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At least 91 records · Page 5

Mechanical degradation of duplex SiC-fiber reinforced SiC matrix composite tubes under a controlled high-temperature steam environment

This paper describes results from the mechanical evaluation of unirradiated SiC fiber–reinforced SiC matrix composite tubes under a controlled high-temperature steam environment. The experiments were aimed at identifying key material degradation behavior under environments relevant to loss-of-coolant accidents of light water reactors. Mechanical tests of the SiC composite tubes at 1000 °C under steam and inert environments were conducted using a unique test capability. Further, the material tested was a duplex tube with a thick monolithic SiC layer on the outer surface. The tubes were subjected to preloading at ~100 MPa in tension before exposure to high-temperature steam with up to 75% of the preload at a constant displacement. In the presence of matrix cracks, the steam exposure caused embrittlement of the SiC composite tubes and failure at a stress level below the pretest stress. The material degradation was explained by a fiber oxidation model, which can be applied to various SiC cladding concepts. The embrittlement could be a limiting factor for using SiC cladding subjected to loss-of-coolant accident conditions.

36 MATERIALS SCIENCE↗

Degradation mechanisms of selected hydrochlorofluorocarbons in the atmosphere: An assessment of the current knowledge

Volatile organic compounds are mainly degraded in the troposphere by attack of OH with abstraction of H atoms or addition to unsaturated linkages. The chlorofluorocarbons (CFC's) do not contain these reactive sites and consequently cannot be degraded in this way in the lower atmosphere. This results in pollution of the stratosphere by these molecules and attendant problems for ozone. The proposed replacements for CFC's, the hydrochlorofluorocarbons (HCFC's), and hydrofluorocarbons (HFC's), contain at least one hydrogen atom in the molecule, which confers on these compounds a greater sensitivity toward oxidation by OH in the troposphere and in the lower stratosphere, resulting in much shorter atmospheric lifetimes than the CFC's. Consequently, the Ozone Depletion Potential and the Atmospheric Warming Potential are reduced substantially compared to the CFC's. All the possible degradation processes of the HCFC's and HFC's proposed to replace the CFC's are examined with the principal aim of identifying chlorine- and fluorine-containing products which are stable under tropospheric conditions.

Cox, Richard A.↗

Collaborative Approach to Identify Degradation Mechanisms and Validate Aging Protocols for a Diverse Set of DAC Materials (TCF Base Technology-Specific Final Report)

This work supports the mission of the U.S. Department of Energy to promote American energy leadership, technological innovation, and economic growth through the development of technologies for cost effective carbon capture. While capture technologies can provide carbon dioxide for enhanced oil recovery, many capture materials suffer from oxidative, hydrolytic and/or thermal degradation which leads to capacity loss and unwanted emissions such as ammonia. Short lifetimes increase operational costs and cost studies suffer from uncertainty because the true lifetimes of many capture materials are unknown. In this study, a suite of capture materials were studied to quantify their degradation, provide insight into the mechanisms that lead to their uptake loss and provide validated accelerated aging protocols for industry.

