 2}/g). Furthermore, the main compositions of mineral ash in the resulting biochar could exist as phosphates, carbonates, or oxides of calcium and other alkali/alkaline earth elements. According to the data on EDS and XRD, more pores could be significantly generated under severe pyrolysis (>700 °C) due to the high aromaticity via the thermal decomposition of lignocelluloses and the volatilization of inorganic minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and optical characterization of NaGdF{sub 4}: Ho{sup 3+}/Yb{sup 3+} UC nano-particles for lateral finger mark detections

Ho{sup 3+}/Yb{sup 3+} co-doped NaGdF{sub 4} up-conversion (UC) nano-particles were synthesized by thermal decomposition method. X-ray diffraction and FE-SEM image analysis were done to confirm the structure, morphology and determination of particle size. The UC emission spectra for as prepared as well as 100°C, 200°C, 300°C, 400°C, 800°C, 1000°C and 1200°C heated for 3h samples were recorded and there emission intensities were compared at a constant pump power of excitations 98.1 W/cm{sup 2}. The effect of emission intensity on decay time was also studied through focused and unfocused excitations. The synthesized material was successfully utilized in lateral finger mark detections on the glass substrate through powder dusting method.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

0D and 2D: The Cases of Phenylethylammonium Tin Bromide Hybrids

Tin halide perovskites and perovskite-related materials have emerged as promising lead-free hybrid materials for various optoelectronic applications. While remarkable progress has been achieved in the development of organic tin halide hybrids with diverse structures and controlled dimensionalities at the molecular level, some controversial results that have been reported recently need to be addressed. For instance, different photophysical properties have been reported for two-dimensional (2D) (PEA) 2 SnBr 4 (PEA = phenylethylammonium) by several groups with distinct emission peaks at around 468 and 550 nm. Here we report our efforts in the synthesis of phenylethylammonium tin bromide hybrids with zero-dimensional (0D) and 2D structures, and characterizations of their structural and photophysical properties. 0D [(PEA) 4 SnBr 6 ][(PEA)Br] 2 [CCl 2 H 2 ] 2 was found to exhibit strong yellow emission peak at 566 nm with a photoluminescence quantum efficiency (PLQE) of ~90%, while 2D (PEA) 2 SnBr 4 had weak emission peak at 470 nm with a PLQE of <0.1%. Interestingly, 0D [(PEA) 4 SnBr 6 ][(PEA)Br] 2 [CCl 2 H 2 ] 2 can be converted into 2D (PEA) 2 SnBr 4 upon drying, which would return to 0D [(PEA) 4 SnBr 6 ][(PEA)Br] 2 [CCl 2 H 2 ] 2 upon addition of dichloromethane. Powder X-ray diffraction results confirmed the reversible transformation between 0D and 2D structures. Density functional theory calculations showed that excitons in 0D [(PEA) 4 SnBr 6 ][(PEA)Br] 2 [CCl 2 H 2 ] 2 are highly localized, resulting in a strongly Stokes shifted broadband emission, while delocalized electronic states in 2D (PEA) 2 SnBr 4 result in weaker exciton binding, a higher exciton mobility, and a higher nonradiative decay.

36 MATERIALS SCIENCE↗

Synthesis and Properties of Bulk Mg 3 WN 4 in a Wurtzite-Derived Structure

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to the realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are ternary nitrides in the Mg−W−N composition space, where several stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg 3 WN 4 in a wurtzite-derived crystal structure via a solid-state metathesis reaction. In situ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li 6 WN 4 + MgCl 2 precursors to Mg 3 WN 4 + LiCl products, with the reaction starting slowly near 380 °C and completing by 600 °C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 °C. The follow-up ex situ powder synthesis at 400 °C for 0.5 h with 10% excess MgCl 2 reveals the cation-ordered nature of the wurtzite-derived Mg 3 WN 4 structure with polar symmetry confirmed by second-harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggest that bulk Mg 3 WN 4 obtained via metathesis reaction is prone to defect formation. Overall, this study shows that selective ex situ synthesis of the phase-pure ternary nitrides, informed by in situ measurements, is possible by carefully controlling the thermal budget of the reaction and paves the way toward property characterization of the Mg 3 WN 4 wurtzite-derived material.

