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Zwoster, Andy

Publications and source records attributed to Zwoster, Andy.

Assessment of Amine-Based CO2BOLs for Direct Air Capture

Direct air capture (DAC) technologies extract CO 2 from the atmosphere for CO 2 storage, or utilization. Capturing CO 2 from the air is the most expensive application of carbon capture because CO 2 in the atmosphere is very dilute. There are limited number of CO 2 capture technologies for DAC application. This project aims at developing an energy efficient technology for DAC, leveraging two PNNL’s chemistries (solid and liquid CO 2 capture). Three CO 2 capture sorbents consisting of amine based CO 2 BOLs immobilized in mesoporous silica were designed, synthesized, and tested. These sorbents had ~ 19-23 wt.% amine loadings which is lower than typical amine-based silica sorbents. The surface area and pore volumes of these solid supported CO 2 BOLs are lower compared to those of the pristine silica support. The CO 2 capture performance of these materials was significantly lower than the typical silica supported amines due to low amine loading and higher molecular weight with low amine density. These results show that immobilize CO 2 BOLs in silica are not viable materials for removing CO 2 from ambient air. This project also designed, synthesized at tested liquid solvents for DAC application. Solvent properties that is vapor pressure, CO 2 uptake capacity, kinetics, and viscosity for three novel solvents were evaluated. The CO 2 uptake capacity for one of the most promising amine-based solvent BEPBEGDA was the highest at 13.2 wt% corresponding to 97 mol%. The vapor pressure of the BEPBEGDA solvents were very low at 80 °C compared to other solvents making them suitable for DAC application. The effect of humidity on the CO 2 capture performance of these solvents was evaluated which shows that presence of moisture doesn’t have a negative effect on the CO 2 uptake performance but makes it slightly better. The performances of these solvents were slightly below that of the 0.1M NaOH solution tested under similar conditions. Despite of the slightly lower CO 2 uptake, it is expected that these liquid solvents will have lower regeneration temperature and minimum evaporative losses due their low vapor pressure. Future work will focus on optimization of the liquid solvents for DAC application to improve both CO 2 capture efficiency and capacity without viscosity and vapor pressure increase. Testing of these solvents under DAC conditions using a gas liquid contactor that mimic industrial applications is needed. Solvent cost projection, techno-economic analysis and life cycle analysis are required to evaluate economic viability of this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Energy-effective and low-cost carbon capture from point-sources enabled by water-lean solvents

Aqueous amines, as the most mature carbon capture technology, are subject to high energy and cost penalties due to the large water content in their formulations. Emerging technologies are in demand to enable a transition to a low-carbon global economy. However, rigorous process modeling and techno-economic analyses are limited for emerging carbon capture technologies. Here, four CO 2 -Binding Organic Liquids (CO 2 BOLs), all water-lean solvents were presented as promising options towards energy-effective and low-cost carbon capture from point sources. Rigorous solvent property and process models were developed in Aspen Plus for a coal-fired power plant with CO 2 BOL-based carbon capture unit. Techno-economic analyses were conducted in 2018 US pricing basis. The results suggest that water-lean formulations can minimize water condensation and vaporization, leading to a 36% energy saving compared with aqueous amines. Indeed, these CO 2 BOLs can capture up to 97–99% CO 2 from coal fired plant. The estimated carbon capture cost is about $40/tonne CO 2 at 90–97% carbon capture rate, about 12–23% less expensive than the conventional aqueous amine technology. The comparison between these CO 2 BOLs showed that in addition to vapor liquid equilibrium and kinetics (key properties for aqueous solvents), viscosity, volatility, and hydrophobicity, also have strong impacts on the performance of water-lean solvents. The methods presented in this work can be used to evaluate other emerging carbon capture technologies, while the results linking costs and performance of carbon capture solvents with their properties. Additionally, this work identifies research directions and targets for further reductions in total costs of capture from either cost or energy perspectives for these leading water-lean solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dose Rate Effects in the Aging of Nuclear Cable Insulation Subjected to Gamma Radiation

In nuclear power plants (NPPs), the aging of polymer-based electrical cable insulation must be effectively monitored to ensure the safe and reliable operation of NPPs. Gamma radiation is one of the main environmental stressors causing degradation of cable insulation. For a given total dose of absorbed gamma radiation, damage due to gamma irradiation may be dose rate dependent. The purpose of this work is to confirm whether a dose rate effect exists for the cable insulation made by crosslinked polyethylene (XLPE) and ethylene propylene rubber (EPR), quantify the relationship between degradation rate and dose rate, and explore the correlation of different measured properties. The dose rate effects at 1800 Gy/h, 200 Gy/h, and 100 Gy/h using 60Co gamma irradiation on cable aging was studied. Different types of cable insulation, including two XLPEs and one EPR, were irradiated at the different dose rates with a total dose around 300 kGy at 26 °C. The properties of unirradiated and irradiated samples were characterized by mass change, yellowness index, and other ongoing measurements. Dose rate effects were observed for mass change data of XLPE and EPR.

