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Comparison of Irradiated and Unirradiated Graphite Oxidation Performance

This work examines the oxidation behavior of NBG-25 graphite using irradiated specimens and (not irradiated) companion specimens from the Advanced Graphite Creep (AGC) Experiment. Irradiated and companion specimens were quartered, split into four small samples, to enable four oxidation test runs for each (0.5 inch diameter by 0.25 inch tall) piggyback button obtained from the AGC Experiment inventory. These split samples were oxidized in air in a thermogravimetric analyzer (TGA) and benchmarked against observations with separately sourced same-grade specimens of three geometries oxidized either in the TGA or in a vertical furnace built and operated to satisfy the specifications of ASTM D7542. The study considers both irradiation damage and relief of damage by thermal annealing. A range of isothermal oxidation temperatures were tested for specimens exposed to a similar irradiation environment, nominally 6.5 dpa at 650°C. To assess the dose dependency of observed oxidation behavior, specimens with a range of irradiation exposures (up to 6.8 dpa) were tested at the single oxidation temperature of 650°C. In the conventional analysis (rate determined over the 5-10% mass loss range) any annealing effects appear to be negligible, while irradiation to ~6.5 dpa may double or triple the subsequent oxidation rate. However, examination of rate with extent of reaction (over incremental ranges from initial onset up to 5% mass loss) illustrates that (at least for ~6.5 dpa) irradiation initially inhibits oxidation. Slower rates of oxidation than companion split samples are clearly indicated across all oxidation temperatures tested up to ~0.5% mass loss. Over the range of 0.5-1% mass loss, regardless of normalization strategy, there is no statistically meaningful difference in oxidation rate. However, beyond 0.5% mass loss oxidation of the irradiated sample becomes progressively faster than the companion sample (up to the 10% mass loss level observed).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Summary of Graphite Data Stored within NDMAS

The Graphite Technology Development Project provides data to support the design of graphite core components within specific reactor service conditions of the next generation of high-temperature, gas-cooled nuclear reactors. Physical, mechanical, and thermal properties of nuclear grade graphite were characterized for specimens that were unirradiated, irradiated, and irradiated under various stress conditions. The material properties include diameter, length, mass, density, compressive strength, tensile strength, flexural strength, modulus, resistivity, thermal diffusivity, and thermal expansion coefficient. Baseline graphite specimens are unirradiated from different grades (2114, IG-110, NBG-17, NBG-18, and PCEA) and different types used in different characterization tests (compressive, flexural, tensile, one-inch cylinder, and quarter-inch cylinder). The Advanced Graphite Creep (AGC) irradiation specimens are from a much larger number of grades and cylinder types (creep, piggyback, and pencil). For baseline graphite, characterization data for 7,756 specimens extracted from thirteen graphite billets were captured to the NDMAS database. For AGC experiments, four irradiation campaigns have been completed: AGC-1, AGC-2, AGC-3, and AGC-4. The ongoing HDG-1 (High-Dose Graphite) experiment, which began irradiation with Cycle 168B on August 26, 2020, includes specimens previously irradiated in AGC-2 in addition to the specimens originally destined for AGC-5.. Besides the characterization data, the AGC data includes irradiation monitoring and physics data representing the irradiation conditions of AGC specimens. Currently, all data for AGC-1, AGC-2, and AGC-3 have been captured to the NDMAS database. Only AGC-4 pre-irradiation and irradiation monitoring data have been captured, and HDG-1 pre-irradiation data are in process of being captured for unirradiated specimens. To date, a total of 38,149 material property records have been captured into NDMAS database for baseline and AGC specimens. All characterization data are qualified for use according to their perspective data verification reports. For the AGC irradiation campaigns, a total of 41,502 qualified physics calculation records were added for AGC-1, AGC-2, and AGC-3. Finally, a total of 173,698,505 AGC irradiation monitoring data records (thermocouple temperature, gas flow rate, gas pressure, gas moisture, applied load, and specimen displacement) have been captured to NDMAS; the majority of those records (~94%) are qualified data records.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Drawings

These are drawings that display dimensions and orientation of specimens for the graphite baseline program test specimens.

