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At least 163 records · Page 9

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Oxidation behaviors of matrix-grade graphite during water vapor ingress accidents for high temperature gas-cooled reactors

Water ingress into cores of high temperature gas-cooled reactors (HTGRs) can cause serious safety problems in graphitic components, especially for matrix graphite, which is more vulnerable than nuclear graphite. Here in this study, oxidation behaviors of a matrix-grade graphite, ARB-B1, were investigated under simulated water ingress accidental conditions. The oxidation tests were conducted in water vapor/helium mixed atmospheres at elevated temperatures up to 1200 °C. Oxidation rates and activation energy were evaluated by mass loss measurements. The activation energy was 121.5 kJ/mol in the considered temperature range, indicating only one oxidation regime-in-pore diffusion assisted by cracks. The cracks originated from the fabrication process, acting as penetration paths for the oxidant, played an important role in the oxidation behaviors. Ungraphitized binder oxidation occurred at all temperatures, while apparent oxidation of filler particles started from 1100 °C. Moreover, oxidation effects on compressive properties and hardness of the matrix graphite were discussed in terms of oxidized microstructures. This first detailed study on matrix graphite oxidation in water vapor provides important kinetics knowledge and microstructural and mechanical data for accidental scenarios of HTGRs as well as for development of new matrix graphite materials.

36 MATERIALS SCIENCE↗

DOE OSTI2015

VACUUM ULTRAVIOLET PHOTON-STIMULATED OXIDATION OF BURIED ICE: GRAPHITE GRAIN INTERFACES

The vacuum ultraviolet (VUV) synthesis of CO and CO{sub 2} on ice-coated graphite and isotopic labeled {sup 13}C graphite has been examined for temperatures between 40 and 120 K. The results show that CO and CO{sub 2} can be formed at the buried ice:graphite interface with Lyα photon irradiation via the reaction of radicals (O and OH) produced by direct photodissociation and the dissociative electron attachment of the interfacial water molecules. The synthesized CO and CO{sub 2} molecules can desorb in hot photon-dominated regions and are lost to space when ice coated carbonaceous dust grains cycle within the protoplanetary disks. Thus, the nonthermal formation of CO and CO{sub 2} at the buried ice:grain interface by VUV photons may help regulate the carbon inventory during the early stage of planet formation. This may contribute to the carbon deficits in our solar system and suggests that a universal carbon deficit gradient may be expected within astrophysical bodies surrounding center stars.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

Catalyzed oxidation of IG-110 nuclear graphite by simulated fission products Ag and Pd nanoparticles

To evaluate the stability of nuclear materials in high temperature gas reactors under air ingress conditions, catalytic oxidation of IG-110 graphite by two simulated fission products, metallic Pd and Ag, was studied in oxidative atmosphere and at temperatures up to 1000°C using an integrated furnace, mass spectroscopy and infrared spectroscopy system. Transmission electron microscopy and X-ray diffraction studies show that Pd and Ag nanoparticles were successfully introduced onto powdery IG-110 graphite through an impregnation and subsequent heat-treatment process. The combined mass spectroscopy and infrared spectroscopy methods allow simultaneous analysis of two gaseous products, CO and CO 2 , and separate measurements of activation energy for their formation reactions. It was found that the introduction of Pd or Ag to IG-110 graphite substantially catalyzed the oxidation of graphite, characteristic of decreased onset temperatures for the oxidation of graphite. Moreover, the catalytic effects by Pd and Ag are considerably different based on measured concentration ratios of CO 2 to CO as a function of oxidation temperatures. Ag makes the graphite oxidation commence at approximately 400°C with CO 2 being the dominant product. In contrast, Pd significantly increases the concentration ratio of CO 2 to CO at temperatures higher than approximately 690°C, although it decreases the onset temperature for the oxidation reaction to around 525°C. To understand the catalytic difference, the mechanism of the graphite oxidation was discussed based on the changes of surface oxygen species on Ag and Pd.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1989

CdO Pretreatment For Graphite Lubricant Films

Lubrication of rubbing steel surfaces with graphite improved by sputtering cadmium oxide onto surfaces, according to report. Lubricating films consisting of mixtures of cadmium oxide and graphite did not perform as well as films of graphite alone on surfaces pretreated with cadmium oxide. Primary beneficial effect obtained by sputtering pretreatment with cadmium oxide, which apparently improves bond between metallic substrate and graphite.

