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At least 253 records · Page 14

Stresses within rare-earth doped yttria-stabilized zirconia thermal barrier coatings from in-situ synchrotron X-ray diffraction at high temperatures

There is a growing interest for smart coatings that can be integrated into turbine engines for in-situ temperature measurements or health monitoring. The addition of rare-earth dopants into standard thermal barrier ceramic top coat materials is used to obtain luminescent coatings that enable spectral measurements, for real-time temperature or health monitoring. The thermomechanical performance and durability of such novel coating compositions in extreme environments still remains to be evaluated. Consequently, the ability to manufacture sensor coatings which present suitable thermal properties needs to be demonstrated. For this study, highly luminescent erbium and europium doped yttria-stabilized zirconia and state-of-the-art yttria-stabilized zirconia coatings manufactured by air plasma spray were characterized to determine the effects of the embedded rareearth dopants on coating internal strain and stress and to quantify and compare their high temperature response using synchrotron X-ray diffraction. In-situ depth-resolved strain measurements were performed at 15 μm intervals along the depth of the coatings to evaluate materials response at key locations, specifically at layer interfaces. In-plane stress was calculated for the coatings and a finite element model was implemented to supplement the results and enable further predictions. The results show that the sensor coatings that were manufactured in this work revealed only minor variations in the strain response of sensor coatings under a typical thermal cycle and especially at temperatures closer to that of gas turbine operating conditions, compared to state-of-the-art coatings. This work demonstrates the viability of manufacturing rare-earth doped yttria-stabilized zirconia coatings that provide beneficial spectroscopic monitoring capabilities while having minimal impact on the thermomechanical response of the thermal barrier coatings.

Air plasma spray↗

Surface triggered stabilization of metastable charge-ordered phase in SrTiO 3

Charge ordering (CO), characterized by a periodic modulation of electron density and lattice distortion, has been a fundamental topic in condensed matter physics, serving as a potential platform for inducing novel functional properties. The charge-ordered phase is known to occur in a doped system with high d-electron occupancy, rather than low occupancy. Here, we report the realization of the charge-ordered phase in electron-doped (100) SrTiO 3 epitaxial thin films that have the lowest d-electron occupancy i.e., d 1 -d 0 . Theoretical calculation predicts the presence of a metastable CO state in the bulk state of electron-doped SrTiO 3 . Atomic scale analysis reveals that (100) surface distortion favors electron-lattice coupling for the charge-ordered state, and triggering the stabilization of the CO phase from a correlated metal state. This stabilization extends up to six unit cells from the top surface to the interior. Our approach offers an insight into the means of stabilizing a new phase of matter, extending CO phase to the lowest electron occupancy and encompassing a wide range of 3d transition metal oxides.

36 MATERIALS SCIENCE↗

Thermal dynamics of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials for sodium ion batteries studied by in situ analysis

Cobalt-free layered Na 0.67 Ni 0.33 Mn 0.67 O 2 is an attractive cathode material for sodium ion batteries. The thermal stability of cathode materials is crucial to their practical applications. In the current work, we investigate structural and morphological evolution in P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials during annealing via in situ synchrotron X-ray diffraction and transmission electron microscopy. Insights are obtained from the two complementary in situ characterizations (at different length scales) in term of the thermal stability of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials. Here, the results indicate that the hexagonal P2 phase remains unchanged during the heat treatment process, and thermally driven expansion/contraction of lattice parameters exhibit an anisotropic character in the a and c directions. In addition, interfaces/grain boundaries play an important role in the structural stability, which leads to the distinct morphological evolution between the polycrystalline and single-crystal particles.

25 ENERGY STORAGE↗

Understanding the Hydronium Cation in the Solid State: A Study in Synthetic Hydronium Uranyl Phosphate and Arsenate Mineral Systems and Their Irradiation Stability

