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Aging mechanisms of filled cross-linked polyethylene (XLPE) cable insulation material exposed to simultaneous thermal and gamma radiation

Thermal and simultaneous thermal and gamma radiation aging experiments were conducted on an industry grade cross-linked polyethylene (XLPE) cable insulation material, which is a composite material with XLPE as polymer matrix and various additives and fillers. Reverse engineering was conducted to identify and quantify the material composition given that this information was not revealed by the cable manufacture. Samples were then aged at temperatures of 60, 90, and 115 °C, exposed to gamma radiation for total doses of 0 to 324 kGy, and at dose rates of 0 to 540 Gy/h. Aging mechanisms were studied using various materials characterization techniques including pyrolysis gas chromatography mass spectrometry (Py-GCMS), differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (NMR), and gel-fraction tests. Results show that the flame-retardant components were decomposed into smaller molecules when the material was exposed to gamma radiation, while no changes were observed when the samples were aged thermally without gamma radiation. With exposure to gamma radiation, the crystalline phase of the XLPE were damaged by gamma radiation introducing defects in the crystals, resulting in smaller and less perfect crystals. The dominance of chain scission or chain reformation process largely depends on the chain mobility, which is decided by the aging temperature. Chain scission was seen to dominate when the material was exposed to gamma radiation at 60 °C. Chain cross-linking slightly dominated when the material was exposed to gamma radiation at 90 °C and became more dominant with exposure to gamma radiation at 115 °C. No significant change to the XLPE polymer matrix was observed when the samples were exposed to thermal aging without gamma radiation. Finally, antioxidant is more effective in protecting the XLPE polymer matrix under thermal aging, but less effective with sample exposure to gamma radiation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Sequential versus Simultaneous Aging of XLPE Nuclear Cable Insulation Subjected to Elevated Temperature and Gamma Radiation

Electrical cables constitute a critical component of nuclear power generation. The aging behavior of electrical cable insulation under combined exposure to thermal and radiation stress is not additive, complicating lifetime prediction of cable performance based on sequential accelerated aging. In this work we explore the relative effects of simultaneous and sequential thermal and gamma radiation aging on cross-linked polyethylene (XLPE), which is commonly found in commercial nuclear power plants in the United States. Samples of XLPE were subjected to up to 320 kGy of gamma irradiation at a dose rate of 300 Gy/hr in two heating scenarios. In the first, simultaneously-aged samples were heated at 150°C during irradiation. In the second, sequentially aged samples were heated at 150°C for designated durations followed by corresponding periods of irradiation without heating. The mass, total color difference, and density were characterized to quantify aging of the insulation polymer. Sequential aging is hypothesized to be more damaging to XLPE insulation due to an increased trend in mass gain, total color difference, and density.

Cross-linked polyethylene, XLPE, nuclear cable, ac↗

Repurposing Post-Consumer Polyethylene to Access Cross-Linked Polyethylene with Reprocessabilty, Recyclability, and Tunable Properties

Polyethylene (PE) is the most widely produced plastic but accumulation and resistance to degradation has significantly contributed to the plastic waste crisis. Upcycling has presented promising solutions to transform PE waste into value-added products. In this study, mixed post-consumer PE was successfully repurposed into reprocessable and chemically recyclable cross-linked polyethylene (XLPE). This process involved converting PE into telechelic oligomers, followed by repolymerization using a hybrid cross-linking system consisting of a dynamic cross-linker 2,4,6-triethoxy-1,3,5-triazine (TETA) and non-dynamic cross-linker tris(6-isocyanatohexyl)isocyanurate (Tri-HDI). In the resulting XLPE, TETA facilitated iterative reprocessing with minimal property degradation across cycles, whereas Tri-HDI helped preserve functional performance throughout service life. Compared to PE, XLPE exhibited enhanced mechanical properties, reduced creep deformation under application-relevant temperatures, and high temperature structural stability. Notably, copolymerizing PE oligomers with commercial macrodiols was employed to create composite XLPEs, enabling tuning material properties. After use, XLPE can be efficiently and selectively depolymerized under mild conditions, even when mixed with commercial insulator cables. This depolymerization allows for the recovery of the constituent building blocks, enabling purification and subsequent repolymerization for reuse. This approach demonstrates the potential of repurposing plastic waste into sustainable materials and fostering the development of a circular economy.