36 MATERIALS SCIENCE↗

Insight into the Radiolytic Degradation Mechanism of TODGA

Partitioning and transmutation schemes, where americium is separated from other components of used nuclear fuel and burned in a fast neutron reactor, offer a path to dramatically decrease the space requirements for storage of nuclear fuel cycle wastes, allowing more efficient usage of potentially scarce storage resources.[1] Improvements in the efficiency of processes for separating americium from used nuclear fuels can thus have a significant impact on the costs of future nuclear fuel cycles. Understanding separation ligand radiation chemistry is important for development of new ligands and processes, as the ligand degradation products can have a deleterious effect on a separation process. Tetraoctyl diglycolamide (TODGA) has been studied as a ligand for lanthanide/minor actinide extraction for partitioning and transmutation schemes. However, the mechanism of initial energy transfer from products of solvent radiolysis to TODGA is still under debate. One proposed mechanism is attack by a n-dodecane radical cation resulting in electron abstraction and formation of a TODGA radical cation,[2] while later work has proposed hydrogen abstraction from sites adjacent to the central ether oxygen by other radical species.[3] The latter mechanism is proposed to result in degradation products from rupture of the ether bond. However, radiolytic degradation of TODGA in n-dodecane shows products that would result from rupture of all the backbone bonds. There is little information on what degradation products would be expected to form from the TODGA radical cation. In this work, we have begun to investigate this by examining the electron impact (EI) ionization mass spectrum of TODGA, which initially produces a TODGA radical cation in the gas phase. The EI spectrum shows fragments that would result from most backbone bond cleavages, similar to what is observed in the radiolysis of TODGA in n-dodecane. As the lifetime of the solvent radical cation decreases from n-dodecane to n-hexane,[4] irradiation of TODGA in n-hexane should have less solvent radical cations available for reaction with TODGA, and instead should favor reactions with longer-lived radicals. In contrast to n-dodecane, radiolytic degradation of TODGA in n-hexane produces only N,N-dioctylacetamide, which would result from rupture of the ether bond. The n-dodecane radical cation lifetime is long enough to produce TODGA radical cations but the n-hexane radical cation is mostly consumed before reaction with TODGA, so other radical processes that abstract hydrogen from TODGA dominate. This suggests that electron abstraction by the n-dodecane radical cation is an important component of TODGA radiolysis, although it does not rule out the presence of mechanisms involving hydrogen abstraction adjacent to the ether oxygen. References [1] J. Serp et al., Energies 2017, 10 (9), DOI: 10.3390/en10091445. [2] C. Zarzana et al., Solvent Extr. Ion Exch. 2015, 33 (5), 431–447, DOI: 10.1080/07366299.2015.1012885. [3] T. Koubský et al., Prog. Nucl. Energy 2017, 94, 208–215, DOI: 10.1016/j.pnucene.2016.07.010. [4] F. Sviridenko et al., Chem. Phys. Lett. 1998, 297 (3), 343–349, DOI: 10.1016/S0009-2614(98)01099-9.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Study of the thermal degradation mechanism of a composite propellant

The current experimental program was designed to systematically investigate the role of the oxidizer in the thermal degradation process of composite propellants. The scanning electron microscope (SEM) was used to examine the failure sites in thermally degraded propellant samples. The formulation variables tested were oxidizer purity, oxidizer particle size, and oxidizer to binder bonding agent. The binder, a saturated hydrocarbon, was kept constant throughout the experiments. The oxidizers were: AP, chlorate-doped AP, arsenate-doped AP, and phosphate-doped AP. The oxidizer particle size distribution was 60% of the large fraction and 40% of the small fraction. The bonding agent, when present, was used at the 0.15% level. The data showed that both the oxidizer purity and particle size had an important affect on the thermal degradation process. The affect of the oxidizer particle size was more noticeable at the higher temperature and stress levels. An examination of the failure site, by SEM, of propellants subject to these latter conditions indicated that the fracturing of the large oxidizer particles led to the propellant cracking.

Schmidt, W. G.↗

Analysis of Microwave Resonant Cavity Transducer Degradation Mechanisms

We are investigating a microwave resonant cavity transducer for flow sensing in the vessel of a high temperature fluid advanced reactor (AR), such as a molten salt cooled reactor (MSCR) or a sodium fast reactor (SFR). This transducer is a hollow metallic cylindrical cavity, with the flat wall of the cylinder flexible enough to undergo microscopic deflection due to dynamic fluid pressure. Membrane deflection leads to a shift in the resonant frequency, which can be detected with a spectrum analyzer. Because the transducer is intended for immersion in a high temperature corrosive fluid, understanding of material degradation is crucial for estimation of transducer performance lifetime, and development of measurement interpretation algorithms. We conducted a preliminary computational investigation of relevant damage mechanisms of a stainless steel 316 cylindrical resonator in FLiBe salt. The two main damage mechanisms, creep and corrosion, were modeled using multiphysics COMSOL software. Degradation was modeled for a temperature range 500°C to 700°C. Coupling of the damage mechanisms was not considered. These models predict significant inelastic deformation at most temperatures due to creep, and qualitatively predict chromium depletion both along the liquid/solid interface and along the grain boundaries. An algorithmic approach for compensation of these degradation effects during fluid flow measurements will be developed in the future work.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Degradation mechanisms of 1.3 μm C-doped quantum dot lasers grown on native substrate