36 MATERIALS SCIENCE↗

Structure and Dynamics Investigations of Sr/Ca-Doped LaPO 4 Proton Conductors

Proton conductors loom out of the pool of candidate materials with great potential to boost hydrogen alternatives to fossil-based resources for energy. Acceptor doped lanthanum orthophosphates are considered for solid oxide fuel cells (SOFCs) for their potential stability and conductivity at high temperature. By exploring the crystal and defect structure of x% Sr/Ca-doped LaPO 4 with different nominal Sr/Ca concentrations (x = 0 – 10) with Neutron powder diffraction (NPD) and X-ray powder diffraction (XRD), we confirm that Sr/Ca-doped LaPO 4 can exist as self-supported structures at high temperatures during solid oxide fuel cell operation. Thermal stability, surface topography, size distribution are also studied to better understand the proton conductivity for dry and wet compounds obtained at sintering temperatures ranging from 1200 to 1400 °C using a combination of scanning electron microscopy (SEM), Atomic Force Microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and electrochemical impedance spectroscopy (EIS). In conclusion, the results suggest that Sr doped samples exhibit the highest proton conductivity of our samples and illustrate the impact of material design and versatile characterization schemes on the development of proton conductors with superior functionality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Empirical Investigation of Properties for Additive Manufactured Aluminum Metal Matrix Composites

Laser additive manufacturing with mixed powders of aluminum alloy and silicon carbide (SiC) or boron carbide (B4C) is investigated in this experiment. With various mixing ratios of SiC/Al to form metal matrix composites (MMC), their mechanical and physical properties are empirically investigated. Parameters such as laser power, scan speed, scan pattern, and hatching space are optimized to obtain the highest density for each mixing ratio of SiC/Al. The mechanical and thermal properties are systematically investigated and compared with and without heat treatment. It shows that 2 wt% of SiC obtained the highest strength and Young’s modulus. Graded composite additive manufacturing (AM) of MMC is also fabricated and characterized. Various types of MMC devices, such as heat sink using graded SiC MMC and grid type three-dimensional (3D) neutron collimators using boron carbide (B4C), were also fabricated to demonstrate their feasibility for applications.

36 MATERIALS SCIENCE↗

X-ray nanotomography and focused-ion-beam sectioning for quantitative three-dimensional analysis of nanocomposites

Knowing the relationship between three-dimensional structure and properties is paramount for complete understanding of material behavior. In this work, the internal nanostructure of micrometer-size (~10 µm) composite Ni/Al particles was analyzed using two different approaches. The first technique, synchrotron-based X-ray nanotomography, is a nondestructive method that can attain resolutions of tens of nanometers. The second is a destructive technique with sub-nanometer resolution utilizing scanning electron microscopy combined with an ion beam and `slice and view' analysis, where the sample is repeatedly milled and imaged. The obtained results suggest that both techniques allow for an accurate characterization of the larger-scale structures, while differences exist in the characterization of the smallest features. Using the Monte Carlo method, the effective resolution of the X-ray nanotomography technique was determined to be ~48 nm, while focused-ion-beam sectioning with `slice and view' analysis was ~5 nm.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Ductile-Phase Toughened Tungsten for Plasma Facing Materials (Final Report)