99 GENERAL AND MISCELLANEOUS↗

Performance of Graphite Oxidation with Environment and Specimen Geometry

Introduction -Motive for the study (a modest request) •Issues that must be considered -Pertinent oxidation background information •Three oxidation regimes -ASTM D7542 • The primary parameters for oxidation control -Energy of the System -Atmosphere -Reaction Interface

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Sectioning of NBG-17 Graphite Billet

The Advanced Reactor Technologies (ART) Baseline Graphite Characterization program at the Idaho National Laboratory (INL) is performing a comprehensive evaluation of inter-billet variations in as-produced nuclear-grade graphite. Before graphite test specimens are machined, the full-size billets must be pre-sectioned into sub-blocks that can be more easily handled and shipped. As manufactured, NBG-17 billets are rectangular in shape, nearly 6 feet in length, and may exceed 1,500 pounds in weight. Sectioning of these billets must be accomplished via a supplier that is capable of handling and cutting the billets into individual slabs and quartering these slabs into sub-blocks. Billets will be pre-labeled by the Purchaser prior to leaving controlled storage such that traceability of any individual sub-block is never lost during sectioning operations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Materials property changes in ETU-10 graphite due to neutron irradiation at elevated temperatures

Graphite grade ETU-10, from IBIDEN Co., Ltd. Has been irradiated in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL). The irradiation program was developed to provide a preliminary study the irradiation-induced property changes to the dimensions/volume, elastic properties, strength, electrical resistivity, coefficient of thermal expansion, and thermal diffusivity/conductivity over a range of temperatures and neutron exposures that may be relevant for future nuclear reactors. The irradiation envelope covers a range of irradiation temperatures (300°C–900 °C) and fluences (up to 40 × 10 25 n/m 2 [E > 0.1 MeV] or ~30 dpa) that would be relevant for advanced nuclear reactors. Further, the dimensional change was observed to be anisotropic for an isotropic graphite, the specimen dimensions, volume, Young's modulus, shear modulus, and strength all displayed a parabolic fluence dependence, the electrical resistivity had a rapid rise followed by a decrease and a later increase, at high fluence the mean coefficient of thermal expansions was similar for all irradiation temperatures, and thermal conductivity rapidly decreased followed by a continued loss.

36 MATERIALS SCIENCE↗

Graphite Oxidation Rate Study on ET-10 and ETU-10 Grades - Task 4: QA Support and Testing for Structural Graphite Oxidation

INL performed targeted oxidation tests to measure oxidation rates for samples of ET-10 and ETU-10 graphite under CRADA No. 21CRA22 Mod. 3, Annex A, “Tritium Testing to Support Kairos Power Advanced Reactor Demonstration” (04/02/2024). All testing was conducted within INL’s Carbon Characterization Laboratory (CCL) using test standard ASTM D7542-21 "Standard Test Method for Air Oxidation of Carbon and Graphite in the Kinetic Regime" [ASTM International, 2021]. Kairos Power provided all test specimens through its graphite vendor Ibiden, Inc. to INL and ASTM specimen specified dimensions. Information within this report only provides the Arrhenius oxidation rate plots as a function of temperature for each graphite grade tested. The raw mass loss per time data will be provided on the Nuclear Data Management and Analysis System (NDMAS) portal located on the INL information system.

36 MATERIALS SCIENCE↗

Investigation of nonlinear mechanical behavior of two superfine-grained graphites with DIC assisted disc splitting test

Using standardized uniaxial tensile test specimens is not practical due to the limited volumes in irradiation capsules, molten salt degradation facilities, or oxidation apparatus. The ASTM International Standard Test Method for Tensile Strength Estimate by Disc Compression of Manufactured Graphite (ASTM D8289) was developed to provide a convenient way for estimating tensile strength. Unlike the traditional uniaxial tensile test in ASTM C749 (International Standard Test Method for Tensile Stress–Strain of Carbon and Graphite), which uses dog-bone shaped specimens larger than 12.95 mm × 120.65 mm, the ASTM D8289 standard uses smaller discs with diameters of 6–12.7 mm. A digital image correlation (DIC) system, which uses a full-field noncontact surface displacement measurement technique, was applied along with the ASTM D8289 disc splitting test on IG-110 samples and compared with previous measurements from Mersen 2114 samples. Results confirmed that the DIC technique can measure the surface displacement/strain on these small (Ø6 mm × 3 mm) graphite specimens with good repeatability. However, Mersen 2114 and IG-110 samples exhibited strain discrepancies when DIC measurements were compared with analytical and finite element simulation values. The loading history and strain results also indicated different mechanical behaviors between Mersen 2114 and IG-110, particularly the nonlinear behavior of the IG-110 samples. Good agreement was observed by comparing the splitting tensile strengths of two superfine-grained grades with results from other work. The specimen size effect is discussed when comparing the splitting tensile strength with corresponding uniaxial tensile strength of these two graphite grades.

