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Reactor antineutrino flux and anomaly

Reactor antineutrinos have played a significant role in establishing the standard model of particle physics and the theory of neutrino oscillations. In this article, we review the reactor antineutrino flux and in particular the reactor antineutrino anomaly (RAA) coined over a decade ago. RAA refers to a deficit of the measured antineutrino inverse beta decay rates at very short-baseline reactor experiments compared to the theoretically improved predictions (i.e. the Huber–Mueller model). Since the resolution of several previous experimental anomalies have led to the discovery of non-zero neutrino mass and mixing, many efforts have been invested to study the origin of RAA both experimentally and theoretically. The progress includes the observation of discrepancies in antineutrino energy spectrum between data and the Huber–Mueller model, the re-evaluation of the Huber–Mueller model uncertainties, the potential isotope-dependent rate deficits, and the better agreement between data and new model predictions using the improved summation method. Importantly, these developments disfavor the hypothesis of a light sterile neutrino as the explanation of RAA and supports the deficiencies of Huber–Mueller model as the origin. Looking forward, more effort from both the theoretical and experimental sides is needed to fully understand the root of RAA and to make accurate predictions of reactor antineutrino flux and energy spectrum for future discoveries.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Neutron time-of-flight reflectometer GRAINS with horizontal sample plane at the IBR-2 reactor: Possibilities and prospects

A new time-of-flight neutron reflectometer GRAINS with a horizontal sample plane (vertical scattering plane) has recently been put into operation at the pulsed reactor IBR-2 (JINR, Dubna). The scattering geometry applied makes it possible to carry out complex studies of nanostructured interfaces in solid and liquid states by measuring the specular reflectivity and the intensity of diffuse scattering of thermal neutrons from open surfaces and hidden interlayer boundaries, including solid-liquid interfaces, over a wide momentum transfer range. The classical analysis of specular reflectivity allows one to determine the scattering length density profile in the object under study in a direction perpendicular to the interface for a thickness of ~100 nm with a resolution of 1 nm. The analysis of off-specular (diffuse) neutron scattering makes it possible to characterize lateral correlations on surfaces and interlayer boundaries. The paper summarizes the first experience in the operation of the GRAINS reflectometer. The instrument characteristics are presented together with the possibilities for experiments with solid and liquid samples illustrated with simple systems. Further steps for the development of the reflectometer are discussed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Nuclear Data to Reduce Uncertainties in Reactor Antineutrino Measurements

The large quantities of antineutrinos produced through the decay of fission fragments in nuclear reactors provide an opportunity to study the properties of these particles and investigate their use in reactor monitoring. The reactor antineutrino spectra are measured using specialized, large area detectors that detect antineutrinos through inverse beta decay, electron elastic scattering, or coherent elastic neutrino nucleus scattering; although, inverse beta decay is the only demonstrated method so far. Reactor monitoring takes advantage of the differences in the antineutrino yield and spectra resulting from uranium and plutonium fission providing an opportunity to estimate the fissile material composition in the reactor. Recent experiments reveal a deviation between the measured and calculated antineutrino flux and spectra (the reactor anomaly) indicating either the existence of yet undiscovered neutrino physics, uncertainties in the reactor source term calculation, incorrect nuclear data, or a combination of all three. To address the nuclear data that impact the antineutrino spectrum calculations and measurements, an international group of over 180 experts in antineutrino physics, reactor analysis, detector development, and nuclear data came together during the Workshop on Nuclear Data for Reactor Antineutrino Measurements (WoNDRAM) to discuss nuclear data needs and achieve concordance on a set of recommended priorities for nuclear data improvements. Three topical sessions focused on the reactor source term, the antineutrino spectrum, and the detector response, provided a forum to gain consensus amongst the participants on the most important data improvements to address two goals: 1) understand the reactor anomaly and 2) improve the ability to monitor reactors using antineutrinos. This report summarizes the outcomes of the workshop discussions and the recommendations for nuclear data efforts that reduce reactor antineutrino measurement uncertainties.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

