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At least 253 records · Page 14

Accelerated Stress Testing of Perovskite Photovoltaic Modules: Differentiating Degradation Modes with Electroluminescence Imaging

Herein, electroluminescence (EL) and thermal imaging are used to examine p–i–n metal halide perovskite (MHP) photovoltaic (PV) mini-modules (MA0.6FA0.4PbI3, 20 cells, 78 cm2) before and after indoor-accelerated stress testing or outdoor deployment. Distinct spatial patterns in the EL images emerge, which depend on the external stress conditions experienced by the mini-module. Imaging results highlight a distribution of dark speckle features that dominate after UV stress, attributed to widespread interfacial contact degradation. Lateral intensity gradients across cells dominate after thermal cycling (TC) stress, attributed to current crowding near scribe defects. While current–voltage analysis alone does not give full insight on the degradation process, this study shows that distinct degradation modes can be further defined by multimodal electro-optical imaging (i.e., EL combined with photoluminescence and dark lock-in thermography). Neither UV exposure nor TC-accelerated stress testing alone replicates the same degradation signatures observed after outdoor deployment, suggesting that multiple degradation modes occur under concurrent stressors outdoors. Finally, spatial characterization of degradation modes in MHP PV mini-modules before and after accelerated stress testing lays the groundwork for developing targeted accelerated stress testing procedures through comparison with outdoor aging.

14 SOLAR ENERGY↗

Quantifying optical loss of high-voltage degradation modes in photovoltaic modules using spectral analysis

The direct current bias for photovoltaic (PV) modules interconnected in series-strings may include both high voltage negative (“HV-”) and positive (“HV+”) polarity with respect to the electrical ground. Multiple degradation modes, resulting in quantifiable optical loss, were found to occur during HV-/HV+ sequential stress, including corrosion of the external glass surface, encapsulant delamination (at its interfaces with the glass and the PV cell), internal haze formation (resulting from a chemical interaction between the glass and the encapsulant), corrosion and migration of the gridlines, and corrosion of the silicon nitride (Si x N y ) antireflective coating on the cell. The effects of these separate modes were examined using monolithic (e.g., glass or PV cell) and laminated-coupon (glass/encapsulant/glass or glass/encapsulant/cell/encapsulant/backsheet) specimens. Characterizations during and after unbiased accelerated testing at 85°C/85% relative humidity included spectrophotometry, optical microscopy, electron microscopy, and ellipsometry. For some module components (i.e., the glass and the Si x N y coating), the optical performance was determined through iterative analysis of empirical measurements. Concentrating on just their spectral effect, a novel model was then developed to estimate the transfer of light to the PV cell and the return of light from the PV module with simultaneous degradation mechanisms, which was compared with a mini-module previously subjected to HV-/HV+ stress. Here the model suggests that one third of the current loss observed for the mini-module can be attributed to the optical degradation of the packaging materials. The dominant degradation modes include encapsulant delamination and corrosion of the Si x N y coating. Recommendations are given so that the optical model may be improved relative to accelerated testing and validated relative to field aging.

14 SOLAR ENERGY↗

Thermal stability of filler‐based ethylene/vinyl acetate/vinyl alcohol terpolymer in nitroplasticizer oxidative environment

Abstract To study the thermal stability of ethylene/vinyl acetate/vinyl alcohol (EVA‐OH) composite with filler particles, systematic thermogravimetric analysis (TGA) investigation was conducted in both nonisothermal and isothermal modes. The effect of polymer concentration on the aging behavior of EVA‐OH was investigated in the nitroplasticizer (NP) environment. Fourier transform infrared spectroscopy was used to probe chemical structural changes in the EVA‐OH polymer before and after thermal aging. The results suggest that filler addition accelerates the rate of NP exudation out of the EVA‐OH composites and deteriorates the thermal stability of NP at moderate temperatures (up to 70°C). The degradation of NP, in turn, accelerates the degradation of EVA‐OH polymer in its composite form through oxidation and hydrolysis indicating the importance of antioxidants in such phase blends.