Tungsten (W) and W-alloys are the leading candidates for plasma-facing components in nuclear fusion reactors because of their high melting point, high temperature strength, good thermal conductivity and low sputtering yield, however, they are too brittle to serve a structural function. A variety of processing approaches were employed to fabricate ductile-phase-toughened (DPT) tungsten (W) composites, that includes consolidating elemental W powder with Cu- or WC-coated W-wires via spark plasma sintering (SPS). Laminated W-composites with Cu-foils were also fabricated by hot-pressing or brazing. Mechanical testing and analytical modeling were used to guide composite development. The fracture toughness of thin W plate or laminated W-composites was measured in three-point bending (3PB) at room temperature (RT). Crack arrest and crack bridging were observed for the laminated composites, and fracture resistance curves were successfully calculated. An analytical model of crack bridging was developed using the specimen geometry, matrix properties, and the stress-displacement function of a ductile reinforcement (“bridging law”) to calculate the fracture resistance curve (R-curve) and load-displacement curve (P-D curve) for any test specimen geometry. The code was also implemented to estimate the bridging law of an arbitrary composite using R-curve data. In another approach, commercially available liquid-phase sintered W alloys with four different compositions were characterized in terms of microstructure, tensile and fracture toughness at different specimen, size, geometry and testing temperatures. The room temperature (RT) average maximum load fracture toughness values (KIc or KJm ≈ 38 to 107 MPa√m) of WHA, containing only 3 to 10 wt.% of a NiFe-based ductile phase (DP), are ≈ 5 to 13 times higher than for monolithic W (≈ 8 MPa√m). Most RT tests show extensive stable ductile tearing (DT) at all W contents, including 97W (KJm ≈ 69 MPa√m), for small baseline bend bars (B=1.65mm, W=2B). Exceptions to DT, include RT elastic fracture at 97W observed in 3x larger specimens than the baseline specimens. However, the WHA KIc was still almost 5 times higher than that for monolithic W. The other exception to RT ductile tearing was for some of the 6 to 8x larger 95W alloy specimens that contained large ceramic initiating inclusions at the precrack front, along with lower DP%, with a KIc ≈ 59 MPa√m, compare to their stable DT KJm ≈ 82 MPa√m. Small specimen tests down to -196°C, to partially emulate irradiation hardening, also transition to elastic fracture at a temperature (-150 for 90W to -25ºC for 97W) that depends on the W content. However, even at -196°C, the KIc at 97W is ≈ 3 times that of monolithic W at RT. In contrast to classical ductile phase toughening by macrocrack bridging, WHA toughening mainly involves new mechanisms associated with arrest, blunting and bridging of numerous process zone microcracks. Later, these WHAs were used to fabricate W-WHA hybrid composites by coating elemental W powder on WHA using SPS. Three-point bend bars were fabricated and fracture toughness was tested at room temperature. Crack initiated and propagated from W-part to the WHA part for the well-bonded (interface) W-WHA composites for 90 and 92.5WHAs, however, crack arrested and diverted at/or through the interface for loosely bonded W-95/97WHAs with increasing load.

36 MATERIALS SCIENCE↗

Sensitivity of Liquation Cracking to Deposition Parameters and Residual Stresses in Laser Deposited IN718 Alloy

The laser deposited IN718 alloys were fabricated with laser cladding system under different conditions to estimate the sensitivity of weld metal liquation cracking. The microstructure and the crack characterization of the laser deposited IN718 alloy were investigated, and the effect of metallurgical factors and residual stress on the crack sensitivity was analyzed. The results showed that the continuous dendritic Laves was precipitated and formed a Lave–austenite interface with ambiguous nanohardness distribution. The weld metal liquation cracking was propagated along the laser scanning direction and the buildup direction in the laser deposited IN718 alloy simultaneously, and the Nb-/Mo-riched fine granular clusters were formed in the crack surface. The precipitation amount of the coarse eutectic phases, presented as dendrite or network, was increased in the laser deposited alloy fabricated with IN718/C-Fe-Cr composite powder and slow cooling rate. The total crack length and the maximum crack length were decreased by increasing cooling rate, and the transverse residual stress was increased with increasing buildup layer number. The crack sensitivity of the laser deposited IN718 alloy was increased by the crack initiation provided by the metallurgical defects and the eutectic phases with low melting temperatures, and then, crack propagated along the continuous phase under the transverse residual stress.

36 MATERIALS SCIENCE↗

In situ TEM and synchrotron characterization of U–10Mo thin specimen annealed at the fast reactor temperature regime

U–Mo metallic alloys have been extensively used for the Reduced Enrichment for Research and Test Reactors (RERTR) program, which is now known as the Office of Material Management and Minimization under the Conversion Program. This fuel form has also recently been proposed as fast reactor metallic fuels in the recent DOE Ultra-high Burnup Fast Reactor project. In order to better understand the behavior of U–10Mo fuels within the fast reactor temperature regime, a series of annealing and characterization experiments have been performed. Annealing experiments were performed in situ at the Intermediate Voltage Electron Microscope (IVEM-Tandem) facility at Argonne National Laboratory (ANL). An electro-polished U–10Mo alloy fuel specimen was annealed in situ up to 700 °C. At an elevated temperature of about 540 °C, the U–10Mo specimen underwent a relatively slow microstructure transition. Nano-sized grains were observed to emerge near the surface. At the end temperature of 700 °C, the near-surface microstructure had evolved to a nano-crystalline state. In order to clarify the nature of the observed microstructure, Laue diffraction and powder diffraction experiments were carried out at beam line 34-ID of the Advanced Photon Source (APS) at ANL. Phases present in the as-annealed specimen were identified with both Laue diffraction and powder diffraction techniques. The U–10Mo was found to recrystallize due to thermally-induced recrystallization driven by a high density of pre-existing dislocations. A separate in situ annealing experiment was carried out with a Focused Ion Beam processed (FIB) specimen. A similar microstructure transition occurred at a lower temperature of about 460 °C with a much faster transition rate compared to the electro-polished specimen. - Highlights: • TEM annealing experiments were performed in situ at the IVEM facility up to fast reactor temperature. • At 540 °C, the U-10Mo specimen underwent a slow microstructure transition where nano-sized grains were observed to emerge. • UO{sub 2} phase exists at the thin area of the as-annealed specimen whereas U-10Mo γ phase dominated at the thicker part. • Bcc γ U-10Mo recrystallized to become nano-meter sized crystallites near the specimen surface. • A separateannealing experiment was conducted with a FIB processed specimen where similar transition occurred at a lower temperature of 460 °C with a faster rate.