In-Line Method for Calculating Peak Neutron Absorption by Fission Products Following a Change in Reactor Power

When the power level in an operating reactor is reduced the concentration of xenon-135 and samarium-149 temporarily increases as the nuclides (and their immediate precursors) equilibrate to the new power level. During this period, the increased inventory of these fission products causes an insertion of negative reactivity that can last for tens of hours. Understanding and predicting this transient reactivity effect is important in reactor design and operation. Explicit depletion calculations are often used to predict the reactivity behavior following a power change. However, these calculations require many time-steps to fully resolve the reactivity trend, and are correspondingly expensive. In 2010 an in-line method for estimating the peak xenon mass in a core following shutdown was described. However, there is no guarantee that the peak negative reactivity condition for a core will occur at peak xenon mass. Therefore, in this summary, we extend this original work using a new method that can predict the peak neutron absorption rate in the core due to {sup 135}Xe and {sup 149}Sm following any reduction in power. The proposed method can also be used to calculate the peak positive reactivity transient due to an increase in reactor power, but this scenario is of less interest in most reactor design applications. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Bond Strength of Plasma Sprayed Zr Diffusion Barrier on U-Mo Fuels

The United States government is continually committed to strengthening nuclear security and nonproliferation for reducing the threat of radioactive materials acquisition by terrorists. To meet this important mission, the US Department of Energy and National Nuclear Security Agency's (NNSA) Office of Material Management and Minimization (M{sup 3}) Reactor Conversion Program (CONVERT) seeks to minimize the use of highly enriched uranium (HEU) in civilian applications through work with governments and facilities around the world to convert research reactors to the use of non-weapons-usable low enriched uranium (LEU) fuels. Each reactor converted not only eliminates the need for HEU at civilian sites, but also reduces the amount of HEU being manufactured, stored, and transported, where the nuclear material is most vulnerable. In instances where suitable LEU fuels do not exist for the conversion of particular reactors, CONVERT contributes to development of new LEU fuels. Currently, the CONVERT Program is committed to development of a high-density U-Mo fuel that will be able to convert high performance research reactors, while establishing an efficient and economic fabrication capability to manufacture the fuel. To that end, Los Alamos National Laboratory (LANL) has been tasked with development of a method to affix zirconium (Zr) metal fuel diffusion barrier via plasma spraying, which will prevent a reaction between the U-Mo fuel and the 6061 aluminum cladding. A successful diffusion barrier requires adequate Zr layer thickness, uniform coverage, sufficient bonding at the Zr/fuel and Zr/aluminum cladding interface, and maintenance of the original nuclear fuel properties i.e. physical dimensions, alloy composition and dispersion, crystallographic phase concentration, neutronics, etc. This work outlines development of the Zr plasma spray processing techniques, parameters affecting the diffusion barrier/nuclear fuel bond strength, and characterization of the Zr diffusion barrier. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Elucidating the Roles of Electric Fields in Catalysis: A Perspective

This Perspective illustrates how the presence of internal and external electric fields can affect catalytic activity and selectivity, with a focus on heterogeneous catalysts. Specifically, experimental investigations of the electric field influence on catalyst selectivity in pulsed field mass desorption microscopes, scanning tunneling microscopes, probe–bed–probe reactors, continuous-circuit reactors, and capacitor reactors are described. Through these examples, we show how the electric field, whether externally applied or intrinsically present, can affect the behavior of a wide number of materials relevant to catalysis. Here, we review some of the theoretical methods that have been used to elucidate the influence of external electric fields on catalytic reactions, as well as the application of such methods to selective methane activation. In doing so, we illustrate the breadth of possibilities in field-assisted catalysis.

