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Evaluation of Copper Catalytic Effects in Cable Insulation Polymers

This paper summarizes work performed to evaluate a phenomenon that occurs in electrical cable insulation polymers subjected to accelerated aging while in contact with copper metal. This effect, commonly known as the copper catalytic effect, is a result of chemical reactions that occur when copper ions diffuse into insulation polymers. This diffusion process is observed in various types of polymeric materials exposed to elevated temperatures and happens at the interface between the insulation and metallic components (e.g., conductor, shielding, etc.) in a cable. This polymer-metal interaction has only been observed in cables constructed with copper components (i.e., no interactions observed in cables with aluminum or other metal conductor/shielding) and results in a significant catalytic effect that increases the oxidation rate (e.g., aging) of the material. Under this research, the copper catalytic effects observed in cross-linked polyethylene, cross-linked polyolefin and ethylene propylene rubber insulated cables subjected to thermal accelerated aging were evaluated. These evaluations involved applying infrared spectroscopy, microscopy, and energy dispersive X-ray spectroscopy cross-sectional depth profiling to obtain an in-depth understanding of the aging characteristics of the materials under accelerated conditions. Based on the results of these assessments, the copper catalytic effect can have a significant impact on the mechanical, thermal, chemical, and electrical properties of cable insulation polymers. Here, the results acquired from this research provided the information needed to characterize the copper catalytic effects observed in these polymers, analyze how this phenomenon affected the polymer degradation process, and compare and understand the differences in the properties of the materials.

42 ENGINEERING↗

Accelerated Aging in Electrolytic Capacitors for Prognostics

The focus of this work is the analysis of different degradation phenomena based on thermal overstress and electrical overstress accelerated aging systems and the use of accelerated aging techniques for prognostics algorithm development. Results on thermal overstress and electrical overstress experiments are presented. In addition, preliminary results toward the development of physics-based degradation models are presented focusing on the electrolyte evaporation failure mechanism. An empirical degradation model based on percentage capacitance loss under electrical overstress is presented and used in: (i) a Bayesian-based implementation of model-based prognostics using a discrete Kalman filter for health state estimation, and (ii) a dynamic system representation of the degradation model for forecasting and remaining useful life (RUL) estimation. A leave-one-out validation methodology is used to assess the validity of the methodology under the small sample size constrain. The results observed on the RUL estimation are consistent through the validation tests comparing relative accuracy and prediction error. It has been observed that the inaccuracy of the model to represent the change in degradation behavior observed at the end of the test data is consistent throughout the validation tests, indicating the need of a more detailed degradation model or the use of an algorithm that could estimate model parameters on-line. Based on the observed degradation process under different stress intensity with rest periods, the need for more sophisticated degradation models is further supported. The current degradation model does not represent the capacitance recovery over rest periods following an accelerated aging stress period.

Celaya, Jose R.↗

Experimental Characterization of Hygrothermal Aging: Competition Between Thermo-Oxidation and Hydrolysis Phenomena

Abstract In this work, we have presented a comparison between effects of accelerated thermo-oxidative, hydrolytic and hygrothermal aging on the mechanical and chemical properties of a polyurethane based (PUB) adhesive. The adhesive is a flexible adhesive which is extensively used in automobile industry as a glass sealant. During service life it gets exposed to the hygrothermal environment and the integrity of matrix interface is most vulnerable. This study focuses on weighing and comparing effects of different aging environments on material behavior; and it shows that hygrothermal aging environment results as a competition between two sub-aging phenomena i.e., thermo-oxidation and hydrolytic aging. Samples were exposed to 0%RH, 80%RH and submerged condition in distilled water. Uni-axial tensile tests, and cross-link density analysis by swelling test were carried out on as-received and aged samples. The aging process was conducted at three different temperatures (60°C, 80°C and 95°C) and for four different exposure durations of 1, 10, 30, and 90 days. This work confirms that the effect of hygrothermal aging is a result of competition between thermo-oxidation and hydrolytic aging environments. The total mechanical and environmental damage incurred by specimens is a collaborative effect of all exposure environments involved i.e., aging time, temperature, oxygen, water and humidity. The results are in agreement with the chemical test outcomes as well.