36 MATERIALS SCIENCE↗

Heterogeneous creep deformation behavior of functionally graded transition joints (GTJs)

Dissimilar metal welds (DMWs) made between ferritic steels and austenitic alloys are used extensively in high-temperature power plant components. These DMWs experience premature creep failure in the ferritic steel’s heat affected zone (HAZ), close to the weld interface. Steep variations in microstructure and chemical composition across the dissimilar weld interface have been the contributing factors for the failure. Graded transition joints (GTJs), developed by functionally grading the chemical composition in layers, have been proposed as potential candidates to replace DMWs. In this research, GTJ coupons were fabricated between 2.25Cr-1Mo steel and Alloy 800H base material using two filler materials: (i) Inconel 82 and (ii) P87. These samples were aged at 600°C for 2000h to accelerate high-temperature microstructural evolution seen in service conditions, before subjecting them to short-term (~1 month) creep tests. Surface strains were measured using digital image correlation (DIC) technique to extract creep strain rates at different locations within GTJs. Both the GTJs exhibited heterogeneous creep strain distribution. Creep strain accumulated in the FGHAZ of 2.25Cr-1Mo steel, similar to type IV failure associated with Cr-Mo steel weldments. Microstructure based creep model framework was developed to describe the discrete creep strain rates observed in various 2.25Cr-1Mo steel regions of GTJs.

36 MATERIALS SCIENCE↗

Hydration of potassium citrate-activated BOF slag

Basic Oxygen Furnace (BOF) slag is currently utilized with low-grade applications or landfilled. Here, we investigate a novel route to upgrade BOF slag to a high-performance binder by chemical activation with tri-potassium citrate. The impact of tri-potassium citrate on hydration and phase assemblage of BOF slag is analyzed with a multi-technique approach. Results reveal that the addition of tri-potassium citrate considerably enhances the reactivity of brownmillerite and accelerates the hydration of belite at early ages. The majority of brownmillerite hydrates within 24 h, and the reaction kinetics is controlled by the activator dosage. The main products of BOF slag hydration are siliceous hydrogarnet and C-S-H gel. Acting as a strong water reducer, tri-potassium citrate enables the manufacture of slag pastes with high compressive strength (up to 75 MPa at 28 days) and low porosity. Leaching of heavy metals from the slag pastes fulfills the Dutch Soil Quality Decree limits.

36 MATERIALS SCIENCE↗

Quantifying Optical Loss of High-Voltage Degradation Modes in PV Modules Using Spectral Analysis [Slides]

The direct current bias for photovoltaic (PV) modules interconnected in series-strings may include both high voltage negative ("HV-") and positive ("HV+") polarity with respect to the electrical ground. Multiple degradation modes, resulting in quantifiable optical loss, were found to occur during HV-/HV+ sequential stress, including: corrosion of the external glass surface, encapsulant delamination (at its interfaces with the glass and the PV cell), internal haze formation (resulting from a chemical interaction between the glass and the encapsulant), corrosion and migration of the gridlines, and corrosion of the silicon nitride (SixNy) antireflective coating on the cell. The effects of these separate modes were examined using monolithic (e.g., glass or PV cell) and laminated-coupon (glass/encapsulant/glass or glass/encapsulant/cell/encapsulant/backsheet) specimens. Characterizations during and after unbiased accelerated testing at 85 degrees C/85% relative humidity included: spectrophotometry, optical microscopy, electron microscopy, and ellipsometry. For some module components (i.e., the glass and the SixNy coating), the optical performance was determined through iterative analysis of empirical measurements. Concentrating on just their spectral effect, a novel model was then developed to estimate the transfer of light to the PV cell and the return of light from the PV module with simultaneous degradation mechanisms, which was compared to a mini-module previously subjected to HV-/HV+ stress. The model suggests one-third of the current loss observed for the mini-module can be attributed to the optical degradation of the packaging materials. The dominant degradation modes include encapsulant delamination and corrosion of the SixNy coating. Recommendations are given so that the optical model may be improved relative to accelerated testing and validated relative to field aging.

14 SOLAR ENERGY↗

Chromosome duplication causes premature aging via defects in ribosome quality control

Down syndrome, caused by an extra copy of Chromosome 21, causes lifelong problems. One of the most common phenotypes among people with Down syndrome is premature aging, including early tissue decline, neurodegeneration, and shortened life span. Yet the reasons for premature systemic aging are a mystery and difficult to study in humans. Here we show that chromosome amplification in wild yeast also produces premature aging and shortens life span. Chromosome duplication disrupts nutrient-induced cell-cycle arrest, entry into quiescence, and cellular health during chronological aging, across genetic background and independent of which chromosome is amplified. Using a genomic screen, we discovered that these defects are due in part to aneuploidy-induced dysfunction in Ribosome Quality Control (RQC). We show that aneuploids entering quiescence display aberrant ribosome profiles, accumulate RQC intermediates, and harbor an increased load of protein aggregates compared to euploid cells. Although they maintain proteasome activity, aneuploids also show signs of ubiquitin dysregulation and sequestration into foci. Remarkably, inducing ribosome stalling in euploids produces similar aging phenotypes, while up-regulating limiting RQC subunits or poly-ubiquitin alleviates many of the aneuploid defects. We propose that the increased translational load caused by having too many mRNAs accelerates a decline in translational fidelity, contributing to premature aging.