Li, Donghui↗

Evaluation of a Third Generation Single-Component Water-Lean Diamine Solvent for Post-Combustion CO 2 Capture

Here this study describes a comprehensive evaluation of a recently developed water-lean diamine solvent, N1-(2-ethoxyethyl)-N2, N2-diisopropylethane-1,2-diamine (2-EEDIPEDA), to probe its potential post-combustion CO 2 capture performance. This evaluation includes (1) fundamental sorption characterization such as vapor-liquid equilibria, sorption kinetics and viscosity impacts; (2) continuous capture characterization using laboratory scale flow system using flue gas simulant; as well as (3) technoeconomic analysis of the capture process at industrial scale with projections for critical capture performance metrics. Using this evaluation, we compare the performance of 2-EEDIPEDA to our current leading water-lean amine-based solvent, 2-EEMPA, using the same baseline process plant configuration/pricing. From this comparison, we observe lower total cost of capture as low as $46.8/tonne CO 2 with 2-EEDIPEDA (20% cheaper than CANSOLV), as a direct result of solvent chemistry tuning leading to notable cost savings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlation of Diffusion Limited Oxidation to Color Difference in Accelerated Aging of Electrical Cable Insulation

Diffusion limited oxidation (DLO) as a phenomenon has complicated material lifetime predictions from accelerated aging studies. Many methods to analyze DLO have been developed in recent years. However, an analytical tool for high throughput and low-cost analysis of DLO affected samples remains absent from the literature. Color differences in polymers exposed to oxidative conditions have recently been observed and correlated to increased concentrations of oxidation products. Herein, total color difference was utilized to rapidly quantify DLO in ethylene propylene rubber (EPR) polymeric cable insulation specimens. Insulation specimens were aged at 121 °C, 136 °C, 150 °C, and 165 °C and a 10% ?E*ab difference between the specimen edge and specimen center was used as the threshold for DLO. Based on these specifications DLO was observed in EPR insulation specimen at temperatures of 136 °C and above, with an increasing degree of DLO observed as the time of exposure increased. The method presented in this work represents a quantitative and high-throughput method for the investigation of DLO with a low cost barrier for entry.

diffusion limited oxidation, DLO, nuclear, electri↗

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↗

Detection of diffusion limited oxidation in thermally aged ethylene propylene rubber cable insulation material

The lifetime prediction of electrical cable insulation in nuclear power plants (NPPs) is primarily based on accelerated aging. Polymeric insulation exposed to accelerated aging at high temperatures may demonstrate diffusion limited oxidation (DLO) where oxygen within the material is consumed faster than can be supplied by diffusion from the surrounding air. This situation leads to equilibrium oxidation at the exposed surfaces and limited oxidation away from the surfaces. Therefore, DLO results in a heterogeneously aged material which can lead to underestimation of lifetime for in-service cable insulation. In this study, the presence of inhomogeneous aging caused by DLO was evaluated on cross-sectioned cable insulation specimens made of ethylene propylene rubber (EPR). The studies were performed on thermally aged specimens (165 °C, 1 day and 165 °C, 16 days) using local measurement techniques including nanoindentation, micro-Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) - energy dispersive spectroscopy (EDS). All the results indicate some degree of heterogenous aging, with 165 °C, 16 days, aging demonstrating highest degree of oxidative degradation on the inside edges presumably caused due to copper catalyzed oxidation.

Pallaka, Madhusudhan Reddy↗

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↗

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↗

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

Electrical cables are integral to power, control, and instrumentation systems within nuclear power plants (NPPs). Exposure of cable systems within nuclear containment to elevated temperatures and gamma radiation during decades-long operation of NPPs can lead to degradation of cable polymeric insulation. Prediction of nuclear cable insulation degradation is complicated as thermal and radiation stress are not additive. In this work, we explore the relative effects of simultaneous and sequential thermal and gamma irradiation on the aging of ethylene-propylene-diene (EPDM) elastomer insulation to better understand realistic scenarios of cable insulation degradation. Cable insulation samples of EPDM were subjected to up to 320 kGy of gamma radiation at a dose rate of 300 Gy/hr in two heating scenarios: (1) simultaneously aged samples were heated at 150°C during irradiation and (2) sequentially aged samples were heated at 150°C for designated durations followed by corresponding periods of irradiation at ambient temperature. The mass, tensile elongation at break, and carbonyl index were assessed to quantify aging of the polymers. The simultaneous aging scenario was found to the more severe of the two for EPDM insulation degradation.

ethylene-propylene-diene elastomer, EPDM, nuclear ↗

A single-component water-lean post-combustion CO 2 capture solvent with exceptionally low operational heat and total costs of capture – comprehensive experimental and theoretical evaluation

A comprehensive evaluation of a recently developed water-lean amine-based solvent, namely N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (2-EEMPA), has been performed to analyze its post-combustion CO 2 capture performance. This evaluation comprises (1) fundamental characterization of the solvent–CO 2 interaction using vapor–liquid equilibria, kinetics and viscosity measurements; (2) process characterization of the CO 2 capture performance as measured in a laboratory scale continuous flow system and via Aspen Plus® simulation using a flue gas simulant; as well as (3) a full techno economic analysis of the capture process at industrial scale with corresponding projections of critical metrics. This paper summarizes the many parts of this comprehensive evaluation and shows how the various parts come together to empower validated conclusions about its process performance. Notably, it is projected that this solvent can operate at a regeneration heat rate of 2.0 GJ per tonne CO 2 for post-combustion capture, and at a total cost of capture of $50.6/tonne CO 2 . Overall, with further process optimization significant reductions in the capture cost are predicted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