Here, we present neutron diffraction, electronic structure calculations, and optical vibrational spectroscopic characterization of hydronium uranyl phosphate (HUP), the synthetic analog of chernikovite ((H 3 O)(UO 2 )(PO 4 )·3H 2 O) to gain insight into structural features of the hydronium cation in the solid state. HUP crystallizes in P2 1 /c instead of previously reported P4/ncc 1 at room temperature and Pccn below 302 K. Lower symmetry was required due to hydronium and interstitial water positions within the structure. Crystallographic positions of hydronium cations determined from powder neutron diffraction data are bolstered by Raman and attenuated total reflectance infrared spectroscopic measurements and are further informed by density functional theory with phonon eigenvector analysis for spectral assignments. Finally, HUP and its arsenate analog (trogerite, (H 3 O)(UO 2 )(AsO 4 )·3H 2 O), (HUAs) were studied using He 2+ irradiation as an analog for α radiolysis to investigate the irradiation stability of these phases and the stability of hydronium cations in the solid state. Dose studies were employed wherein each sample was irradiated to 5, 10, 15, 25, and 50 MGy. Structural insight regarding irradiated materials is gained using optical vibrational spectroscopy and powder X-ray diffraction. Surprising irradiation stability of HUAs was found up to 50 MGy of dose, which may have important implications for understanding and modeling the geologic stability of legacy U.

actinides↗

Characterization of groove density variation of VLS gratings with ALS XROL LTP-II in different operation modes

The long trace profiler, LTP-II, available at the Advanced Light Source (ALS) X-ray Optics Laboratory (XROL), was recently upgraded by replacing a multimode diode laser light source with a single-mode, wavelength-stabilized, fibercoupled diode laser system. The upgrade enables us to reliably characterize the lateral variation of groove density of variable-line-spacing (VLS) x-ray diffraction gratings. Here, we discuss the LTP-II performance with an example of measurements with a VLS grating with the groove density at the grating center of 300 lines/mm. For the measurements, we use the LTP-II in two different operation arrangements, the single Gaussian beam and the pencil beam interferometer arrangements. For each operation arrangement, we apply two data processing algorithms: with calculating the centroid position and with determining the position of a characteristic features of the detected beam intensity distributions. Additionally, we discuss the observed strong correlation between the LTP-II modes of operation and the resulted (extracted) groove density variations. We also speculate on possible origin of the correlation.

42 ENGINEERING↗

Mechanical and Ionic Characterization for Organic Semiconductor–Incorporated Perovskites for Stable 2D/3D Heterostructure Perovskite Solar Cells

Hybrid metal halide perovskite (MHP) materials, while being promising for photovoltaic technology, also encounter challenges related to material stability. Combining 2D MHPs with 3D MHPs offers a viable solution, yet there is a gap in the understanding of the stability among various 2D materials. The mechanical, ionic, and environmental stability of various 2D MHP ligands are reported, and an improvement with the use of a quater-thiophene-based organic cation (4TmI) that forms an organic-semiconductor incorporated MHP structure is demonstrated. It is shown that the best balance of mechanical robustness, environmental stability, ion activation energy, and reduced mobile ion concentration under accelerated aging is achieved with the usage of 4TmI. It is believed that by addressing mechanical and ion-based degradation modes using this built-in barrier concept with a material system that also shows improvements in charge extraction and device performance, MHP solar devices can be designed for both reliability and efficiency.

14 SOLAR ENERGY↗

Thermal Stability and Mechanical Properties of Cold-Sprayed Nickel-Yttria Coating

The microstructural evolution under the extreme environments imposed during cold spray deposition of cermet coatings and the microstructural recovery during post-processing annealing treatments is rather complex and not well understood. Here, Ni-Yttria cermet coatings on an SS304 substrate were produced using cold spray technique, resulting in a bimodal grain structure. The grain growth, phase stability, hardness, and wear properties are observed in as-deposited and annealed (at 400 °C) Ni-Yttria and pure Ni coatings. A multimodal microstructural characterization using electron microscopy, and atom probe tomography shows the structural and compositional stability of yttria particles and Ni grains. A fragmentation of Y-rich particles and dispersion in Ni was observed, however, no forced mixing/dissolution of Y in Ni is detected. Nano-yttria dispersed within the Ni grains slowed the grain growth during annealing. After annealing, Yttria reinforced coating was 1.5 times harder and showed better thermal and mechanical stability compared to the Ni coating.