Fusaro, Robert L.↗

DOE OSTI2021

Initial Developments in Modeling Graphite Behavior

Graphite is used in High Temperature Reactor designs as a moderator, reflector and core material responsible for protecting the fuel and maintaining structural stability. From a safety perspective, it is imperative to be able to predict how graphite will behave under reactor operating conditions which may compromise the core’s structural integrity or fuel’s safety performance. The following report summarizes recent modeling work undertaken at Idaho National Laboratory which focuses on graphite degradation behavior. One phenomenon which is explored in this report and can cause significant degradation to graphite properties is oxidation. Oxidation behavior in graphite is highly temperature dependent. At low temperatures, oxygen can fully penetrate a component and cause a homogeneous damage profile. At high temperatures, only the graphite near the surface of a component is affected. Understanding and modeling this temperature dependence is essential to predicting graphite behavior. In this report, three graphite models are discussed. The first model is used to investigate strength loss after low temperature oxidation. It does this by generating an approximate graphite microstructure then determining the required load to cause crack propagation. It has been shown that the model reproduces the quasi brittle stress versus strain relationship observed in graphite. Strength loss results from the model are shown to match experimental values. The second model investigates strength loss under high temperature oxidation conditions. This model is more applicable to full scale graphite components where the oxidation damage is often inhomogeneous throughout a component. The third model computes stresses in graphite under reactor conditions. Specifically, the model incorporates the effect of creep, irradiation dose, thermal strains, and oxidation in order to predict internal stresses in a component. All of these models are implemented in the Multiphysics Object-Oriented Simulation Environment (MOOSE), an open source, parallel finite element framework.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Determination of oxidation rates and volatile oxidation products for HTGR graphite matrix material exposed to steam atmospheres

High-temperature gas-cooled reactors (HTGRs) in operation use tristructural isotropic (TRISO) particles embedded in graphite and carbonized resin matrix to form the fuel element. This graphite matrix material serves as a supportive structural element, heat transfer medium, and neutron moderator. In HTGR designs, fuel compacts are exposed to helium coolant, which facilitates high outlet temperatures (750°C 2 O, 800°C 2 , and H 2 , are quantified in varied oxidant atmospheres using a coupled thermogravimetric analyzer and mass spectrometer. Furthermore, oxidation rates reported here for varied steam (H 2 O [g]) atmospheres are predominantly linear and comparable with literature values in the range of tested temperatures (800–1200°C). Changes in dominant matrix oxidation products from primarily CO to a mixture of CO, CO 2 , and H 2 were observed at higher temperatures (≥1000°C) and steam atmospheres (≥5 kPa pH 2 O). Kinetic data indicates that there was no shift in oxidation regime with chemical oxidation occurring at all temperatures and H2O (g) atmospheres tested. These data provide insight into the oxidation behavior of graphite matrix material and will inform future testing conditions, notably mixed atmospheric conditions, of HTGR fuel elements.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Water vapor oxidation behaviors of nuclear graphite IG-110 for a postulated accident scenario in high temperature gas-cooled reactors

Water leakage in accidental conditions of high temperature gas-cooled reactors is one of the most critical problems that can compromise the integrity of different nuclear components. In this study, oxidation behaviors of nuclear graphite IG-110 in water ingress accidental conditions were investigated. Mass loss and oxidation rates were evaluated after oxidation tests at temperatures up to 1400 °C in an Ar-20 vol% H 2 O mixed atmosphere. The activation energy decreased from 318.6 to 148.9 kJ/mol with temperature, indicating two different oxidation regimes. The cross-sections of the oxidized samples were systematically characterized. The corresponding logarithmic porosity profiles showed a temperature dependency. Pore formation moved toward near-surface regions with increasing temperature and preferential binder oxidation, with filler particle degradation. Furthermore, oxidant concentration profiles and oxidation depths were estimated using a theoretical model and compared with the experimental results. This work provides important benchmark data and safety analysis guidance for the accident scenario in high temperature gas-cooled reactors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2015

Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetime of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2017

Oxidation Behavior of Matrix Graphite and Its Effect on Compressive Strength

Matrix graphite (MG) with incompletely graphitized binder used in high-temperature gas-cooled reactors (HTGRs) is commonly suspected to exhibit lower oxidation resistance in air. In order to reveal the oxidation performance, the oxidation behavior of newly developed A3-3 MG at the temperature range from 500 to 950°C in air was studied and the effect of oxidation on the compressive strength of oxidized MG specimens was characterized. Results show that temperature has a significant influence on the oxidation behavior of MG. The transition temperature between Regimes I and II is ~700°C and the activation energy ( E a ) in Regime I is around 185 kJ/mol, a little lower than that of nuclear graphite, which indicates MG is more vulnerable to oxidation. Oxidation at 550°C causes more damage to compressive strength of MG than oxidation at 900°C. Comparing with the strength of pristine MG specimens, the rate of compressive strength loss is 77.3% after oxidation at 550°C and only 12.5% for oxidation at 900°C. Microstructure images of SEM and porosity measurement by Mercury Porosimetry indicate that the significant compressive strength loss of MG oxidized at 550°C may be attributed to both the uniform pore formation throughout the bulk and the preferential oxidation of the binder.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2022