Lin, Lianshan [ORNL] (ORCID:0000000203399219)↗

Mechanical behavior analysis using small-size graphite disc compression testing with digital image correlation methods

The ASTM International Standard Test Method for Tensile Stress-Strain of Carbon and Graphite (ASTM C749) requires dog-bone shaped specimens. Unfortunately, specimen sizes required in ASTM C749 are much too large for irradiation within a test reactor and are incompatible with irradiation capsule volumes, molten salt degradation facilities, or oxidation apparatus. The ASTM International Standard Test Method for Tensile Strength Estimate by Disc Compression of Manufactured Graphite (ASTM D8289) was developed as an alternative that provides a means for testing tensile properties using smaller specimens when geometric constraints are present. However, the important stress–strain relation throughout the test loading history that could be recorded using ASTM C749 is lost by using ASTM D8289 because of the difficulties involved with using traditional strain gauges or extensometers on such a small specimen. In this work, a digital image correlation (DIC) method, which uses a full-field noncontact surface displacement measurement technique, was applied along with the ASTM D8289 splitting tensile test on eight small samples of graphite grade Mersen 2114 to track their deformation during compressive loading. Initial results showed that the DIC technique can measure the surface displacement/strain on these small (Ø6 × 3 mm) graphite specimens with high accuracy and good repeatability, indicating that the DIC technique, combined with the small-disc splitting tensile test in ASTM D8289, can capture the strain evolution in the test. In conclusion, further comparison of measured strains with analytical and numerical simulation results provides additional understanding of the mechanical behaviour of this nuclear graphite material in complex stress states.

36 MATERIALS SCIENCE↗

Dynamic Deformation in Nuclear Graphite and Underlying Mechanisms

Time-dependent deformation in nuclear graphite is influenced by the creation and migration of radiation-induced defects in the reactor environment. This study investigates the role of pre-existing defects such as point defect clusters and Mrozowski cracks in nuclear graphite IG-110. Separate specimens were irradiated with a 2.8 MeV Au 2+ beam with a fluence of 4.38 × 10 14 cm −2 and an 8 MeV C 2+ beam with a fluence of 1.24 × 10 16 cm −2 . Microscopic specimens were either mechanically loaded inside a transmission electron microscope (TEM) or subjected to ex situ indentation-based creep loading. In situ TEM tests showed significant plasticity in regions highly localized around the Mrozowski cracks, resembling slip or ripplocation bands. Slip bands were also seen near regions without pre-existing defects but at very high stresses. Ex situ self-ion irradiation embrittled the specimens and decreased the creep displacement and rate, while heavy ion irradiation resulted in the opposite behavior. We hypothesize that the large-sized gold ions (compared to the carbon atoms) induced interplanar swelling as well as cross-plane channels for increased defect mobility. These findings illustrate the role of pre-existing defects in the dynamic relaxation of stresses during irradiation and the need for more studies into the radiation environment’s impact on the mechanical response of nuclear graphite.

creep deformation↗

AGC-4 Specimen Post-Irradiation Examination Data Interim Report

This interim report documents preliminary results of the post-irradiation examination material property testing from the fourth advanced graphite creep (AGC), AGC 4, capsule specimens. This is the fourth of a series of six irradiation test trains planned as part of the AGC experiment to fully characterize the neutron irradiation effects and radiation creep behavior of current nuclear graphite grades to moderate dose levels (=7 dpa). The AGC 4 capsule was irradiated in the Idaho National Laboratory Advanced Test Reactor at a nominal temperature of 800°C and to a peak dose of 8 dpa. Half of the AGC-4 specimens were subjected to compressive stresses to induce irradiation creep. Post-irradiation testing and measurement results are reported with the exception of thermal testing, which is still in progress, and irradiation mechanical strength testing. Additionally, some specimens initially deemed too hot to be examined in the ART Graphite laboratory may still be measured. The data reported includes specimen dimensions for both stressed and unstressed specimens to establish the irradiation creep rates, mass and dimensional data necessary to derive density, elastic constants (Young?s modulus, shear modulus, and Poisson?s ratio) from ultrasonic time of flight velocity measurements, Young?s modulus from the fundamental frequency of vibration, and electrical resistivity. A more complete evaluation of trends in the material property changes, as well as irradiation-induced creep due to the irradiation environment and applied load on the specimens, will be discussed later in AGC 4 post-irradiation examination analysis reports.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