Shaafaey, Mamoon↗

Small-scale production of bespoke accelerated aging plutonium alloy

Here, this study demonstrates the 100 g scale manufacture of a plutonium alloy that ages at an accelerated rate. The resulting alloy ages six times faster than typical weapons-grade plutonium due to the addition of 238 Pu. As a major innovation, the process involved using a partial direct oxide reduction technique. This method was achieved by developing a new, complex geometry stirrer using additive manufacturing to reduce the 238Pu oxide and efficiently incorporate it into weapons-grade plutonium metal. The material was then purified by molten salt extraction and electrorefining before being alloyed with gallium. The alloy was then cold-rolled and annealed in a homogenization heat treatment. The resulting disk was characterized by metallography and differential scanning calorimetry, and the impurity content was determined using analytical chemistry techniques. The results show that a homogeneous delta phase plutonium alloy was achieved with expected microstructure and minimal impurities. This study was also successful in changing the plutonium isotopic composition by incorporating additional 238 Pu to accelerate the effects of radiation damage. This enables researchers to study long-term aging phenomena in a reduced time frame, thus avoiding the need for large-scale material production and circumventing the limitations of using naturally aged, archived plutonium.

Aging theory↗

Aging of Concrete for the Evaluation of Repair Materials to Protect the Walls of the HCAEX Tunnel at Savannah River - 20301

H-Canyon, located in the Savannah River site, is a unique facility for chemical reprocessing of plutonium, highly-enriched uranium, and other radioactive materials. The exhaust gases of the H-Canyon are sent through the H-Canyon Exhaust (HCAEX) tunnel for contamination removal. Robotic inspections of the tunnel revealed significant degradation of the reinforced concrete structure that was associated with acid attack, and could compromise the structural stability of the tunnel. Thus, the identification and evaluation of potential repair materials that could be applied on the degraded walls to mitigate and prevent further degradation is of significant interest to the Department of Energy and the Savannah River representatives. This research effort has been divided into two phases: 1) Development and evaluation of aged concrete under accelerated aging conditions (which is the focus of this paper) and 2) Evaluation of potential repair materials applied on aged and non-aged concrete under simulated aggressive conditions. In order to develop and evaluate concrete samples exposed to accelerated aging conditions in simulated aggressive environments, a literature review of the HCAEX tunnel was conducted that included 1) characterization and extent of the concrete damage, 2) environmental conditions inside the tunnel and 3) primary deterioration mechanisms. In addition, potential coatings and/or repair materials for degraded concrete surfaces exposed to aggressive environments (primarily acidic) were selected from the literature review and the most common testing and measurements for evaluating acid attack phenomena, erosion, etc. were reviewed. From the literature review findings, a preliminary bench-scale test plan for the concrete aging was developed, including accelerated aging tests with aggressive conditions (acid fumes, humidity, etc.). Concrete samples were exposed to the aging accelerated conditions (e.g. immersion in acid solutions) and visual inspection, mass loss and pH change (acid solution) were recorded over time. Correlations between the visual inspection, mass loss and pH changes results and the aging time or the aging conditions were developed. Specimens submitted to the highest acid concentration showed the fastest and most intense degradation. The type of coarse aggregate (limestone) used for the concrete seemed to be the cause of the fastest aging observed, compared to the cement paste. The research findings created the foundation for the ongoing investigation, in which new concrete samples with a mix design similar to the HCAEX tunnel will be tested and will serve as the substrate for testing the selected coatings and /or repair materials. In this paper, the literature review and preliminary results from the aging tests are provided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Independence of Environmental and Mechanical Damages on Silicone Adhesive Stored in a Thermo-Oxidative Environment