03 NATURAL GAS↗

Benefits of Trash-to-Gas Versus Jettison of Waste Via Trash-Lock for Mars Transit

Human exploration missions to Mars pose difficulties due to the significant waste that will be generated during transit, which will need to be carried along or disposed of in some fashion. Waste removal from the spacecraft decreases the spacecraft’s mass as well as the associated logistic items necessary for storing the waste. A mission propellant analysis was performed to highlight the mass benefits that may be accessed via waste removal. The propellant mass savings were determined for different waste removal rates (2.9 – 11.6 kg/day) with the highest removal rate leading to the greatest propellant savings of 7,785 kg for an 850-day round-trip mission. Due to these benefits, two methods for waste reduction were studied for the 850-day Mars mission: Trash-to-Gas (TtG) and physical jettison via a trash-lock. The trash-to-gas methods considered were combustion, steam reforming, and pyrolysis, which convert waste into ventable gases (e.g., CO2, CO, CH4, etc.). Combustion and steam reforming require a co-reactant (O2 and/or H2O). Therefore, additional processing units or integration with the spacecraft’s environmental control and life support system (ECLSS) are required to facilitate recycle of the pertinent species. In contrast, pyrolysis is a purely thermal degradation process, which can operate as a standalone system; however, a lower percentage of waste is gasified with pyrolysis. The study herein compares standalone TtG (e.g., Advanced Organic Waste Gasifier, Plasma Pyrolysis, etc.), integrated TtG-ECLSS (e.g., Orbital Syngas Commodity Augmentation Reactor, Incineration/Gasification, etc.), and physical jettison. Each system’s mass, volume, power, and cooling requirements were compared via an equivalent system mass (ESM) analysis to ascertain potentially promising technologies that can achieve efficient waste removal while minimizing their own spacecraft load. This study highlights the advantages and disadvantages of the different waste management technologies and provides recommendations on the promising technologies based on the ESM metric and propellant mass savings.

Jettison↗

Q3 Report for FY25 Theory and Simulation Performance Target: Development of an integrated modeling framework for fusion reactor design and assessment

This report describes the work and activities carried out towards the completion of each of the following milestones in FY25 Q3: 1. Demonstrate workflow for generating self-consistent CESOL plasma profiles + first wall and divertor loading prediction and generate the CAT plasma and neutron loading needed for further engineering analysis. • Benchmark between two first wall heat flux mapping methods, identify importance of various heat flux sources and physics impact of using fully coupled CESOL vs post-analysis evaluation. 2. Generate medium fidelity parametrized CAD. • Generate parametrized CAD components for the CAT example case via either user-defined modules called within the geometry generation or by defeatured/parametrized CAD, including DCLL blanket matched to divertor boundary and magnets. Define materials, labels, and boundary conditions for passing the mesh to CFD tools. 3. Demonstrate multiphysics magnet analysis. • Demonstrate magnet analysis workflow called from the FREDA workflow, and 4. Demonstrate nuclear analysis. • Add model to OpenFOAM and/or other codes possibly including Diablo to account for tritium diffusion in solids.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

TREAT HODOSCOPE – A Predictive Simulation Model

The Transient Reactor Test Facility (TREAT) reactor is being restarted after over two decades of standby operation. TREAT is designed to test the time-dependent behavior of nuclear fuel during simulated reactor accidents. One of the principle data collection systems of TREAT is the fast neutron hodoscope which is used to observe the motion of the fuel test specimen as it is being damaged, deformed, or melted over the course of the power transient. The hodoscope is a grid of ex-core collimator channels paired with a bank of fast neutron sensitive radiation detectors. These detectors have historically been calibrated using empirical methods utilizing measurement data from smaller power pulses. Given modern computational capabilities this work sets out to establish a predictive computational capability of the fast neutron flux field exiting the hodoscope to support these calibrations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Cell Dancoff-based embedded self-shielding capability for doubly heterogeneous particulate fuels in SCALE/Polaris

Polaris is a two-dimensional (2D) transport lattice physics capability in the SCALE code system for light-water reactor (LWR) analysis. SCALE/Polaris is being extended to treat doubly heterogeneous particulate fuels in LWRs with accident-tolerant fuels and prismatic high-temperature gas-cooled reactor (HTGR) fuel. Recently, a Dancoff-based Wigner-Seitz approximation capability based on the embedded self-shielding method (DWA-ESSM) was implemented into Polaris for efficient computation. A new double heterogeneity treatment capability based on DWA-ESSM in conjunction with the Hebert's collision probability method for double heterogeneity was developed and implemented for Polaris. The new capability was verified by performing benchmark calculations for the prismatic HTGR fuel compact problems with various design parameters through a code-to-code comparison between the Polaris and continuous-energy Monte Carlo results. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