36 MATERIALS SCIENCE↗

Electrochemical Recovery of Iron from Spent Pickle Liquor by Chloride-Based Molten Salt Electrolysis

Spent pickle liquor (SPL) is a waste stream generated in the steel industry that presents both a disposal challenge and a potential resource for metal recovery. This study investigates the electrochemical extraction of high-purity iron metal from SPL using chloride-based molten salt electrolysis (CMSE). Electrochemical characterization of diluted SPL confirmed Fe 2+ as the dominant species. Thermal dehydration of SPL under inert atmosphere yielded FeCl 2 -rich solids, which were directly employed as feedstock for electrolysis in LiCl–KCl eutectic melts at 500 °C. Cyclic voltammetry of FeCl 2 in this melt revealed well-defined Fe 2+ /Fe 0 redox behavior within the electrochemical stability window of the supporting electrolyte. High coulombic efficiency (>85%) electrodeposition was achieved demonstrating that iron metal can be produced from dehydrated SPL by CMSE. The electrodeposited iron exhibited >98 wt% purity, which was further enhanced to 99.9 wt% via arc melting. The resulting iron powder was ferromagnetic, and its size distribution was found to be suitable for powder metallurgy applications. This work demonstrates a scalable, energy-efficient pathway for valorizing SPL into high-purity iron metal, advancing circular economy strategies in the steel industry.

Materials science↗

Quantifying irradiation defects in zirconium alloys: a comparison between transmission electron microscopy and whole-pattern diffraction line-profile analysis - 2016-0089

Irradiation-induced dislocations significantly affect the mechanical properties of zirconium alloys, altering slip and influencing creep and growth. Thus, the quantitative characterization of irradiation defects as a function of fluence, cold work, and/or thermal treatments is important for models that attempt to predict their impact on properties. Whole-pattern diffraction line-profile analysis (DLPA) is a well-established modern tool for microstructure characterization based on first-principle physical models for dislocation density measurements in plastically deformed materials. However, applying these DLPA methods directly to irradiated materials yields higher than expected dislocation density values compared with historical transmission electron microscopy (TEM) measurements and past line-broadening analysis studies calibrated to TEM observations. In an effort to understand these differences, a new microstructural model was developed for DLPA to specifically address dislocation structures consisting of elliptical - and -component loops. To compare the refined DLPA method with TEM measurements, high-resolution neutron diffraction patterns on nonirradiated and irradiated Zr-2.5Nb samples were collected with the Neutron Powder Diffractometer instrument at the Los Alamos Neutron Science Center and were evaluated. High-resolution TEM measurements were performed at the Reactor Materials Testing Laboratory, Queen's University, for comparison with the DLPA results. The capabilities and inherent uncertainties of both the refined DLPA and TEM methods are compared and discussed in detail. We show that the differences between the density values provided by DLPA and TEM are inherent to the methods and can be reconciled with the interpretation of the data. (authors)

36 MATERIALS SCIENCE↗

Preliminary results addressing material qualification using combined ion irradiation and modeling data