Here, the aim of this paper is to analyse the degradation modes of 1.3 μm InAs quantum dot laser diodes (QD LDs) grown by using carbon as a p-type dopant, as an alternative to beryllium. The devices were stressed at high current densities, to favor the onset of excited-state (ES) emission, and to study the related degradation phenomena. The study of QD LDs is of fundamental importance for the photonic integrated circuits (PICs). The investigation is based on two types of stress tests: 1) a current step stress and 2) a constant current stress. With these experiments we demonstrate that a) the current is a determining factor for the onset of the ES during the operation of such devices. b) the onset of ES is responsible for a rapid quenching of the ground state (GS) emission. c) stress induces a significant increase in the threshold current of the devices, that is ascribed to the lowering of the injection efficiency, which in turn can be explained by the easier escape of carriers from quantum dots (QDs) from ES energy levels. d) the contribution of defects on the optical and electrical degradation is also discussed.

42 ENGINEERING↗

A study of degradation mechanisms in PVDF-based photovoltaic backsheets

Abstract Commercial backsheets based on polyvinylidene fluoride (PVDF) can experience premature field failures in the form of outer layer cracking. This work seeks to provide a better understanding of the changes in material properties that lead to crack formation and find appropriate accelerated tests to replicate them. The PVDF-based backsheet outer layer can have a different structure and composition, and is often blended with a poly(methyl methacrylate) (PMMA) polymer. We observed depletion of PMMA upon aging with sequential (MAST) and combined (C-AST) accelerated stress testing. In field-aged samples from Arizona and India, where PVDF crystallizes in its predominant α-phase, the degree of crystallinity greatly increased. MAST and C-AST protocols were, to some extent, able to replicate the increase in crystallinity seen in PVDF after ~ 7 years in the field, but no single-stress test condition (UV, damp heat, thermal cycling) resulted in significant changes in the material properties. The MAST regimen used here was too extreme to produce realistic degradation, but the test was useful in discovering weaknesses of the particular PVDF-based outer layer structure studied. No excessive β-phase formation was observed after aging with any test condition; however, the presence of β-phase was identified locally by Fourier transform infrared spectroscopy (FTIR). We conclude that both MAST and C-AST are relevant tests for screening outdoor failure mechanisms in PVDF backsheets, as they were successful in producing material degradation that led to cracking.

14 SOLAR ENERGY↗

A Numerical Solution Routine for Investigating Oxidation-Induced Strength Degradation Mechanisms in SiC/SiC Composites

The stress rupture strength of silicon carbide fiber-reinforced silicon carbide (SiCSiC) composites with a boron nitride (BN) fiber coating decreases with time within the intermediate temperature range of 700-950 C. Various theories have been proposed to explain the cause of the time dependent stress rupture strength. Some previous authors have suggested that the observed composite strength behavior is due to the inherent time dependent strength of the fibers, which is caused by the slow growth of flaws within the fibers. Flaw growth is supposedly enabled by oxidation of free carbon at the grain boundaries. The objective of this paper is to investigate the relative significance of the various theories for the time-dependent strength of SiCSiC composites. This is achieved through the development of a numerically-based progressive failure analysis routine and through the application of the routine to simulate the composite stress rupture tests. The progressive failure routine is a time marching routine with an iterative loop between a probability of fiber survival equation and a force equilibrium equation within each time step. Failure of the composite is assumed to initiate near a matrix crack and the progression of fiber failures occurs by global load sharing. The probability of survival equation is derived from consideration of the strength of ceramic fibers with randomly occurring and slow growing flaws as well as the mechanical interaction between the fibers and matrix near a matrix crack. The force equilibrium equation follows from the global load sharing presumption. The results of progressive failure analyses of the composite tests suggest that the relationship between time and stress-rupture strength is attributed almost entirely to the slow flaw growth within the fibers. Although other mechanisms may be present, they appear to have only a minor influence on the observed time dependent behavior.