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMI↗

On the mechanism of radiation and thermal-induced degradation of the insulation cables in nuclear power plants-the presence of long-lived polyenyl C-centered radicals

Radiolytically and thermally produced long-lived polyenyl C-centered radicals in the nuclear power plants’ insulation cables are detected and measured after more than 45 months of aging since the irradiation and the thermal treatment. Electron Paramagnetic Resonance (EPR) results of the irradiated Cross-linked Polyethylene (XLPE) and Ethylene Propylene Rubber (EthProRu), used as primary insulation materials at Nuclear Power Plants (NPP), clearly demonstrate the presence of polyenyl radicals along with allyl and peroxyl radicals. The yields of these free radicals are dose-rate dependent. EPR results also show the presence of the long-lived polyenyl along with allyl and peroxyl free radicals in the thermally treated XLPE, and EthProRu. These free radicals can cause a major failure in the performance of these cables in NPPs. Besides, the results showed the enhancement in the oxidation reactions due to the migration of copper ions from the conductor to the bulk of the insulation. Further, this study also shows that the oxidation index (OI) and Elongation at Break (EAB) increases and decreases respectively at higher doses and temperatures.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Application of Cable Condition Monitoring Technologies to Assess Age-Related Degradation of Industrial Cables Installed in Harsh Environments

The aging of electrical cables has been the subject of substantial research and development (R&D) projects performed by national and international laboratories, universities, and private organizations for many years. This R&D was conducted to develop guidance, equipment, and techniques to support aging management of in-service cables in industrial facilities such as nuclear power plants, research reactors, waste facilities, and fuel fabrication plants. Through these research efforts, condition monitoring technologies have been developed that can determine the severity of age-related degradation that occurs in industrial cables and insulation polymers during service. This paper summarizes the results of aging assessments that were performed for cables installed in two U.S. nuclear power plants, one a pressurized water reactor and one a boiling water reactor. These cables had been in service for over 40 years and during plant operation were exposed to harsh environmental conditions including elevated temperatures and radiation. For these assessments, a comprehensive series of measurements was performed to assess the aged condition of the cables. These cables came from different manufacturers, were manufactured in different years, and were constructed with a variety of jacket and insulation polymers including chloro-sulfonated polyethylene (CSPE), cross-linked polyethylene (XLPE)/cross-linked polyolefin (XLPO), neoprene, and ethylene propylene rubber (EPR). The goal of these assessments was to determine the current aged condition of the cable polymers and provide an estimate of how long the cable insulation materials could remain exposed to their in-service environmental conditions before reaching their end-of-life condition. Both nuclear power plants have received license renewals to extend their operation from 40 to 60 years, and the utilities need objective evidence to show that critical components such as cables will be able to function safely and reliably during the extended operating period. Furthermore, the results of these assessments showed that the cables exhibited different aged conditions depending on the type of polymers they were constructed with and the environment they were exposed to during service. Some of the cables and insulation polymers showed signs of significant age-related degradation and were estimated to have approximately 5 years of remaining service life. Other cables exhibited no signs of significant age-related degradation and were estimated to have 50 years or more of remaining service life. Using the results of these cable aging assessments, plant personnel were able to (1) determine the overall aged condition of cables and insulation polymers using objective test results, (2) identify aged or degraded cables before they caused operability issues, and (3) avoid unnecessary and costly replacement of cables that can continue to operate safely and reliably.