Aneuploidy↗

Nondestructive Evaluation (NDE) of Cable Anomalies using Frequency Domain Reflectometry (FDR) and Spread Spectrum Time Domain Reflectometry (SSTDR)

This report presents a comparative assessment of the performance of frequency domain reflectometry (FDR) and spread spectrum time domain reflectometry (SSTDR) in detecting a wide range of electrical cable anomalies. All tests and results reported herein were performed at the PNNL Accelerated and Real-Time Environmental Nodal Assessment (ARENA) cable and motor test bed. The primary objective of this work was to evaluate the effectiveness of SSTDR, a fledgling cable monitoring technique that shows promise for application in online monitoring of energized cable systems, against FDR, an offline technique widely employed in the nuclear power plant (NPP) industry. FDR tests are becoming more widely used in nuclear power plant cable aging management and test programs – particularly for low voltage cables. FDR capabilities for these kinds of tests have been reported by PNNL and others. The FDR test is performed on de-energized cables by connecting the FDR instrument to two of the cable conductors, or one conductor and the shield. A broad band low voltage (< 5 V) chirp is introduced in the cable, and any reflected response is captured in the frequency domain. The captured reflection is then processed by performing an inverse Fourier transform to a time domain response which can then be converted to a distance response based on the cable velocity of propagation (VoP). SSTDR measurements are functionally similar to FDR measurements in that a broad-band voltage signal composed of a square or sine wave modulated pseudo-random sequence of chips (< 5 volts), is injected onto one of the cable conductors. The injected signal will experience partial energy reflection and transmission at each impedance discontinuity along the transmission line. Any reflected response is detected by computing a cross-correlation between the reflected signals and a delayed copy of the incident SSTDR signal. the time delay for the reflected signal to experience the best matched correlation with the incident signal, indicates the travel time for the signal to reach a change in impedance. By knowing this time delay and velocity of propagation (VoP) of the signal, one can compute the physical distance. A big advantage that SSTDR measurements have over other methods is the ability to be connected to energized or live wires (currently up to 1kV) thereby enabling online monitoring of cables. SSTDR has been used successfully in several applications, e.g., aircraft, rail, and photovoltaic systems. In this work FDR and SSTDR cable assessment techniques were used to characterize a variety of cable anomalies and faults including: (1) Presence or absence of a motor; (2) Ground faults and short circuit faults; (3) Moist environments and water ingress faults; (4) Accelerated thermal aging. Both shielded and non-shielded cables were evaluated in this report. Offline measurements were made using FDR and online measurements were made by SSTDR for a range of test scenarios. Based on the results across all cable anomalies evaluated in this study, FDR displayed high sensitivity towards cable condition assessment, while SSTDR showed promise for future application in monitoring NPP cable systems. However, further developments are suggested to improve the resolution and sensitivity of SSTDR towards faults and anomalies in low voltage cables.rt presents a comparative

42 ENGINEERING↗

Calibration of CDM-Based Creep Constitutive Model Using Accelerated Creep Test (ACT) Data