AGC-4 Specimen Post-Irradiation Examination Data Interim Report

This interim report documents preliminary results of the post-irradiation examination material property testing from the fourth advanced graphite creep (AGC), AGC 4, capsule specimens. This is the fourth of a series of six irradiation test trains planned as part of the AGC experiment to fully characterize the neutron irradiation effects and radiation creep behavior of current nuclear graphite grades to moderate dose levels (=7 dpa). The AGC 4 capsule was irradiated in the Idaho National Laboratory Advanced Test Reactor at a nominal temperature of 800°C and to a peak dose of 8 dpa. Half of the AGC-4 specimens were subjected to compressive stresses to induce irradiation creep. Post-irradiation testing and measurement results are reported with the exception of thermal testing, which is still in progress, and irradiation mechanical strength testing. Additionally, some specimens initially deemed too hot to be examined in the ART Graphite laboratory may still be measured. The data reported includes specimen dimensions for both stressed and unstressed specimens to establish the irradiation creep rates, mass and dimensional data necessary to derive density, elastic constants (Young?s modulus, shear modulus, and Poisson?s ratio) from ultrasonic time of flight velocity measurements, Young?s modulus from the fundamental frequency of vibration, and electrical resistivity. A more complete evaluation of trends in the material property changes, as well as irradiation-induced creep due to the irradiation environment and applied load on the specimens, will be discussed later in AGC 4 post-irradiation examination analysis reports.

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AGC-2 Specimen Post Irradiation Data Package Report

This report documents results of the post-irradiation examination material property testing of the creep, control, and piggyback specimens from the irradiation creep capsule Advanced Graphite Creep (AGC)-2 are reported. This is the second of a series of six irradiation test trains planned as part of the AGC experiment to fully characterize the neutron irradiation effects and radiation creep behavior of current nuclear graphite grades. The AGC-2 capsule was irradiated in the Idaho National Laboratory Advanced Test Reactor at a nominal temperature of 600°C and to a peak dose of 5 dpa (displacements per atom). One half of the creep specimens were subjected to mechanical stresses (an applied stress of either 13.8, 17.2, or 20.7 MPa) to induce irradiation creep. All post-irradiation testing and measurement results are reported with the exception of the irradiation mechanical strength testing, which is the last destructive testing stage of the irradiation testing program. Material property tests were conducted on specimens from 15 nuclear graphite grades using a similar loading configuration as the first AGC capsule (AGC-1) to provide easy comparison between the two capsules. However, AGC-2 contained an increased number of specimens (i.e., 487 total specimens irradiated) and replaced specimens of the minor grade 2020 with the newer grade 2114. The data reported include specimen dimensions for both stressed and unstressed specimens to establish the irradiation creep rates, mass and volume data necessary to derive density, elastic constants (Young’s modulus, shear modulus, and Poisson’s ratio) from ultrasonic time of flight velocity measurements, Young’s modulus from the fundamental frequency of vibration, electrical resistivity, and thermal diffusivity and thermal expansion data from 100–500°C. No data outliers were determined after all measurements were completed. A brief statistical analysis was performed on the irradiated data and a limited comparison between pre- and post-irradiation properties is presented. A more complete evaluation of trends in the material property changes, as well as irradiation-induced creep due to irradiation, temperature, and applied load on specimens will be discussed in later AGC-2 post-irradiation examination analysis reports.

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AGC Experiment Status

AGC Experiment Status to include: History and status of the AGC-4, Review of the AGC experiment, AGC graphite grades and samples, The AGC-4 capsule and specimens, and HDG-1 and HDG-2. Description of the Experiment, AGC graphite grades and samples, AGC-1 Test Train, AGC-1 Test Train Design Features, New AGC Irradiation Schedule (2018) and update in schedule, Irradiation and disassembly history, present and future status, and shipment and initial PIE. Initial PIE strategy, recovered specimens, PIE results, and status of experiments.