36 MATERIALS SCIENCE↗

Color Change During Thermal Degradation of Polyolefin Electric Cable Insulations

Color change of electric cable insulations used in nuclear power plants (NPPs) is a non-destructive, quick and inexpensive technique to measure degradation. Quantification of color change is facilitated by a light booth of CIE D65 illuminant, a commercial camera and open-source software ImageJ with micaToolbox plugin. Yellowness index (YI) and total color difference (?E) are calculated from calibrated photos of a white cross-linked polyethylene (XLPE) and a black ethylene-propylene rubber (EPR) based specimens aged at 110°C, 121°C, 136°C and 150°C after 1~640 days. Using the same setup and software, pixelwise ?E profile is determined for the cross-sectional photo of a white EPR specimen, where heterogeneous aging is detected.

cable aging, color analysis↗

Application of Principal Component Analysis for the Monitoring of the Aging Process of Nuclear Electrical Cable Insulation

To ensure the safe operation of nuclear power plants (NPPs), it is critical to understand how NPP electrical cable insulation will degrade under different service environments. In this study, various nondestructive examination methods were selected to evaluate degradation of electrical cable insulation after aging. Elongation at break, indenter modulus, relaxation constant, mass change, total color difference, and carbonyl index were collected stepwise on cross-linked polyethylene (XLPE) cable insulations after predetermined exposure intervals. Three different insulation aging scenarios were investigated: 1) simultaneous irradiation and heating at 150°C, 2) heating at 150°C followed by corresponding times of irradiation at ambient temperature, and 3) irradiation at ambient temperature followed by heating at 150°C for the same duration. A constant dose rate of 300 Gy/hr was selected with a total gamma irradiation absorbed dose up to 320 kGy. To gain insight into the long-term performance of NPP electrical cable insulation, principal component analysis (PCA), a data-driven approach, was utilized to identify key indicators of cable insulation degradation. By reducing the dimensionality of the data while retaining degradation information, PCA was used to highlight the changes in the measured properties under gamma irradiation according to total absorbed dose and the different aging scenarios.

Li, Donghui↗

Principal Component Analysis of Nuclear Cable Insulation Subjected to Elevated Temperature and Gamma Radiation

In nuclear power plants (NPPs), the aging of electrical cable insulation occurs due to elevated temperature, ionizing radiation, and other environmental factors. To ensure the safe and efficient operation of NPPs, determination of key indicators of cable aging is critical to predict the remaining useful lifetime of electrical cable insulation. In this work, the effects of simultaneous and sequential thermal and gamma radiation on the aging of cross-linked polyethylene (XLPE) electrical cable insulation are investigated. The chemical changes of the insulation were monitored non-destructively through the use of Fourier transform infrared (FTIR) spectroscopy. The FTIR spectra were measured stepwise after predetermined exposure intervals, with a total irradiation dose up to 320 kGy at a dose rate of 300 Gy/hr in two exposure scenarios; simultaneously aged samples were heated at 150 °C during irradiation, while sequentially aged samples were heated at 150 °C for designated durations followed by corresponding times of irradiation at ambient temperature. A data-driven approach using principal component analysis (PCA) was developed to highlight changes in the carbonyl region of the infrared spectra of the aged samples due to oxidation and to differentiate oxidation rates under the simultaneous and sequential exposure conditions. Findings indicate that the sequential aging scenario may be more conservative than the simultaneous aging scenario for XLPE electrical cable insulation.