Gwalani, Bharat↗

Atmospheric Exposure Triggers Light-Induced Degradation in 2D Lead-Halide Perovskites

Quasi-2D perovskites have been pivotal in recent efforts to stabilize perovskite solar cells. Despite the stability boost provided when these materials are introduced in perovskite solar cells, little is known about the intrinsic light and environmental stability of quasi-2D perovskites. In this study, we characterize the photostability of exfoliated quasi-2D perovskite single crystals in air using photoluminescence, infrared, X-ray fluorescence, and energydispersive X-ray spectroscopy. Photoexcitation leads to severe material loss with oxygen as a prerequisite for material breakdown. The effect can be traced to the formation of reactive oxygen species, as demonstrated by increases in the photostability under oxygen-free conditions. We show the effect of combined passivation steps, showcasing the stability enhancement offered by 2D-capping layers in combination with an oxygen-free atmosphere. Our results reveal that the stability of illuminated quasi-2D perovskites depends critically on oxygen exposure, highlighting the importance of oxygen-blocking passivation strategies for stable 2D perovskite-based devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. Here we present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

36 MATERIALS SCIENCE↗

Understanding the Stability of Manganese Chromium Antimonate Electrocatalysts through Multimodal In Situ and Operando Measurements

Herein, we utilize an on-line electrochemical flow cell coupled with an inductively coupled plasma-mass spectrometer (ICP-MS) to characterize the impact of composition and reactant gas on the multielement dissolution of Mn(-Cr)-Sb-O electrocatalysts. Compared to Mn 2 O 3 and Cr 2 O 3 oxides, we find that the antimonate framework stabilizes Mn at OER potentials and Cr at both ORR and OER potentials. Furthermore, dissolution of Mn and Cr from Mn(-Cr)-Sb-O is found to be driven by ORR reaction rate, with minimal dissolution under N 2 . We observe preferential dissolution of Cr totaling 13% over 10 minutes at 0.3, 0.6, and 0.9 V vs RHE, with only 1.5% loss of Mn, indicating an enrichment of Mn at the surface of the particles. Despite this asymmetric dissolution, in situ X-ray absorption spectroscopy (XAS) showed no measurable changes in the Mn K-edge at comparable potentials. This lack of change could suggest that modification to the Mn oxidation state in the surface layer is too small or that layer is too thin to be measured with the bulk XAS measurement. Lastly, on-line ICP-MS was used to assess the effects of applied potential, scan rate, and current of Mn-Cr-Sb-O during cyclic voltammetry and accelerated stress tests. With this deeper understanding of the interplay between oxygen reduction and dissolution, testing procedures were identified to maximize both activity and stability. This work highlights the use of multi-modal in situ characterization techniques in tandem to build a more complete model of stability and develop protocols for optimizing catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancement of low-temperature solid oxide fuel cell performance and durability via surface chemistry modification

The development of active cathodes is one of the most critical challenges to lowering the operating temperature for solid oxide fuel cells (SOFCs). Here, in this work, we demonstrated that by modifying the cathode surface chemistry at a relatively low temperature, the cathode activity and durability can be simultaneously enhanced on high-performing, low-temperature cathodes such as (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ (LSCF) and Sr 0.5 Sm 0.5 CoO 3-δ (SSC). This low-temperature modification using multi-valent cations activates the highly defected surface and maintains the nanoscale electrocatalysts by bypassing the high-temperature sintering procedure for SOFC fabrication. The modified cathode at 600°C shows an order of magnitude reduction in impedance to only 0.05 Ωcm 2 with a peak power density of 1.1 W/cm 2 and increases stability over 2000 h. The combination of in situ characterization, distribution of relaxation time analysis on impedance spectroscopy, and surface chemistry analysis reveals the importance of surface chemistry control on the gas-solid reaction activity and durability and provides the design principle for numerous future solid oxide cells.

25 ENERGY STORAGE↗

Effect of microstructural and environmental variables on ductility of austenitic stainless steels

Austenitic stainless steels are used extensively in harsh environments, including for high-pressure gaseous hydrogen service. However, the tensile ductility of this class of materials is very sensitive to materials and environmental variables. While tensile ductility is generally insufficient to qualify a material for hydrogen service, ductility is an effective tool to explore microstructural and environmental variables and their effects on hydrogen susceptibility, to inform understanding of the mechanisms of hydrogen effects in metals, and to provide insight to microstructural variables that may improve relative performance. In this study, hydrogen precharging was used to simulate high-pressure hydrogen environments to evaluate hydrogen effects on tensile properties. Several austenitic stainless steels were considered, including both metastable and stable alloys. Room temperature and subambient temperature tensile properties were evaluated with three different internal hydrogen contents for type 304L and 316L austenitic stainless steels and one hydrogen content for XM-11. Significant ductility loss was observed for both metastable and stable alloys, suggesting the stability of the austenitic phase is not sufficient to characterize the effects of hydrogen. Internal hydrogen does influence the character of deformation, which drives local damage accumulation and ultimately fracture for both metastable and stable alloys. While a quantitative description of hydrogen-assisted fracture in austenitic stainless steels remains elusive, these observations underscore the importance of the hydrogen-defect interactions and the accumulation of damage at deformation length scales.