An Overview of the Molten Salt Thermal Properties Database–Thermophysical, Version 2.1.1 (MSTDB-TP v.2.1.1)

The current status of the Molten Salt Thermodynamic Database- Thermal Physical (MSTDB-TP) is reported. Building off of MSTDB-TP and through the direction of the Roadmap for thermal property measurement of Molten Salt Reactor systems, MSTDB-TP 2.1.1 has now been released containing a total 448 salt entries (data from 140+independent studies) compared to the original commit of 62, containing thermophysical properties including density, viscosity, thermal conductivity, and heat capacity. Along with the new database release, further advancement of Saline, a C++application programming interface (API), and a graphical user interface (GUI) has facilitated increased user/developer interaction with the database. Furthermore, estimation techniques, first principles calculations (Ab-Initio) and interpolation/extrapolation methods (Redlich-Kister/Muggianu), have shown great promise in the future of thermophysical property determination for filling out compositional spaces and investigating experimentally difficult salts (hazardous/expensive). This report describes the database composition, development and advancement of database tools, and the strategy of advancing and implementing estimation data into future iterations of the database for MSTDB-TP.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Coupled Calculations in Helical Steam Generator: Validation on Legacy Data

The NEAMS program aims to develop an integrated multi-physics simulation capability “pellet-to-plant” for the design and analysis of future generations of nuclear power plants. In particular, the Reactor Product Line code suite's multi-resolution hierarchy is being designed to ultimately span the full range of length and time scales present in relevant reactor design and safety analyses, as well as scale from desktop to petaflop computing platforms. Flow-induced vibration (FIV) is widespread problem in energy systems because they rely on fluid movement for energy conversion. Vibrating structures may be damaged as fatigue or wear occurs. Given the importance of reliable components in the nuclear industry, flow-induced vibration has long been a major concern in safety and operation of nuclear reactors. In particular, nuclear fuel rods and steam generators have been known to suffer from flow-induced vibration and related failures. Advanced reactors, such as integral Pressurized Water Reactors (PWRs) considered for Small Modular Reactors (SMR), often rely on innovative component designs to meet cost and safety targets. One component that is the subject of advanced designs is the steam generator, some designs of which forego the usual shell-and-tube architecture in order to fit within the primary vessel. In addition to being more cost- and space-efficient, such steam generators need to be more reliable, since failure of the primary vessel represents a potential loss of coolant and a safety concern. A significant amount of data exists on flow-induced vibration in shell-and-tube heat exchangers, and heuristic methods are available to predict their occurrence based on a set of given assumptions. In contrast, advanced designs have far less data available. Advanced modeling and simulation based on coupled structural and fluid simulations have the potential to predict flow-induced vibration in a variety of designs, reducing the need for expensive experimental programs, especially at the design stage. Over the past five years, the Reactor Product Line has developed the integrated multi-physics code suite SHARP. The goal of developing such a tool is to perform multi-physics neutronics, thermal/fluid, and structural mechanics modeling of the components inside the full reactor core or portions of it with a user-specified fidelity. In particular SHARP contains high-fidelity single-physics codes Diablo for structural mechanics and Nek5000 for fluid mechanics calculations. Both codes are state-of-the-art, highly scalable tools that have been extensively validated. These tools form a strong basis on which to build a flow-induced vibration modeling capability. In this report we discuss one-way coupled calculations performed with Nek5000 and Diablo aimed at simulating available FIV experiments in helical steam generators in the turbulent buffeting regime. In this regime one-way coupling is judged sufficient because the pressure loads do not cause substantial displacements. It is also the most common source of vibration in helical steam generators at the low flows expected in integral PWRs. The legacy data is obtained from two datasets developed at Argonne and B&W.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Demonstration of Fully Coupled Calculations in Helical Steam Generator: Toward Predictions of Fluid Elastic Instability