Li, Donghui↗

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↗

Assessment of EPRI’s Tan Delta Approach to Manage Cables in Submerged Environments: Statistical Review of EPRI Data

Research conducted by the Electric Power Research Institute (EPRI) and other research institutions have concluded that water-trees are one of the leading degradation mechanisms that contribute to the loss of dielectric insulation strength in medium-voltage cable insulating materials in wet or submerged environments. The electrochemical reactions are caused by the combined effect of water presence and relatively high electrical stress. Records of cable failures provided by the licensees in response to Generic Letter (GL) 2007-01 (NRC 2007) have called into question the reliability of medium voltage cables in wetted or submerged environments. EPRI’s dissipation factor or Tan Delta testing guidelines and acceptance criteria have been adopted by most nuclear power plant operators as the primary tool for condition monitoring of medium voltage cables in wet or submerged environments. EPRI has been collecting member data since late 2009 to analyze and provide feedback to members, validate the EPRI-developed acceptance criteria guidelines, support analysis of test results, recommend appropriate actions for the "action required" category, and gather candidate cables for EPRI-sponsored forensic research on causes for insulation degradation. EPRI has collected data from 37 nuclear sites, which represent 44 operating units. The test results have been organized by insulation type, such as cross-linked polyethylene (XLPE); butyl rubber; black, pink, and brown ethylene-propylene rubber (EPR); and compact insulation (black and pink EPR)1. The data have been analyzed, and follow-up information was obtained from members for “action required” test results. EPRI has also performed correlations between Tan Delta tests and the information gathered under the EPRI forensic research on medium-voltage cables. In addition, EPRI has developed guidance by cable insulation type on how to systematically analyze Tan Delta test results. The analysis described here reviewed the two primary EPRI reports (EPRI 3002000557 and EPRI 3002005321) as well as two precedent EPRI reports (EPRI 1028262 and EPRI 1021070) that were cited in the primary reports. The principal results and conclusions from the project analyses are provided.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Dose Rate Effects on Degradation of Nuclear Power Plant Electrical Cable Insulation at a Common Dose

The intent of this report is to address an identified knowledge gap in relating accelerated aging of nuclear electrical cables to service aging: dose rate effects (DRE). Here, DRE refer to gamma radiation-induced polymer degradation being a function of dose rate in addition to total absorbed dose. The concern raised is that historical qualification conducted at higher dose rates to simulate service lifetime may underestimate insulation degradation that occurs at lower dose rates in service. In the work described herein, common nuclear cable insulation materials—cross-linked polyethylene (XLPE) and ethylene propylene diene elastomer (EPDM)—were subjected to accelerated aging at ambient temperature (26°C) at different gamma dose rates of 100, 200 and 1800 Gy/h for select exposure durations to achieve constant total doses of 170, 210 and 300 kGy to evaluate DRE. First, the cable insulation material types investigated are described. Then, the accelerated aging experimental process involving gamma irradiation applied to the insulation specimens at room temperature and different dose rates is discussed. Then, the experimental characterization techniques used to perform this work are elucidated. These include elongation at break (EAB), mass change, yellowness index (YI), carbonyl index (CI), density, indenter modulus (IM), and relaxation constant (t). Theory of polymer degradation is discussed, and characterization results and discussion are provided. Finally, concluding remarks are made. The findings from this work and cited prior work reveal that DRE are material dependent, even between similar material categories (e.g., XLPE). In the case of the EPDM studied, degradation of ductility was observed to be greater at higher dose rate for the same total dose, indicating accelerated gamma aging to be more conservative than extended aging. Thus, conclusions regarding the conservatism of historical qualification likely require additional consideration for specific materials and conditions in question. The results of this study support the contention that, due to inherent limitations and uncertainties associated with prediction of cable remaining useful life from accelerated aging experiments, trending of installed cable insulation health status will be more practical and useful for safe and efficient cable aging management repair and replace decisions than lifetime prediction from historical qualification. The combination of material robustness demonstrated by the qualification process and ongoing monitoring of cable health status combine to provide confidence in continued safe use of existing nuclear cables. Additional research into effective and efficient condition monitoring methods for non-destructive evaluation of installed cables is needed to support aging cable management, including material studies to inform interpretation of measured results.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Evaluation of Oxygen Consumption as a Sensitive Measure of Electrical Cable Polymer Insulation Degradation