36 MATERIALS SCIENCE↗

Impact of Cr and Co on 99Tc retention in magnetite: A combined study of ab initio molecular dynamics and experiments

This work explores the effect of co-mingled dopants, Co(II) and Cr(III), on Tc(IV) incorporation and retention in magnetite when heat treated to 625 or 700 °C. Key trends in Tc retention in the high temperature regime were identified using a combination of density-functional-theory based ab initio molecular dynamics (AIMD) simulations, and batch experiments including solid phase characterization techniques, e.g. X-ray absorption spectroscopy. A stabilizing effect on Tc(IV) was observed when the number of Tc and Cr atoms are equal or when the magnetite surface is oversaturated with Tc and Cr inclusions. Here, oversaturation is hypothesized to force Cr from the magnetite surface to form a Cr2O3 phase, which may act as a protective layer that prevents Tc release. With the addition of Co, Tc(IV) is stabilized via redox processes. The presence of Cr in low concentrations interferes with this redox stabilization and Cr is preferentially stabilized as opposed to Tc. As a result, using Co as a stabilizing dopant for Tc may be compromised in the presence of Cr. When the relative concentration of Tc, Cr and Co is the same, or more Co atoms are added to high Cr incorporated systems, the formation of the Cr2O3 phase may be suppressed. Although waste streams with co-mingled Tc and Cr potentially may benefit from a Co dopant, since the formation of a Cr2O3 passivation layer may protect incorporated Tc from being released, the relative concentration of the three elements will be a critical parameter for maximizing effectiveness of this strategy.

Lee, Mal Soon↗

Optical transmission and dimensional stability of single-crystal sapphire after high-dose neutron irradiation at various temperatures up to 688 °C

The use of single-crystal sapphire optical fibers has been considered to extend fiber-optic sensing to the extreme temperature (>1000 °C) environments encountered in nuclear applications. However, before these sapphire fiber–based sensors can be deployed, their optical transmission and dimensional stability (which impacts drift of some sensors) must be characterized under representative testing conditions. Data regarding the optical transmission of sapphire following high-dose neutron irradiation at temperatures >100 °C is extremely limited. This work provides measurements of optical density (i.e., attenuation) and directional dimensional changes in bulk single-crystal sapphire materials irradiated to a fast neutron fluence of 2.4 × 10 21 n/cm 2 (3.5 displacements per atom) at temperatures ranging from 95 to 688 °C. Optical density measured after irradiation at 95 and 298 °C showed ultraviolet and visible absorption bands corresponding to known defect centers and temperature trends that were generally consistent with previous ex situ and in situ measurements made at much lower neutron fluence. However, optical density measured after irradiation at 688 °C was as much as two orders of magnitude higher, indicating that the fundamental mechanism for radiation-induced attenuation changes at this irradiation temperature. Additional analysis and comparison with previous works suggest that the attenuation may result from void formation, leading to increased Rayleigh scattering losses in the material and increased swelling that would also result in drift of Bragg grating-based sensors in sapphire fibers. These results pose serious questions regarding the feasibility of sapphire fiber–based sensors for high-temperature nuclear applications.

36 MATERIALS SCIENCE↗

Tuning Uranium Redox Chemistry in Asymmetric Polyoxometalate Complexes: Access to U(IV), U(V), and Transient U(VI)

We report the synthesis and characterization of asymmetric sandwich-type complexes [TpU IV EW 11 O 39 ] x– (E = P; x = 4, E = Si; x = 5, Tp = trispyrazolylborate). These complexes represent rare examples of the selective formation of asymmetric actinide-polyoxometalate (An-POM) complexes. Oxidation studies show that the U V analogues are stable and accessible, with both complexes isolated. Attempts to access U VI with this framework yield mixed results. Attempts to produce [TpU VI PW 11 O 39 ] 2– only led to decomposition, while electrochemical oxidation experiments gave evidence of transient formation of [TpU VI SiW 11 O 39 ] 3– in solution. Rapid decomposition of [TpU VI SiW 11 O 39 ] 3– inhibits full characterization. These studies indicate that the redox properties and stability of An-POM complexes containing actinides in higher valencies are dependent on the anionic charge of the assembly.