The NEAMS program aims to develop an integrated multi-physics simulation capability “pellet-to-plant” for the design and analysis of future generations of nuclear power plants. In particular, the Reactor Product Line code suite's multi-resolution hierarchy is being designed to ultimately span the full range of length and time scales present in relevant reactor design and safety analyses, as well as scale from desktop to petaflop computing platforms. Flow-induced vibration (FIV) is widespread problem in energy systems because they rely on fluid movement for energy conversion. Vibrating structures may be damaged as fatigue or wear occurs. Given the importance of reliable components in the nuclear industry, flow-induced vibration has long been a major concern in safety and operation of nuclear reactors. In particular, nuclear fuel rods and steam generators have been known to suffer from flow-induced vibration and related failures. Advanced reactors, such as integral Pressurized Water Reactors (PWRs) considered for Small Modular Reactors (SMR), often rely on innovative component designs to meet cost and safety targets. One component that is the subject of advanced designs is the steam generator, some designs of which forego the usual shell-and-tube architecture in order to fit within the primary vessel. In addition to being more cost- and space-efficient, such steam generators need to be more reliable, since failure of the primary vessel represents a potential loss of coolant and a safety concern. A significant amount of data exists on flow-induced vibration in shell-and-tube heat exchangers, and heuristic methods are available to predict their occurrence based on a set of given assumptions. In contrast, advanced designs have far less data available. Advanced modeling and simulation based on coupled structural and fluid simulations have the potential to predict flow-induced vibration in a variety of designs, reducing the need for expensive experimental programs, especially at the design stage. Over the past seven years, the Reactor Product Line has developed the integrated multi-physics code suite SHARP. The goal of developing such a tool is to perform multi-physics neutronics, thermal/fluid, and structural mechanics modeling of the components inside the full reactor core or portions of it with a user-specified fidelity. In particular SHARP contains high-fidelity single-physics codes Diablo for structural mechanics and Nek5000 for fluid mechanics calculations. Both codes are state-of-the-art, highly scalable tools that have been extensively validated. These tools form a strong basis on which to build a flow-induced vibration modeling capability. In the last two years a significant effort was devoted to 1) develop and validate a fully coupled capability in SHARP for Fluid-Structure calculations (FSI) and 2) validate the use of SHARP for one-way coupled calculations in helical steam generators on legacy data available as well as novel experiments. In this report we discuss an extension of previous one-way coupled calculations performed with Nek5000 and Diablo aimed at simulating available FIV experiments in helical steam generators in the turbulent buffeting regime. It was demonstrated that in the buffeting regime one-way coupling was judged sufficient because the pressure loads do not cause substantial displacements. However, higher speeds led to a reduction in accuracy and the need for a fully coupled capability for velocity or approaching the critical velocity and fluid elastic instability. In this report we demonstrate such fully coupled capability on the Argonne test case discussed in previous reports.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Damage development in neutron-irradiated concrete in a test reactor: Hygro-thermal and mechanical simulations

This paper reports the development of a 3D mesoscale hygro-thermal-mechanical simulation approach to predict damage in concrete irradiated in a test reactor. This framework, developed in MOOSE, considers the effects of elevated temperature, moisture content, and high neutron fluence (energy threshold, E > 0.1 MeV) on the mortar and aggregates separately. The first-stage simulation implements hygro-thermal analysis to determine the temperature and RH inside the specimen as a function of imposed radiation energy. These are used as inputs to the second stage, which considers radiation-induced volumetric expansion (RIVE) of aggregates, and creep, shrinkage, and stress-strain response of mortar to predict the expansion, stresses, and damage in specimens made using different coarse aggregates and subjected to different irradiation times. The irradiation time-dependent damage in the mortar is expressed using an isotropic damage parameter. This multi-physics model serves as a predictive tool for damage quantification in concrete due to neutron irradiation.