Additively-manufactured (AM) materials have attracted increasing attention in recent years as a new method to make novel and customized components. While AM and conventionally produced materials are compositionally similar, they do possess different microstructures, necessitating assessment of materials produced via AM for their behavior in reactor environments. Some microstructures unique to AM materials, such as compositional micro-inhomogeneity and dislocation cell structures, are of particular importance since they may lead to different radiation performance. The performance of AM materials for advanced nuclear reactor applications is of interest to the Advanced Materials and Manufacturing Technologies (AMMT) program under the Department of Energy Office of Nuclear Energy. The AMMT program aims to demonstrate its new accelerated development and qualification methods via laser powder bed fusion (LPBF) 316 stainless steel (SS). Focusing on material bearing both 316L and 316H specifications, we integrate ion irradiation and modeling. This year, we focus on answering foundational questions related to process variability, alloy chemistry variation, and microchemical segregation. Experimental results provide information and motivate questions to the modeling effort, which aims to develop the ability to model radiation-driven microstructural evolution in additively-manufactured 316 stainless steel under a variety of advanced reactor conditions, including different temperatures, neutron spectra, and fluxes, in a sort of "virtual experiment". We perform in-situ and ex-situ ion irradiations and microstructural characterizations to support the development of AM materials for reactor applications, develop a phase field model of radiation-induced segregation in additively manufactured material with high angle grain boundaries and dislocation cells, and investigate the effect of carbon and chromium content on point defect behavior.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Perspective on Solid-State Additive Manufacturing of Aluminum Matrix Composites Using MELD

MELD, previously known as additive friction stir, is an emerging solid-state process that enables additive manufacturing of a broad range of metals and metal matrix composites. Here, we discuss its potential for fabricating aluminum matrix composites by showing examples of Al-SiC, Al 6061-Mo, and Al 6061-W composites. Thanks to its solid-state nature, MELD is uniquely suited for the use of high-strength aluminum alloys as matrix material, which would suffer from hot cracking problems in liquid-state processes. Using complementary characterization tools, we show that this process results in aluminum matrix composites with no observed porosity and homogeneous particle distribution. These properties stem from the extensive material flow and mixing during the deposition process. In addition to the high quality of produced composites, its ease of use, versatility of feed materials, and scalability all make MELD an attractive tool for additive manufacturing of aluminum matrix composites. We also discuss the limitations of MELD for composite fabrication, with issues related to maximum reinforcement loading, tool wear, and in-plane resolution. Finally, we compare the benefits and limitations of MELD with other composite fabrication processes such as powder bed fusion, friction stir processing, stir casting, and powder processing.

36 MATERIALS SCIENCE↗

Hygrothermal behavior of polybenzimidazole

Poly[2,2’-(m-phenylene)-5,5’-bibenzimidazole] (PBI) is used in extremely high temperature harsh environment applications. It is a unique engineering material that is formed into parts by powder-sintering at temperatures as high as 500 °C. Recently, ever increasing demands for high temperature polymers have led to significant interest in PBI such that engineering guidelines could be established for its application in high temperature and highly humid environments. The goal of this work was to understand the material science of PBI in hot-wet environments at temperatures up to 288 °C. Thermal gravimetric analysis and mass spectrometry were employed to identify the degraded volatile products. The molecular scale damping behavior of PBI was probed using dynamic mechanical analysis. The changes in tensile properties and fracture toughness due to environmental exposure were also characterized. Upon heating above 250 °C, moisture-containing PBI exhibits obvious molecular structure change. Evidence of crosslinking and degradation is observed. With 288 °C hot water treatment severe degradation of PBI is observed. As a result, fundamental structure-property relationships of PBI affected by these higher temperature, high moisture content environments are discussed.

36 MATERIALS SCIENCE↗

Investigating the Effects of Lithium Deposition on the Abuse Response of Lithium-Ion Batteries

Li deposition at the graphitic anode is widely reported in literature as one of the leading causes of capacity fade in lithium-ion batteries (LIBs). Previous literature has linked Li deposition resulting from low-temperature ageing to diminished safety characteristics, however no current research has probed the effects of Li deposition on the abuse response of well-characterized cells. Using overtemperature testing, a relationship between increased concentrations of Li deposition and exacerbated abuse response in 1 Ah pouch cells has been established. A novel Li deposition technique is also investigated, where cells with n:p < 1 (anode-limiting) have been cycled at a high rate to exploit Li + diffusion limitations at the anode. Scanning Electron Microscopy of harvested anodes indicates substantial Li deposition in low n:p cells after 20 cycles, with intricate networks of Li(s) deposits which hinder Li + intercalation/deintercalation. Peak broadening and decreased amplitude of differential capacity plots further validates a loss of lithium inventory to Li + dissolution, and Powder X-ray Diffraction indicates Li + intercalation with staging in anode interstitial sites as the extent of Li deposition increases. A cradle-to-grave approach is leveraged on cell fabrication and testing to eliminate uncertainty involving the effects of cell additives on Li deposition and other degradation mechanisms.

25 ENERGY STORAGE↗