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. Further, this is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1986

Sputtered cadmium oxide as a surface pretreatment for graphite solid lubricant films

Sputtered films of cadmium oxide were applied to sand blasted AISI 440C HT stainless steel disks as a surface pretreatment for the application of rubbed graphite films. Mixtures of cadmium oxide and graphite were applied to the nonpretreated sandblasted metal and evaluated. The results were compared to graphite films applied to other commercially available surface pretreatments. It is found that sputtered CdO pretreated surfaces increase the endurance lives of the graphite films and decrease the counterface steady state wear rate of the pins almost an order of magnitude compared to commercially available pretreatments. The CdO additions in general improved the tribological properties of graphite. The greatest benefit occurred when it was applied to the substrate rather than mixing it with the graphite and that sputtered films of CdO perform much better than rubbed CdO films.

Fusaro, R. L.↗

DOE OSTI2019

In-situ study of the carbon gasification reaction of highly oriented pyrolytic graphite promoted by cobalt oxides and the novel nanostructures appeared after reaction

Cobalt interaction and its effects on carbon-based systems at the nanoscale have recently attracted much attention in different fields, such as catalysis of carbon nanotubes or graphene and graphite nano-patterning taking advantage of its ferromagnetic behavior. Experiments performed in our laboratories show how the re-oxidation process of two equivalent monolayers of CoO deposited on highly oriented pyrolytic graphite at 400 °C leads to the formation of nanochannels at lower temperature than using other methods. Here we present the in-situ characterization of the carbon gasification reaction that drives this process by means of near ambient pressure X-ray photoelectron spectroscopy performed at the ALBA synchrotron facility. The reason why this reaction takes place at such low temperature compared to other methods is due to the weakening of the carbon σ bonds by the initial CoO wetting layer formed at the early stages of growth on the graphite surface. Besides nanochannels, ex-situ atomic force microscopy measurements also show the appearance of two more kinds of nanostructures: nano-strips and nano-rings. The appearance of these nanostructures reveals the impressive modification of the surface after the re-oxidation process mediated by the cobalt oxide.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Characterisation of reduced graphene oxides prepared from natural flaky, lump and amorphous graphites

Highlights: • Natural flaky, lumpy and amorphous graphites were used to synthesis rGO. • Investigation the effect of the crystal morphology on the oxidation process of GrO and characteristics of prepared rGO. • Low graphitisation degree, big specific surface area and small lateral size were beneficial to the oxidation of graphite. - Abstract: The characterisation of reduced graphene oxides (rGOs) prepared from natural flaky, lumpy, and amorphous graphites using Hummers method was investigated. The prepared graphite oxides (GrOs) and rGOs were characterised by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, UV–vis spectroscopy, atomic force microscopy and electrochemical performance. The results showed that amorphous graphite was much easier to oxidise than lumpy and flaky graphites and was preferable for preparing single or double layer graphene because low graphitisation degree, high defect degree, high specific surface area and small crystal size were beneficial for (1) the oxidants to attack the exposed carbon atoms, (2) the intercalation of oxidants, and (3) the diffusion of oxidants between graphitic layers. In addition, rGO synthesised from amorphous graphite had the most defects and the smallest size of the in-plane sp{sup 2} domains compared to those obtained from the other two nature graphites.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Au nanoparticles and graphene oxide co-loaded graphitic carbon nitride: Synthesis and photocatalytic application