Abstract Elastomeric polymer materials hold a special place in today’s industrial sectors with respect to structural application needs. Low quality materials are detrimental to industries like aerospace, and automotive engineering. Assessment of the durability of elastomers for structural applications has been of much interest among the literary circles for decades and new materials keep outperforming the existing ones. Polymeric adhesives are one of the most abundantly used materials in these industries. All polymeric materials get damaged when in contact with aggressive environments in presence of high temperature and oxygen. Commonly referred to as thermo-oxidation, this environment exposes the material to heat and oxidation reactions in presence of oxygen. Resultantly, during service life, the damage to the polymer matrix is primarily caused by two factors: mechanical damage and environmental aging. Environmental aging is an irreversible phenomenon caused by changes in the molecular structure while mechanical damage maintains the shape of the polymer matrix, and the deterioration is mostly due to polymer chain mobility. Environmental aging can be caused by a single environmental agent or by a synergized impact of several environmental elements. Increasing temperature is found to be proportional to decreasing tensile strength and toughness of material. The rate and extent of degradation can be accessed by scrutinizing the changes in constitutive behavior of material through mechanical and chemical properties. Accelerated thermal aging is among the most common modes of process related degradation, leading generally to chain scission, and crosslinking phenomena and reduced resistance to fracture stress, and strain. In this experimental study, our goal is to separate the environmental degradation from mechanical damage. A silicone-based adhesive was aged in thermo-oxidative at (0%RH) aging environment. The damage and decay mechanisms have been used to draw a distinction between environmental degradation and mechanical damage. Material characterization included uniaxial tensile test (failure and cyclic) and scanning electron microscopy (SEM) tests on as-received and aged samples. Aging was conducted at three different temperatures (60°C, 80°C and 95°C) and six different exposure durations (1, 3, 10, 30, 90 and 200 days). This work confirms that environmental damage is superposed on top of the mechanical damage, and thus, they are separable. The total mechanical and environmental damage is a synergized effect of all exposure conditions and parameters involved i.e., aging time, temperature, and oxygen. The chemistry and mechanics of the polymer degradation were found to be in good agreement with each other.

Alazhary, Sharif↗

Radiation Hardness Assurance for Space Systems

The space radiation environment can lead to extremely harsh operating conditions for on-board electronic box and systems. The characteristics of the radiation environment are highly dependent on the type of mission (date, duration and orbit). Radiation accelerates the aging of the electronic parts and material and can lead to a degradation of electrical performance; it can also create transient phenomena on parts. Such damage at the part level can induce damage or functional failure at electronic box, subsystem, and system levels. A rigorous methodology is needed to ensure that the radiation environment does not compromise the functionality and performance of the electronics during the system life. This methodology is called hardness assurance. It consists of those activities undertaken to ensure that the electronic piece parts placed in the space system perform to their design specifications after exposure to the space environment. It deals with system requirements, environmental definitions, part selection, part testing, shielding and radiation tolerant design. All these elements should play together in order to produce a system tolerant to.the radiation environment. An overview of the different steps of a space system hardness assurance program is given in section 2. In order to define the mission radiation specifications and compare these requirements to radiation test data, a detailed knowledge of the space environment and the corresponding electronic device failure mechanisms is required. The presentation by J. Mazur deals with the Earth space radiation environment as well as the internal environment of a spacecraft. The presentation by J. Schwank deals with ionization effects, and the presentation by T. Weatherford deals with Single particle Event Phenomena (SEP) in semiconductor devices and microcircuits. These three presentations provide more detailed background to complement the sections 3 and 4. Part selection and categorization are discussed in section 5. Section 6 presents the organization of the hardness assurance within a project. Section 7 discusses emerging radiation hardness assurance issues.

Poivey, Christian↗

Lunar transient phenomena /LTP/ - Manifestations, site distribution, correlations and possible causes

More than 1400 observations of lunar transient phenomena (LTP), encompassing brightenings, darkenings, and gaseous, reddish, and bluish events, are analyzed in an attempt to determine the possible causes of LTP. Hypotheses considered include effects of earth tides on the moon, low-angle illumination, thermal luminescence, UV heating, solar-particle acceleration by the magnetopause of earth's magnetotail, terrestrial magnetotail bow-shock-front turbulence, cathode luminescence due to magnetotail effects, and solar-flare particle bombardment. Analysis are performed in terms of histograms of the number of observations vs. phase of anomalistic period and of number vs. moon's age, percentage of numbers of observed phenomena and percentage of expected numbers as well as their ratios, and albedo behavior over a lunation period of chosen permanent points in ten specific features. The results indicate that different phenomena may have different causes, strong tidal effects are dubious, correlations with sunrise are most frequent, and the distribution of all LTP sites is distinct from that of deep- and shallow-focus moonquake epicenters.

Cameron, W. S.↗

Unveiling the Stability of Encapsulated Pt Catalysts Using Nanocrystals and Atomic Layer Deposition

Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. Here, in this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al 2 O 3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C 3 H 6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biological and Organic Chemical Decomposition of Silicates

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geo- chemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth surface.

Silverman, M. P.↗

Biological and Organic Chemical Decomposition of Silicates

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geochemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth's surface.