degradation↗

Understanding Recoverable vs Unrecoverable Voltage Losses and Long-Term Degradation Mechanisms in Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently shown excellent progress in terms of their performance – e.g., achievable power and current density. However, very few AEMFCs have been demonstrated with the ability to operate for a long duration (>1000 h). In addition, it is unknown whether performance losses observed during operation are reversible, irreversible, or a combination of the two. In this study, a high-performance AEMFC operated continuously at 600 mA/cm 2 for 3600 h (150 days) at 80 °C with H 2 /O 2 reacting gases was demonstrated. Throughout testing, the electrochemical properties of the AEMFC were probed to provide information about performance degradation pathways and their degree of reversibility. It was found that a portion of the performance loss that occurs during AEMFC operation was due to suboptimal reaction conditions and can be recovered. At the end of the experiment, the cell was disassembled, and its structure and composition were evaluated at the nanoscale by aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. The structure and composition of the electrode were compared to cells at the beginning of their operational life. It was found that the primary mechanism for long-term AEMFC performance loss was catalyst agglomeration. During the operational time, there was no evidence of significant polymer degradation, likely due to the high hydration state of the cell. By documenting the long-term changes in high-performing AEMFCs, this work provides important information for the systematic design of cell components and demonstrates the importance of controlling cell operation, which can aid in the commercialization and widespread deployment of low-cost, long-life AEMFCs.

30 DIRECT ENERGY CONVERSION↗

Elucidating Cathode Degradation Mechanisms in LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)/Graphite Cells Under Fast Charge Rates Using Operando Synchrotron Characterization

Li-ion batteries capable of extreme fast charging (XFC) are in demand to facilitate widespread electric vehicle (EV) adoption. While the impact of fast charge on the negative electrode has been studied, degradation of state-of-the-art NMC811 under XFC conditions has not been studied in detail. Herein, cathode degradation is probed in NMC811/graphite batteries by analysis of structural and chemical changes for recovered samples previously cycled under XFC conditions and during typical cycling. NMC surface reconstruction, as determined by soft X-ray absorption, was not detected for recovered electrodes. Furthermore, bulk redox activity from X-ray absorption near edge structure measurements showed more change in the oxidation state of Ni and Co under the 1C charge rate compared to the 4C rate consistent with the electrochemistry. Increased unit cell volume contraction under the 1C rate as determined by operando X-ray diffraction suggests that higher charge rates may provide a protective effect on the cathode by reducing structural distortion due to less delithiation.

25 ENERGY STORAGE↗

Degradation Mechanism Due to Water Ingress Effect on the Top Contact of Cu(In,Ga)Se2 Solar Cells

The impact of moisture ingress on the surface of copper indium gallium diselenide (CIGS) solar cells was studied. While industry-scale modules are encapsulated in specialized polymers and glass, over time, the glass can break and the encapsulant can degrade. During such conditions, water can potentially degrade the interior layers and decrease performance. The first layer the water will come in contact with is the transparent conductive oxide (TCO) layer. To simulate the impact of this moisture ingress, complete devices were immersed in deionized water. To identify the potential sources of degradation, a common window layer for CIGS devices—a bilayer of intrinsic zinc oxide (i-ZnO) and conductive indium tin oxide (ITO)—was deposited. The thin films were then analyzed both pre and post water soaking. To determine the extent of ingress, dynamic secondary ion mass spectroscopy (SIMS) was performed on completed devices to analyze impurity diffusion (predominantly sodium and potassium) in the devices. The results were compared to device measurements, and indicated a degradation of device efficiency (mostly fill factor, contrary to previous studies), potentially due to a modification of the alkali profile.