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Progress Report on Graphite-Salt Interaction Studies (FY21)

This report summarizes the activities performed in FY21 to investigate the interactions between nuclear graphite and molten salts, such as FLiNaK. First, building on last year’s achievements, the team improved the procedure for measurements on pressurized salt intrusion in nuclear graphite and performed new experiments at variable pressures with specimens of different sizes and shapes. Additionally, the team actively provided suggestions and comments for ASTM D8091, Standard Guide for Impregnation of Graphite with Molten Salts , which came up for periodic revision in 2021. Second, the team expanded its capabilities to further characterize salt-impregnated graphite by procuring and installing a laser-induced breakdown spectroscopy (LIBS) instrument capable of producing a 3D chemical composition of a surface and subsurface region of specimens. A methodology for accurately analyzing information was developed, and a manuscript was submitted for publication. The LIBS instrument sample cell is sealed in controlled inert atmosphere, which is an advantage for using humidity-sensitive samples and Be-contaminated samples. This aligns with the team’s effort to expand the capabilities of handling FLiBe and Becontaining materials in two newly installed glovebox units. Third, the team performed preliminary tribology tests for pebble graphite wear in contact with stainless steel in dry state and in molten salt at high temperature. These tests are needed to establish the baseline for the wear of pebble graphite by friction against metallic walls. The friction and wear of pebbles in the fluoride salt-cooled hightemperature reactor are expected to generate dust, which is a concern for other components’ properties and safe reactor operation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Intern Poster

Digital Image Correlation (DIC) is an optical technique that combines image registration and tracking methods for accurate two-dimensional and three-dimensional changes in images. DIC software can be used to track the contour, deformation, and strain of a sample. In the Advanced Test Reactor (ATR) at INL (Idaho National Laboratory) there exists a small working window of samples that can become irradiated. Hundreds of graphite disks called piggybacks have undergone this irradiation as part of the Advanced Reactor Technologies (ART) program. After irradiation, it is desirable to understand the change in tensile strength as a function of dose. Due to the limited space in the ATR, typical dog bone tensile tests reduce the number of graphite samples from hundreds to tens. However, there does exist an ASTM standard, D8289, which uses disc compression of graphite to estimate the tensile strength of the specimen with the Brazilian Disk test fixture. While only used as an estimate, which is typically off by a third, it is the purpose of this study to identify how to amend D8289 to remove the word "estimate" with the help of DIC.

36 MATERIALS SCIENCE↗

ECAR-1943 AGC-1 INDIVIDUAL SPECIMEN FLUENCE, TEMPERATURE, AND LOAD CALCULATION AND TABULATION

This ECAR calculates the fluence and temperature of the AGC-1 specimens as they change elevation through the course of the experiment. The specimen elevation varies as the specimen stack shrinks due to irradiation and load induced creep. The compressed specimen stacks (S-1 thru S-6) have a graphite pushrod that applies a gas cylinder load. The top of the pushrod position is measured and recorded in the NGNP Data Management and Analysis System (NDMAS). The bottom of each of these compressed stacks is supported by the lower specimen holder which also shrinks as a result of irradiation and load. The specimen holder post-irradiation length was recorded during post-irradiation examination (PIE). Assuming the specimen holder shrinkage is linear with respect to the fluence received, the position of the top of the specimen holder can be calculated with respect to reactor integrated power. Assuming that individual specimen shrinkage is proportional to the fluence received, and that the shrinkage behavior is similar in all the specimens, the individual specimen position can be calculated.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Irradiation-Induced Defect Evolution in Nuclear Graphite

Graphite has historically been used as a moderator material in nuclear reactor designs dating back to the first man-made nuclear reactor to achieve criticality (Chicago Pile 1) in 1942. Additionally, graphite is a candidate material for use in the future envisioned next-generation nuclear reactors (Gen IV); specifically, the molten-salt-cooled (MSR) and very-high-temperature reactor (VHTR) concepts. Gen IV reactor concepts will introduce material challenges as temperature regimes and reactor lifetimes are anticipated to far exceed those of earlier reactors. Irradiation-induced defect evolution is a fundamental response in nuclear graphite subjected to irradiation. These defects directly influence the many property changes of nuclear graphite subjected to displacing radiation; however, a comprehensive explanation for irradiation-induced dimensional change remains elusive. The objectives of this project were focused on the characterization of irradiation-induced defect evolution in nuclear graphite via transmission electron microscopy (TEM). With the use of novel TEM specimen preparation techniques, high-temperature electron-irradiation and characterization of high-temperature neutron-irradiated nuclear graphite, novel fullerene-like defects are shown to be a dominant defect type, especially at higher temperatures. These results contradict the historical models of defect evolution and provide valuable insight into the macroscopically observed property changes in irradiated nuclear graphite.

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