Sliverman, M. P.↗

A Modified Network Alteration Model to Predict Quasi-Static Behavior of the Cross-Linked Polymers During Hydrolytic Aging

Abstract The network alteration theory is utilized to capture the effects of hydrolytic aging on the mechanical integrity of the polymer matrix. Hydrolytic degradation generally considered as a result of two simultaneous chemical phenomena; (i) reduction of the cross-links, and (ii) active chain loss. Assuming the alteration of the chain density is identical to the change of the number average molecular weight along the aging trajectory, the strain energy of polymer matrix can be rewritten as a function of deformation, deformation history, storage time, and aging temperature. The proposed model includes only five physically inspired material parameters. Thus, while it is computationally efficient, it shows good agreement with own experimental data, which performed on various range of accelerated aging temperatures and times. With respect to its computational efficiency, simplicity, accuracy, and interpret-ability, the model is a good choice for advanced implementations in FE programs.

Bahrololoumi, Amir↗

Pouch cells with 15% silicon calendar-aged for 4 years

Small amounts of high-capacity silicon-based materials are already used in the anode of commercial Li-ion batteries, helping increase their energy density. Despite their remarkable storage capability, silicon continu-ously reacts with the electrolyte, accelerating time-dependent cell performance fade. Nevertheless, very limited information is available on the specific consequences of this reactivity for the calendar aging of Li-ion cells. Here, we analyze aging effects on 450 mAh pouch cells containing 15 wt% of Si (and 73 wt% graphite) after storage at 21 °C for four years. We show that severe losses of Si capacity occurred due to particle isolation when cells were stored at high states of charge (SOC), but not when cells were fully discharged prior to storage. Impedance rise was also significantly higher when cells were kept at high SOCs and was mostly due to phenomena taking place at the cathode; the continuous electrolyte reduction at the anode did not lead to a major increase in bulk electrode resistance. A series of post-test characterization provided additional information on the effects of time and SOC on the calendar aging of Si-containing cells. In conclusion, our study highlights the many challenges posed by Si during calendar aging and can inform future studies in the field.

25 ENERGY STORAGE↗

Lifetime estimation of a BWR core shroud in terms of IGSCC

The continued operation of aging Boiling Water Reactors (BWRs) worldwide requires gradually increasing cost of inspection, maintenance, and repair. Intergranular Stress Corrosion Cracking (IGSCC) in sensitized austenitic stainless steel piping first became a major issue for BWRs in the 1980s, resulting in recognition of the susceptibility of reactor internals to IGSCC. Shroud cracking identified in 1993–1994 confirmed that IGSCC of internals is a significant issue for BWRs. IGSCC is a time-dependent, material degradation process, which is caused and accelerated by the presence of residual stresses, material sensitization, irradiation, cold work, elevated temperature, and corrosive environments. This paper emphasizes the importance of accounting for corrosive environments, or more exactly, electrochemical phenomena in modelling IGSCC and predicting the service life of BWR in-vessel components, and stresses the necessity of performing such modeling not just for a single state point under full power conditions, but for the whole operating history of the reactor, including startups and shutdowns. Overall, this paper demonstrates that ignoring electrochemical considerations may result in underestimating component lifetime and lead to unnecessary expenses for inspection and repair.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A review of black carbon in snow and ice and its impact on the cryosphere

Black carbon (BC) has emerged as an important short-lived climate forcer. Due to its light absorption properties, BC can darken the snow/ice surface, affect the energy balance, and further lead to acceleration of the cryospheric melting. By reviewing the recent published literatures, we present an overview of the historical changes, spatial distribution of BC in snow/ice, and how these changes are related to the melting of the cryosphere (e.g., glaciers, snow cover, and sea ice). Ice core records show an abrupt increase of BC concentrations that began in the 1850s and continued throughout the 20th century, which is consistent with an increase in BC emissions owing to industrialization. A decrease in the amount of BC since 1970s in Arctic and European ice cores has been partially attributed to the Clean Air Act. However, in the Himalayas, BC records show a continuous increase during this period. BC concentrations in snow and ice in the mid-latitude regions are one to two orders of magnitude higher than those in the polar regions. In particular, BC concentrations in aged snow and granular ice in ablation areas of mountain glaciers are one to three orders of magnitude higher than those in fresh snow or snowpits in the glacier accumulation areas due to BC accumulation during melting season. BC in the surface snow/ice is responsible for about 20% of the albedo reduction in the Tibetan Plateau during glacier melt season. Globally, observations and modeling results indicate that radiative forcing (RF) induced by BC in snow and ice is highest in the mid-latitudes, ranging from several W m–2 in fresh snow to hundreds of W m–2 in aged snow and granular ice in glacier ablation areas. The large BC-in-snow RF and associated snow albedo feedback lead to an acceleration in the total glacier melt (approximately 20%) and/or a reduction in the duration of the snow cover by several days, resulting in an increase of glacier discharge. Given our limited understanding of the role of BC in cryospheric melting, it is important to synthesize the existing research on the multi-scale processes related to BC in snow and ice to identify the gaps in our understanding of these processes and to propose a path forward to improve the quality of our observations of the aforementioned phenomena to fill these gaps.