In conventional creep testing (CCT) a specimen is subject to constant load and temperature for a long-duration until creep rupture occurs. Conventional testing can be costly when considering the number of experiments needed to characterize the creep response of a material over a range of stress and temperature. To predict long-term creep-rupture properties, the time-temperature-stress superposition principle (TTSSP) approach has been employed where stress and/or temperature is applied at an elevated level; the result of which are extrapolated down to low stress and/or temperature conditions. These methods have been successful in predicting minimum-creep-strain-rate (MCSR) and stress-rupture (SR) but suffer from an inability to predict the creep deformation curve or account for changes in deformation mechanisms or aging that occurs at long-duration. An accelerated technique, termed the Stepped isostress method (SSM) allows the accelerated testing of materials to determine their creep deformation response. Unlike TTSSP tests, the SSM test employs a single specimen where the stress is periodically step increased until rupture. The SSM creep deformation curve is processed (time and strain shifted) to produce an accelerated creep deformation curve that represent the creep deformation curve at the initial stress level in SSM. A processing procedure for metals has yet to be developed. The research objective of this study is to develop a processing procedure for SSM test data using a creep-damage constitutive model. Triplicate SSM tests were conducted on Ni-based superalloy Inconel 718 at 650°C with stress being periodically increased until rupture. Triplicate CCT tests were conducted at the initial stress level of the SSM tests. The Sine-hyperbolic (Sinh) creep-damage model was employed in this study. The Sinh creep-damage constitutive model is based on coupled creep strain rate and damage evolution equations; where both rates are dependent on the current state of damage. Calibration is two-step: analytical and numerical optimization. Each stepped creep deformation curve is tackled quasi-analytically to determine MCSR and SR related material constants and accumulated damage. The damage accumulated at the end of each step was then passed onto subsequent steps to calibrate the MCSR, rupture prediction, and damage evolution. Numerical optimization was applied to optimize model constants involved in the creep strain constitutive equations in order to generate best-fitted Sinh creep deformation curves. The Sinh model predictions were compared to the SSM and CCT data. The Sinh model satisfactorily predicts the SSM data and thus the calibrated material constants provides a good estimate of rupture found in the CCT data. Calibration using SSM data reduces the number of tests needed to calibrate a model; significantly reducing costs. A single SSM test replaces numerous creep tests at different stresses.

36 MATERIALS SCIENCE↗

The Effect of Size on Postrelease Survival of Head-Started Mojave Desert Tortoises

Abstract Captive-rearing conservation programs focus primarily on maximizing postrelease survival. Survival increases with size in a variety of taxa, often leading to the use of enhanced size as a means to minimize postrelease losses. Head-starting is a specific captive-rearing approach used to accelerate growth in captivity prior to release in the wild. We explored the effect of size at release, among other potential factors, on postrelease survival in head-started Mojave desert tortoises Gopherus agassizii. Juvenile tortoises were reared for different durations of captivity (2–7 y) and under varying husbandry protocols, resulting in a wide range of juvenile sizes (68–145 mm midline carapace length) at release. We released all animals (n = 78) in the Mojave National Preserve, California, United States, on 25 September 2018. Release size and surface activity were the only significant predictors of fate during the first year postrelease. Larger sized head-starts had higher predicted survival rates when compared with smaller individuals. This trend was also observed in animals of the same age but reared under different protocols, suggesting that accelerating the growth of head-started tortoises may increase efficiency of head-starting programs without decreasing postrelease success. Excluding five missing animals, released head-starts had 82.2% survival in their first year postrelease (September 2018–September 2019), with all mortalities resulting from predation. No animals with >90-mm midline carapace length were predated by ravens. Our findings suggest the utility of head-starting may be substantially improved by incorporating indoor rearing to accelerate growth. Target release size for head-started chelonians will vary among head-start programs based on release site conditions and project-specific constraints.

Biodiversity & Conservation↗

Earthquake-triggered submarine canyon flushing transfers young terrestrial and marine organic carbon into the deep sea

Submarine canyons transfer substantial amounts of sediment and organic carbon (OC) into the deep ocean, nourishing deep-sea ecosystems and contributing to the global carbon cycle through OC burial and sequestration. Tracking lateral OC transport through submarine canyon systems is challenged by the deep-ocean setting, difficulties with constraining episodic depositional events, and the need to assess the composition and age of marine and terrestrial organic matter. We apply innovative parallel ramped pyrolysis oxidation accelerator mass spectrometry and pyrolysis-gas chromatography-mass spectrometry with isotope analyses to track OC age and sources in the 2016 Kaikoura earthquake-triggered, canyon-flushing event that deposited along >1300 km of a submarine canyon-channel system, offshore Aotearoa New Zealand. Specifically, these techniques allow us to determine the ages, sources, and partitioning of OC within the Kaikoura turbidite deposit and test hypotheses of how submarine canyon systems contribute to lateral OC flux and burial. Our results show that, despite considerable canyon floor erosion, substantial amounts of young OC were flushed into the deep sea, with relatively little (~2%) pre-Holocene OC contributions. Even without a direct connection between rivers and submarine canyons, most (~55%) of the OC in the Kaikoura event bed is from terrestrial sources. However, the deposit also contains substantial amounts (~22%) of marine-derived OC and ~23% of the material is of unassignable origin. Particle sorting imparts variability on the age and composition of OC within turbidite deposits and along the turbidity current flow path. Terrestrial-derived OC is preferentially older than marine-derived OC and concentrated in coarser particle sizes found more commonly at the deposit base and in proximal settings. Young, marine-derived OC is concentrated at the surface of the deposits and tends to be enriched in finer particle sizes. Such OC partitioning in turbidites supports the relevance of depositional models for predicting and quantifying distribution of OC in deep-sea deposits. Earthquake-triggered, canyon flushing events and resulting turbidites enhance OC burial efficiency and can sequester OC effectively, contributing an important carbon sink to the sedimentary carbon cycle.