14 SOLAR ENERGY↗

Understanding Degradation Mechanisms in SrIrO 3 Oxygen Evolution Electrocatalysts: Chemical and Structural Microscopy at the Nanoscale

Designing acid-stable oxygen evolution reaction electrocatalysts is key to developing sustainable energy technologies such as polymer electrolyte membrane electrolyzers but has proven challenging due to the high applied anodic potentials and corrosive electrolyte. This work showcases advanced nanoscale microscopy techniques supported by complementary structural and chemical characterization to develop a fundamental understanding of stability in promising SrIrO 3 thin film electrocatalyst materials. Cross-sectional high-resolution transmission electron microscopy illustrates atomic-scale bulk and surface structure, while secondary ion mass spectrometry imaging using a helium ion microscope provides the nanoscale lateral elemental distribution at the surface. After accelerated degradation tests under anodic potential, the SrIrO 3 film thins and roughens, but the lateral distribution of Sr and Ir remains homogeneous. A layer-wise dissolution mechanism is hypothesized, wherein anodic potential causes the IrO x -rich surface to dissolve and be regenerated by Sr leaching. Finally, the characterization approaches utilized herein and mechanistic insights into SrIrO 3 are translatable to a wide range of catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation Mechanism of Phosphate‐Based Li‐NASICON Conductors in Alkaline Environment

NASICON-type Li conductors (Li-NASICON) have traditionally been regarded as promising candidates for solid-state Li-air battery applications because of their stability in water and ambient air. However, the presence of water in the cathode of a Li-air battery can induce a highly alkaline environment by modifying the discharge product from Li 2 O 2 to LiOH which can potentially degrade cathode and separator materials. This study investigates the alkaline stability of common Li-NASICON chemistries through a systematic experimental study of LiTi x Ge 2-x (PO 4 ) 3 (LTGP) with varying x = 0–2.0. Density functional theory calculations are combined to gain a mechanistic understanding of the alkaline instability. It is demonstrated that the instability of LTGP in an alkaline environment is mainly driven by the dissolution of PO 4 3– groups, which subsequently precipitate as Li 3 PO 4 . The introduction of Ti facilitates the formation of a Ti-rich compound on the surface that eventually passivates the material, but only after significant bulk degradation. Consequently, phosphate-based Li-NASICON materials exhibit limited alkaline stability, raising concerns about their viability in humid Li-air batteries.

25 ENERGY STORAGE↗

Investigation of the Mechanical Degradation of Zinc-Based Cold Spray Coatings for Steel Pipelines

Internal corrosion in wet natural gas is a big challenge in the oil and gas industry due to corrosive constituents such as carbon dioxide (CO2), hydrogen sulfide (H2S), other forms of sulfur, and water in the gas stream. To mitigate internal corrosion, zinc-based cold spray coatings were designed for use in natural gas pipelines to increase the lifespan of the pipeline network. However, one of the requirements in designing internal coatings is the resistance of the coatings to mechanical forces applied on the pipeline's internal wall during pigging operations. These forces are primarily compressive and shear/friction forces. This study examines material properties that must be considered when evaluating mechanical considerations.

adhesion↗

Degradation Mechanisms in TOPCon/POLO Solar Cells

This presentation shows how Poly-Si/SiO2 contacts show a post firing degradation/regeneration cycle. The following conclusions were made: 1) cycle changes surface passivation (Jo), but not the bulk lifetime; 2) cycle time depends on anneal temperature in light or dark (higher T, faster cycle); 3) 400 degrees Celsius anneal eliminates the cycle - only generation occurs; 4) cycle time and magnitude is not correlated with Tfire; 5) contact passivation is stable after cycling; 6) fundamental nature of defect(s) responsible is not known; 7) TOPCon cells/modules, if constructed well, seem to show minimal degradation issues (PVEL, Jolywood, Jinko, ET Solar), and 8) NREL/ASU are studying TOPCon cells and UC Davis has a molecular dynamics model for TOPCon.

degradation↗