Highlights: • The 0.5%Au/GO/g-C3N4 composite exhibites excellent photocatalytic activity. • GO nanoslice acts as an e- transporter and acceptor Au/GO/g-C3N4 composite. • Au particles in Au/GO/g-C3N4 composite act as electron trap to separate e- and h{sup +}. • Adsorbed OH and h{sup +} are involved in reducing and oxidizing process, respectively. - Abstract: Inhibition of charge-carrier recombination in semiconductors is one of the most efficient methods to enhance the photocatalytic performance in visible light irradiation. Noble metals and graphene oxide (GO) are currently regarded as fine channels to enhance the charge-carrier transfer efficiency. Herein, novel Au nanoparticles and GO co-loaded graphitic carbon nitride (Au/GO/g-C{sub 3}N{sub 4}) composite was obtained by a single step ultrasonic chemical process, and the photocatalytic activity was tested in Rhodamine B (Rh B) photodegradation in visible light region. The Au/GO/g-C{sub 3}N{sub 4} composite containing 0.5%Au (molar Au per unit molar of g-C{sub 3}N{sub 4}) exhibited excellent photocatalytic activity and might be attributed to the important part of GO nanoslices and Au nanoparticles. An electron transporter and acceptor have been acted by the GO nanoslices to facilitate the charge transfer and against the recombination of photoexcited electron-hole pairs. In the meantime, an electron trap was formed on the Au nanoparticles to separate the charges. Furthermore, it was found that the reactive species of adsorbed OH and holes took part in the reduction and oxidization actions in the photocatalytic process, respectively. The design of the Au/GO/g-C{sub 3}N{sub 4} composite provides a novel route to synthesis of highly efficient photocatalysts in environmental application.

36 MATERIALS SCIENCE↗

NASA NTRS1987

Sputtered cadmium oxide as a surface pretreatment for graphite solid-lubricant films

Fusaro, Robert L.↗

DOE OSTI2016

Experimental research of graphite behavior under the air ingress accident condition of High Temperature Gas-cooled Reactor - 18752

As the major component of both cladding and grid spacer materials of High Temperature Gas-cooled Reactor (HTGR), graphite plays an important role on heat removal during the severe accident sequence. However, its heat transfer behavior in high temperature condition may be affected by the oxidation of graphite when the air or steam ingresses in an accident. In this research, an experiment was conducted to analyze the graphite heat transfer behavior in high temperature oxidable environment. An assembly including two graphite rings was used as the test section. It was heated up by a tungsten wire, which is installed inside the inner graphite ring and be joule heated. Temperature was measured by several K-type thermos-couples in certain positions. Argon gas was injected in advance to avoid the unwanted oxidation by the oxygen in the air. Air was injected into the gap between two graphite rings once the temperature of the inner ring reached target point to create the oxidable environment. Based on the results, a rapid increase of inner graphite ring's temperature can be observed after starting injected the air, and a rapid decrease after stopped the injection. It might due to the chemical reaction heat during the graphite surface oxidation. By comparing the steady state before and after air injection, the inner specimen s temperature is a little bit lower after the oxidation, which suggests that its ability of radiation heat transfer might be enhanced a little bit by oxidation. By visualized the test section, coarser surface at the inner graphite ring can be observed after the oxidation. In addition, about 8.9% mass loss of the oxidized graphite can also be found from the posttest examination. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2016

The electric current effect on electrochemical deconsolidation of spherical fuel elements - 18447

For High-Temperature Gas-cooled Reactor in China, fuel particles are bonded into spherical fuel elements by a carbonaceous matrix. In conjunction with the development of a system to determine fuel failure fractions through {gamma}-analysis of individual and undamaged fuel particles, an automated electrochemical deconsolidation apparatus was developed in this study to separate the particles from the carbonaceous matrix by disintegrating the matrix into fine graphite powder, based on the anodic oxidation of graphite in an electrolyte containing nitric acid. A series of tests were conducted under a range of deconsolidation conditions to develop procedures and refine the equipment. The easy-handle un-irradiated spherical fuel elements were used as samples for initial tests. It is found that the morphology, size, and element content of deconsolidated graphite matrix and free particles were notably affected by electric current intensity. During the electrolysis, the nitric acid electrolyte gradually infiltrated into the micropores of graphite matrix, and the electrochemical reaction would take place around micropore structure as well as matrix surface. With much higher surface reaction capability due to the large specific area of micropore structure, the expansion stress originated from inner surface of micropores widened the c-spacing of the layer lattice of carbonaceous matrix, which was thought to be one of the main driving force of deconsolidation. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2022

Diffusion of cesium in oxidized and unoxidized IG-110 nuclear graphite

Time-release diffusion measurements of cesium have been conducted over the temperature range 1073 K – 1973 K on oxidized and unoxidized IG-110 graphite. Four cesium concentrations were tested to investigate the concentration dependence of the diffusion coefficient. Two levels of oxidation were tested and compared to unoxidized concentration-matched sets to explore the effects of graphite oxidation. Here, the results demonstrate that cesium diffusion coefficient in unoxidized IG-110 graphite is independent of concentration within the range 34 – 163 µg Cs/g graphite . Above this, the effective cesium diffusion coefficient changes with concentration. The diffusion coefficient was increased by a factor of 2–12 in the oxidized set with 7.8% mass loss. These results can be used to aid predictive modeling of cesium diffusion in HTGR cores.

36 MATERIALS SCIENCE↗