54 ENVIRONMENTAL SCIENCES↗

Structure-Activity Relationships of Hydrothermally Aged Titania-Supported Vanadium-Tungsten Oxide Catalysts for SCR of NOx Emissions with NH3

Supported V2O5-WO3/TiO2 materials employed as selective catalytic reduction (SCR) catalysts for NOx emission control from power plants. Fresh SCR catalysts usually receive exposure to harsh treatments in industry to accelerate catalyst activation (calcination in air at 650oC) and catalyst aging (hydrothermal aging at 650oC) in a way that represents various points in the catalyst/product lifetime. The present study investigates the catalyst structural and chemical changes occurring during such harsh treatments. Three series of supported V2O5-WO3/TiO2 catalysts were prepared by incipient-wetness impregnation of aqueous ammonium metavanadate and metatungstate precursors. The catalysts were subsequently dried and calcined at 550oC in O2, 650oC in O2, and hydrothermal conditions (10% O2, 8% H2O, 7% CO2 and 75% N2) at 650oC. The resulting catalysts were physically characterized by numerous techniques (in situ Raman, in situ IR, in situ High Field-High Spinning solid-state 51V MAS NMR, in situ EPR, XRD, BET surface area and ICP) and chemically probed with adsorbed ammonia, SCR-TPSR, and the SCR reaction. The surface WOx sites on the TiO2 support behave as a textural promoter that stabilizes the TiO2 (anatase) phase from sintering and transforming to the undesirable crystalline TiO2 (rutile) phase that can lead to formation of a Ti1-xVxO2 (rutile) solid solution with reduced V4+ cations (~7-15%). The surface VOx sites are mostly oligomerized as surface V+5Ox sites (~50-85% oligomers) and the extent of oligomerization tends to increase with surface WOx coverage and calcination temperature. A major difference between the calcined and hydrothermally treated catalysts was the low concentration of surface NH3* species on Lewis acid sites for the hydrothermally treated catalysts, yet the SCR activity was almost comparable for both catalysts. This finding suggests that surface NH4+*, primarily associated with the surface VOx sites, are able to efficiently perform the SCR reaction. Given that multiple catalyst parameters were simultaneously varying during these treatments, it was difficult to correlate the SCR activity with any single catalyst parameter. A correlation, however, was found between the SCR TOF/activity and the sum of the surface NH3* and NH4+* species, which is dominated by the surface NH4+* species.

SCR, NO, NH3, catalyst, V2O5, WO3, TiO2, promotion↗

Photovoltaic Cable Jackets: A Comparison of Representative Products Using Combined-Accelerated Stress Testing [Slides]

Photovoltaic (PV) cables facilitate the distribution of electricity collected from modules to the energy grid. Durable cabling enables continuous operation of PV installations, whereas cables with a lifetime less than the modules must be replaced - reducing electricity generation and adding to the operating expense. This study primarily focusses on the aging of the key cable types using the combined-accelerated stress testing (C-AST) protocol. Representative cables for utility, building, and control/auxiliary applications were examined. Cable jacket materials examined include: polyolefin, polyethylene, polyamide, poly(vinyl chloride), chlorinated polyethylene, thermoplastic elastomer, and ethylene propylene diene monomer rubber. Specimen characterizations applied include: optical microscopy, mechanical profilometry, instrumented indentation, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). A variety of performance and durability characteristics were observed, depending on the base material, polymer formulation, and jacket color. The results from C-AST are analyzed and discussed relative to a recent industry survey on electronic balance of system components in addition to a recent study where similar cables were aged using steady state ultraviolet weathering (International Electrotechnical Commission Technical Specification 62788-7-2). Recommendations are made for the screening, industry qualification, and service life prediction of PV cable jackets.