Kang, Shichang↗

Aging of Self-Assembled Lead Halide Perovskite Nanocrystal Superlattices: Effects on Photoluminescence and Energy Transfer

Excitonic coupling, electronic coupling, and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a red-shifted collective emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by studying CsPbBr 3 nanocrystal superlattices over time with room-temperature and cryogenic micro-photoluminescence spectroscopy, X-ray diffraction, and electron microscopy. It is shown that a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days of keeping such structures under vacuum. As a result, a narrow, low-energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr 3 nanocrystals develop bulk-like CsPbBr 3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low-energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays. Overall, the aging of CsPbBr 3 nanocrystal assemblies dramatically alters their emission properties and that should not be overlooked when studying collective optoelectronic phenomena nor confused with superfluorescence effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aging matrix visualizes complexity of battery aging across hundreds of cycling protocols

To reliably deploy lithium-ion batteries, a fundamental understanding of cycling aging behavior is critical. Battery aging consists of complex and highly coupled phenomena, making it challenging to develop a holistic interpretation. In this work, we generate a diverse battery cycling dataset with a broad range of degradation trajectories, consisting of 359 high energy density commercial Li(Ni,Co,Al)O 2 /graphite + SiO x cylindrical 21 700 cells cycled across 207 unique cycling protocols. We consolidate aging via 16 mechanistic state-of-health (SOH) metrics, including cell-level performance metrics, electrode-specific capacities/state-of-charges (SOCs), and aging trajectory metrics. We develop a framework using interpretable machine learning and explainable features to generate an aging matrix that visually deconvolutes the complex battery degradation behavior. This generalizable data-driven mechanistic framework simplifies the complex interplay between cycling conditions, degradation modes, and SOH, acting as a hypothesis-generation tool to aid battery users in identifying key degradation regimes for further study and experimentation.

25 ENERGY STORAGE↗

Ultra-fast and sensitive magneto-optical hydrogen sensors using a magnetic nano-cap array

Magnetism in curved nano-geometries has opened a new path to design novel characteristics and phenomena that could greatly impact the future fundamental and applied studies of materials. Here, in this report, a hexagonally-packed array of magnetic nano-caps (or nano-patches, NP) exhibiting unique magnetic anisotropy and optimal nanostructure for fast hydrogen kinetics is explored as a sensing element for the spark-free magnetic-circular-dichroism (MCD) H 2 sensor. The MCD H 2 sensor outperforms the state-of-the-art optical sensors reported to date and satisfies the most challenging performance targets imposed by US Department of Energy. In particular, a Pd 67 Co 33 NP sensor exhibits response time of t 90 < 0.9 s, recovery time of t 10 < 9.0 s over the 1-100 mbar H 2 partial pressure range, and limit of detection (LOD) of ~1 ppm. The LOD improves to <700 ppb, when the signal-to-noise ratio is enhanced by stacking three NP arrays. Using a 30-nm TAF (Teflon AF 2400) polymer coating, the sorption kinetics of the Pd 67 Co 33 /TAF sensor are significantly accelerated, with t 90 < 0.4 s and t 10 < 2.8 s over the same pressure range. When the Pd 67 Co 33 /TAF sensor is further coated with a 100-nm poly(methyl methacrylate) (PMMA) layer, a rapid sorption time of t 90 < 0.5 s, LOD < 1 ppm and excellent sensor accuracy (<2.5% full scale) are maintained, while the sensor obtains strong selectivity against interference gases and moisture and a negligible aging effect. The MCD nano-cap sensor platform may have a great impact on the future deployment of H 2 fuel, H 2 environmental monitoring sensors, and fast proton-based magneto-ionic devices.

Fast and sensitive hydrogen sensors↗