Polymers used as dielectric materials in nuclear grade electrical cables, such as cross-linked polyethylene (XLPE) and ethylene-propylene rubber (EPR), are long-lived and durable. Estimating the decades-long useful service life of polymers experimentally in a feasible timeframe of weeks or months requires greatly accelerated aging in the laboratory at elevated temperatures and/or gamma dose rates. Many limitations of accelerated aging, such as due to artefacts of the process including diffusion limited oxidation and dose rate effects, have been identified that can make accurate lifetime prediction at service conditions challenging. This can be due to differences in degradation mechanisms between rapid and extended aging or to the presence of induction periods during which early aging is undetectable using common metrics of polymer insulation characterization such as tensile elongation at break. Conceptually, an ideal measure of aging would track clearly and predictably with material changes throughout the lifecycle of the evolving material state from early aging through end of useful life. With such a metric accelerated aging could be performed at much milder conditions, conditions closer to those found in long term service, and end of life calculated from the early data. Oxygen consumption has previously been proposed as a sensitive measure of insulation polymer oxidation that might meet such desirable characteristics. In this work, nuclear cable insulation samples of the two most common types, XLPE and EPR, from two of the most sourced manufacturers, RSCC and The Okonite Company, were subjected to gamma irradiation at dose rates of 100, 200, and 300 Gy/hr for up to 42 days at 26°C. The aged samples were used to evaluate oxygen consumption as a sensitive measure of aging for these materials and these conditions. For comparison and validation, the aged samples were also characterized using the more conventional tests of mass change, density, carbonyl index, and yellowness index. For both materials, oxygen consumption during irradiation was found to track consistently with applied dose—oxygen consumption rate was linear with time. Mass change and carbonyl index were also clearly proportional to exposure dose. Yellowness index, a surface sensitive measure, was observed to increase linearly with dose at low exposure levels before plateauing. Sample density was not observed to change under the conditions explored. Oxygen consumption was found to be a particularly sensitive metric to measure the degradation of polymeric cable insulation exposed to radiation. Oxygen consumption was compared to Arrhenius and time-temperature-superposition methods for activation energy calculation using literature date and found to be a useful and viable alternative for lifetime prediction. The techniques developed in this work are anticipated to be valuable in the estimation of insulation aging rates under mild conditions approaching service conditions. Direction comparison of useful life prediction by oxygen consumption with prediction via Arrhenius methodology for thermal aging and existing methods for radiation and combined thermal/radiation aging would serve to further validate this promising approach and refine our understanding of material-specific aging rates.

36 MATERIALS SCIENCE↗

Consideration of Decabromodiphenyl Ether Flame Retardant in Thermal and Radiation Aging of Crosslinked Polyethylene Cable Insulation

Decabromodiphenyl ether (decaBDE) has been used as a flame-retardant additive in nuclear-grade electrical cable insulation. However, decaBDE has been identified as a persistent, bioaccumulative and toxic (PBT) substance, leading to regulatory scrutiny. On January 6, 2021, the Environmental Protection Agency (EPA) published a final rule to phase out decaBDE. The 2021 rule set a two-year compliance deadline for “processing and distribution in commerce of decaBDE for use in wire and cable insulation in nuclear power generation facilities.” In recognition of industry concerns following a sudden discontinuation of decaBDE-containing Class 1E wire and cable essential for nuclear power operations and the time needed for qualifying the individual components using the alternative insulation technology, an extended compliance deadline was set in the finalized amendments to the 2021 rule as published by the Environmental Appeals Board on November 12, 2024. The 2024 rule set the compliance deadline for processing and distributing decaBDE-containing wire and cable insulation until the end of the service life of these materials. Since decaBDE has long been relied upon as the flame retardant in one of the most common cross-linked polyethylene (XLPE) nuclear cable insulation formulations, RSCC Firewall III insulation, questions have naturally arisen regarding whether changes in cable performance might be expected for XLPE containing a decaBDE alternative, especially for safety-related cables that must perform their safety function in a design basis event such as a loss of coolant accident.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