Actinides↗

Pyrolyzed Parylene-N for in Vivo Electrochemical Detection of Neurotransmitters

Carbon electrodes are typically used for in vivo dopamine detection, and new types of electrodes and customized fabrication methods will facilitate new applications. Parylene is an insulator that can be deposited in a thin layer on a substrate and then pyrolyzed to carbon to enable its use as an electrode. However, pyrolyzed parylene has not been used for the real-time detection of neurochemicals by fast-scan cyclic voltammetry. In this work, we deposited thin layers of parylene-N (PN) on metal wires and then pyrolyzed them to carbon with high temperatures in a rapid thermal processor (RTP). Different masses of PN, 1, 6, and 12 g, were deposited to vary the thickness. RTP-PN (6 g) produced a 194 nm layer carbon thickness and had optimal electrochemical stability. Pyrolyzed parylene-N modified electrodes (PPNMEs) were characterized for electrochemical detection of dopamine, serotonin, and adenosine. Background-normalized currents at PPNMEs were about 2 times larger than those of carbon-fiber microelectrodes (CFMEs). Rich defect sites and oxygen functional groups promoted the neurochemical adsorption of cationic neurotransmitters. PPNMEs resisted fouling from serotonin polymer formation. PPNMEs were used in vivo to detect stimulated dopamine release and monitor spontaneous adenosine release. Pyrolyzed parylene is a sensitive and fouling-resistant thin-film carbon electrode that could be used in the future for making customized electrodes and devices.

25 ENERGY STORAGE↗

Unprecedented Radiation Resistant Thorium–Binaphthol Metal–Organic Framework

A thorium–organic framework (TOF-16) containing hexameric secondary building units connected by functionalized binaphthol linkers was synthesized, characterized, and irradiated to probe its radiation resistance. Radiation stability was examined using γ-rays and 5 MeV He 2+ ions to simulate α particles. γ-irradiation of TOF-16 to an unprecedented 4 MGy dose resulted in no apparent bulk structural damage visible by X-ray diffraction. To further probe radiation stability, we conducted the first He 2+ ion irradiation study of a metal–organic framework (MOF). Diffraction data indicate onset of crystallinity loss upon approximately 15 MGy of irradiation and total loss of crystallinity upon exposure to approximately 25 MGy of He 2+ ion irradiation. In conclusion, the high radiation resistance observed suggests MOFs can withstand radiation exposure at doses found in nuclear waste streams and highlights the need for a systematic approach to understand and eventually design frameworks with exceptional radiation resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Triphenylphosphine Oxide-Derived Anolyte for Application in Nonaqueous Redox Flow Battery

Recent advances in redox flow batteries have made them a viable option for grid-scale energy storage, however they exhibit low energy density. One way to boost energy density is by increasing the cell potential using a nonaqueous system. Molecular engineering has proven to be an effective strategy to develop redox-active compounds with extreme potentials but these are usually challenged by resource sustainability of the newly developed redox materials. Here, we investigate the utility of phosphine oxides as anolytes with extremely negative potentials. Specifically, we found that cyclic triphenylphosphine oxide (CPO), has a highly negative potential (–2.4 V vs Fc/Fc + ). Importantly, CPO is synthesized from triphenylphosphine oxide, a common industrial chemical waste with no commercial value. Structural and electrochemical characterization of the reduced radical anion showed that enhanced stability is due to cyclization or extended pi-conjugation. Importantly, mechanistic investigation into the decomposition of CPO under various solvents and electrochemical conditions allowed us to utilize an acetonitrile/DMF binary solvent system to enable a long-lived anolyte which exhibited no fade over 350 cycles. In conclusion, this work led to the development of a waste-derived cyclic phosphine oxide that exhibits excellent cycling stability making it an ideal anolyte toward the development of energy-dense RFBs.

25 ENERGY STORAGE↗