36 MATERIALS SCIENCE↗

Augmented Monitoring and Condition Assessment Program for SNF Wet Storage Life Extension - 20489

Approximately 27 MTHM of spent nuclear fuel (SNF) owned and managed by the U.S. Department of Energy, Office of Environmental Management is stored in the L Basin at the Savannah River Site (SRS). This 'DOE SNF' is comprised of approximately 12,000 aluminum-clad, aluminum-based fuel assemblies (∼7 MTHM), and approximately 2000 non-aluminum fuel assemblies (∼20 MTHM). A program is in progress to perform Non-Destructive Examination (NDE) of the fuel and their storage containers to characterize the materials' condition, and to evaluate the effects of service to enable continued safe wet storage of the SNF. The Augmented Monitoring and Condition Assessment Program (AMCAP), a two-part program to develop and implement remote underwater Non-Destructive Examination of the aluminum SNF, and of the containers of the non-aluminum SNF, respectively, is aimed at the characterization and evaluation of corrosion degradation of aluminum fuel and container materials. The predominant design of the aluminum SNF (ASNF) stored in L Basin is the Materials Test Reactor (MTR) equivalent design, a plate fuel design. These SNF are stored in 5'' diameter tubes or 5'' x 5'' squares (called bundles) that are nominally 12' or up to 14' long. The SNF is de-bundled and inspected using a custom-designed MTR Fuel Inspection Table. The inspection table provides for indexed fuel positioning for a video camera examination with controlled lighting. A total of 10 of the SNF originating from foreign research and test reactors were selected for examination based on burnup, enrichment, and prior damage caused by service/storage history. A special inspection campaign of these 10 assemblies is in progress. The observed corrosion damage included minor to moderate attack from general corrosion, pitting, crevice, end grain and galvanic corrosion. Example results from the completed inspections are shown and discussed. The focus is a comparison of the as-received condition versus the as-found current storage condition that will serve to validate Water Chemistry and Corrosion Monitoring Programs. The non-aluminum SNF (NASNF) stored in L Basin are of diverse design that includes various geometries with claddings of stainless steel, Zircaloy, and Hastelloy. The fuel core materials include uranium alloys, oxides/mixed oxides, and carbides. These SNF materials, originating from early experimental and test reactors, are in various physical forms including single fuel elements and cut pieces. The fuel is stored in L Basin in various configurations including in direct bundled storage in aluminum tubes and in isolation cans that are in the bundles or in a larger over-size storage container (OSC). Concern with inside-out corrosion and the potential loss of configuration control and ability to handle the storage containers prompted the development of remote NDE methods that include visual and UT technologies to assess the condition of the containers. Candidate stored materials were selected for a special inspection campaign; the development of the NDE methods for the inspection for galvanic, crevice and sediment-induced corrosion (inside-out) are discussed. A summary of the SNF storage in L Basin at the SRS, and an overview of the AMCAP to enable continued safe storage of DOE SNF are described. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Contribution of Lobe Power to Experiment Heating in the Advanced Test Reactor

In order to ease the computational burden associated with designing irradiation experiments in the Advanced Test Reactor (ATR), scaling factors are often used to estimate design parameters at different lobe powers. Here, this paper examines the validity of long-standing assumptions about the contribution of lobe power to total experiment heating in the ATR. For each of the ATR’s 77 different experiment positions, the fractional contribution of each of the ATR’s five lobes to the total heating in that position is calculated and compared to traditional assumptions. The updated fractional contributions are then used to scale heating rates in a sample problem, and the results are compared to traditional scaling methods as well as explicit MC21 heating calculations. It is concluded that for experiment locations in close proximity to the ATR driver fuel (i.e. flux traps and the A, H, and B positions), heating rates scaled with the updated fractional contributions generally agree better with explicit MC21 calculations than do heating rates scaled using the traditionally assumed contributions. For the I positions, which are located on the very periphery of the ATR core, both scaling methods led to poor results when compared against explicit calculations due to the effect that movement of the outer shim control cylinders has on the experiment heating in those positions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Method for preparing bis-(silylalkyl)carbonate esters