24 POWER TRANSMISSION AND DISTRIBUTION↗

The Role of Topography in Controlling Evapotranspiration Age

Abstract Evapotranspiration (ET) age is a key metric of water sustainability but a major unknown partly due to the extreme difficulty in modeling it. Groundwater is found to be important in ET age variations in small‐scale studies, yet our understanding is insufficient because groundwater systems are nested across scales. Here, we conducted GPU‐accelerated particle tracking with integrated hydrologic modeling to quantify the variations in ET age at a regional scale of ∼0.4 M km 2 . Simulation results reveal topography‐driven flow paths shaping the spatial and temporal patterns of ET age variations. On ridges, where root zone decoupling with deep subsurface storage, ET age is generally young, with seasonal variations dominated by meteorological conditions. In the valley bottom, ET age is generally old, with significant subseasonal variations caused by the convergence of subsurface flow paths. On hillslopes with water table depths ranging from 1 to 10 m, ET age shows strong seasonal variations caused by the connections with lateral groundwater regulated by ET demand. Our modeling approach provides insights into the basic linkages between ET age and topography at large scale. Our work highlights the perspective of multiscale studies of ET age, suggesting new field experiments to test these process connections and to determine if such linkages warrant inclusion in Earth System Models.

54 ENVIRONMENTAL SCIENCES↗

Towards linking lab and field lifetimes of perovskite solar cells

Metal halide perovskite solar cells (PSCs) represent a promising low-cost, thin-film photovoltaic (PV) technology, with unprecedented power conversion efficiencies (PCEs) obtained for both single-junction and tandem applications. To push PSCs toward commercialization, it is critical, albeit challenging, to understand device reliability under real-world outdoor conditions where multiple stress factors (e.g., light, heat, humidity) coexist, generating complicated degradation behaviors. It is necessary to identify accelerated indoor testing protocols - which can correlate specific stressors with observed degradation modes in fielded devices - to quickly guide PSC development. Here, we use a state-of-the-art p-i-n PSC stack (with PCE up to ~25.5%) to show that indoor accelerated stability tests can predict our 6-month outdoor aging tests. Device degradation rates under illumination and at elevated temperatures are most instructive for understanding outdoor device reliability. Further, we also find that the indium tin oxide (ITO)/self-assembled monolayer (SAM)-based hole transport layer (HTL)/perovskite interface most strongly affects our device operation stability. Improving the ion-blocking properties of the SAM HTL increases averaged device operational stability at 50 degree C-85 °C by a factor of ~2.8, reaching over 1000 h at 85 °C and to near 8200 h at 50 °C with a projected 20% degradation, which is among the best to date for high-efficiency p-i-n PSCs.

14 SOLAR ENERGY↗

Transient solute drag and strain aging of dislocations

The transient drag force exerted by mobile solutes on a moving dislocation is computed using continuum theory. These mobile solutes form so-called Cottrell atmospheres around dislocations during static and dynamic strain aging. We evaluate the evolution of the drag force exerted by the atmosphere under two velocity time-histories: impulsive acceleration to a chosen velocity and a constant acceleration rate. A particular focus is on the conditions under which the stationary limit assumed by theories of dynamic strain aging is obeyed. According to our results, two conditions—one on the dislocation velocity and one on the acceleration rate—must be satisfied for the stationary limit to hold. Using the Orowan relation and a line tension model, we obtain estimates for the temperature, stress, strain rate, and dislocation density regimes where the stationary limit is valid, and compare these results with experiments for a few material systems.

36 MATERIALS SCIENCE↗

Synthesis and thermodynamics of uranium-incorporated α-Fe 2 O 3 nanoparticles

Hematite nanoparticles were synthesized with U(VI) in circumneutral water through a coprecipitation and hydrothermal treatment process. XRD, TEM, and EXAFS analyses reveal that uranium may aggregate along grain boundaries and occupy Fe sites within hematite. The described synthesis method produces crystalline, single-phase iron oxide nanoparticles absent of surface-bound uranyl complexes. EXAFS data were comparable to spectra from existing studies whose syntheses were more representative of naturally occurring, extended aging processes. Herein this work provides and validates an accelerated method of synthesizing uranium-immobilized iron oxide nanoparticles for further mechanistic studies. High temperature oxide melt solution calorimetry measurements were performed to calculate the thermodynamic stability of uranium-incorporated iron oxide nanoparticles. Increasing uranium content within hematite resulted in more positive formation enthalpies. Standard formation enthalpies of U x Fe 2–2x O 3 were as high as 76.88 ± 2.83 kJ/mol relative to their binary oxides, or -764.04 ± 3.74 kJ/mol relative to their constituent elements, at x = 0.037. Data on the thermodynamic stability of uranium retention pathways may assist in predicting waste uranyl remobilization, as well as in developing more effective methods to retain uranium captured from aqueous environments.

36 MATERIALS SCIENCE↗