Carbonate esters of Formula (I): (R1)(R2)(R3)Si—R4—O—C(═O)—O—R4—Si(R1)(R2)(R3) are prepared by reaction of a silyl-substituted alcohol of Formula (II): (R1)(R2)(R3)Si—R4—OH with an activated carbonyl compound of Formula (III): C(═O)Z2 in the presence of a catalyst (e.g., an bicyclic amidine, a bicyclic guanidine, or a phosphazene) in an aprotic solvent. In Formulas (I) and (II) each of R1 and R2 independently is alkyl; R3 is alkyl or —X1—Si(R5)(R6)(R7); X1 is O or alkylene; R4 is alkylene; and each R5, R6, and R7 independently is alkyl. In Formula (III), Z is 1-N-imidazolyl or 1-N-succinimidyl. In some embodiments, the catalyst used in the methods described herein comprises at least one base selected from the group consisting of a bicyclic amidine and a bicyclic guanidine. The reaction proceeds readily under both bulk and continuous flow reactor conditions.

25 ENERGY STORAGE↗

Oxidation Behavior and Property Degradation of Nuclear Graphites

During its multidecade operation in the core of nuclear reactors, graphite components are subjected to aggressive and continuous exposure to a high field of ionizing and neutron irradiation, high temperature, and various types of present and postulated chemical attacks. High density, high crystallinity polygranular synthetic graphite is unique among other materials for its extraordinary capacity of resisting and adapting to the aggression inflicted by high temperature, high energy neutron bombardment and ionizing gamma radiation. But, as a carbonaceous material, even though of very high purity, graphite is reactive towards common oxidizing agents: oxygen, carbon dioxide, water. Safe operation of HTGRs relies, among other aspects, on engineered safeguard systems for efficient and continuous protection of graphite components against oxidation. Graphite oxidation behavior was, and continues to be, an important direction of theoretical and experimental research, engineering analyses, models and simulations, and design and safety regulations. The avalanche of publications, reports, experimental data, computer codes, and regulatory documents related to oxidation behavior of nuclear graphite is now accelerating to new levels, prompted by the increased interest for nuclear energy as a clean, carbon-free energy source. Even though public’s perception of nuclear energy advantages may still be influenced by the memories of past accidents of nuclear reactors from generations II and III, the community of informed scientists and engineers, regulators and statemen knows that generation IV of nuclear reactors is designed at very high safety standards, doubled by great advances of scientific knowledge and technological progress. One of routes of these recent advances is directed at better understanding of graphite oxidation behavior, its relationship with graphite manufacturing and microstructural properties, along with the effects of various environmental factors and process variables. Together, the recent progress in manufacturing, properties characterization, and modeling of intricated physical and chemical processes that concur to the oxidation behavior led to development of powerful simulation codes able to analyze various scenarios of normal operation and hypothetical off-normal events, and thus to clearly specify the allowable parameters envelopes for the designers, constructors, and operators of current and future modular HTGRs. This review begins with an introduction on manufacturing methods, structure, and properties of nuclear graphite, including basic requirements that this specialty graphite type must satisfy for nuclear use. It continues with a chapter on environmental effects on nuclear graphite, where emphasis is placed less on irradiation and much more on oxidation phenomena, their safety implications, and the basic traits of chronic and acute oxidation by air (oxygen) and water (humidity, steam). Particular attention is placed on the three graphite grades of interest for this document (IG-110, NBG-18, PCEA). A chapter on properties degradation induced by oxidation follows, with focus on density, dimensional, and mechanical properties changes. The next chapter is intended as a brief review of various approaches used for modeling of graphite oxidation behavior. It summarizes the progress of oxidation models, from the early attempts to complex computational approaches interfaced with specialized computer codes designed for nuclear reactor simulations. Last, a list is presented of knowledge gaps where more research is needed. A short summary concludes the review.

36 MATERIALS SCIENCE↗