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At least 127 records · Page 7

Methane pyrolysis by Joule heating for graphitic carbon and hydrogen production

The global energy transition toward sustainability requires technologies that can decarbonize energy carriers and fuels while producing valuable materials. Methane, a primary component of natural gas, is both a high-energy-density fuel and a significant greenhouse gas. This study reports an approach for methane pyrolysis utilizing Joule heating within the deposition substrate to drive the endothermic reaction. With electric current passing through a resistive porous carbon cloth, heat is generated to break C-H bonds of methane molecules. Here, the decomposition of methane as it flows through the cloth results in hydrogen production and the formation of conformally layered graphite around the carbon fibers. The effects of input power, chamber pressure, feedstock flow rate, and process duration on hydrogen and graphite production are characterized via in situ mass spectrometry and laser absorption spectroscopy, resulting in methane conversion rates up to 88%, with hydrogen and carbon yields of 82% and 72%, respectively. Material characterization verifies uniform high-quality graphite deposition, with a Raman I D /I G ratio of 0.1 and 3.38 Å d-spacing. This Joule heating method for catalyst-free methane pyrolysis offers the potential for advancing hydrogen production technology by simultaneously producing valuable materials such as solid graphite, thus enhancing the economic viability of the fuel decarbonization process.

Energy Resources↗

Microstructural Characterization of Next Generation Nuclear Graphites

This article reports the microstructural characteristics of various petroleum and pitch based nuclear graphites (IG-110, NBG-18, and PCEA) that are of interest to the next generation nuclear plant program. Bright-field transmission electron microscopy imaging was used to identify and understand the different features constituting the microstructure of nuclear graphite such as the filler particles, microcracks, binder phase, rosette-shaped quinoline insoluble (QI) particles, chaotic structures, and turbostratic graphite phase. The dimensions of microcracks were found to vary from a few nanometers to tens of microns. Furthermore, the microcracks were found to be filled with amorphous carbon of unknown origin. The pitch coke based graphite (NBG-18) was found to contain higher concentration of binder phase constituting QI particles as well as chaotic structures. The turbostratic graphite, present in all of the grades, was identified through their elliptical diffraction patterns. The difference in the microstructure has been analyzed in view of their processing conditions.

01 COAL, LIGNITE, AND PEAT↗

Amyloid-like amelogenin nanoribbons template mineralization via a low-energy interface of ion binding sites

Protein scaffolds direct the organization of amorphous precursors that transform into mineralized tissues, but the templating mechanism remains elusive. Motivated by models for the biomineralization of tooth enamel, wherein amyloid-like amelogenin nanoribbons guide the mineralization of apatite filaments, we investigated the impact of nanoribbon structure, sequence, and chemistry on amorphous calcium phosphate (ACP) nucleation. Using full-length human amelogenin and peptide analogs with an amyloid-like domain, films of β-sheet nanoribbons were self-assembled on graphite and characterized by in situ atomic force microscopy and molecular dynamics simulations. All sequences substantially reduce nucleation barriers for ACP by creating low-energy interfaces, while phosphoserines along the length of the nanoribbons dramatically enhance kinetic factors associated with ion binding. Furthermore, the distribution of negatively charged residues along the nanoribbons presents a potential match to the Ca–Ca distances of the multi-ion complexes that constitute ACP. These findings show that amyloid-like amelogenin nanoribbons provide potent scaffolds for ACP mineralization by presenting energetically and stereochemically favorable templates of calcium phosphate ion binding and suggest enhanced surface wetting toward calcium phosphates in general.

59 BASIC BIOLOGICAL SCIENCES↗

TH-C-19A-02: Characterization of An Actively Controlled Graphite Probe Calorimeter

Purpose: To construct and experimentally evaluate the performance of a miniature probe-format graphite calorimeter (GPC) with built-in active control. The GPC is the first ever calorimeter designed specifically for routine clinical use. Methods: The original GPC design, developed as part of our previous work, was modified to accommodate a micro-thin, resistive heating element and sensing thermistors embedded in the outermost graphite layer. A software-based process control loop was written to maintain a predefined set point temperature throughout the detector by precisely modulating the current flowing through the resistive element. Continuous feedback is provided to the controller by the additional thermistors. A functioning prototype was constructed in-house and operated in adiabatic mode in a 6 MV photon beam. Ten sets of measurements of varying duration (10 to 60 seconds) and repetition rate (200 to 600 MU/min) were analyzed. Reproducibility, linearity and dose rate dependence were assessed. Results: A total of 47 individual measurements were performed using the active GPC. The reproducibility, defined here as the sample standard deviation weighted across all 10 measurement sets, was found to be 0.37%. Similarly, the standard error (type A uncertainty) was 0.17%. Linearity was quantified by plotting signal as a function of monitor units delivered at 600 MU/min. The adjusted R-square of the resulting linear fit was 0.9996. Dose rate dependence, evaluated as the change in normalized response (signal/MU) as a function of repetition rate, was found to be statistically insignificant. Conclusions: The incorporation of active control has resulted in a marked improvement in the GPC's reproducibility and it allows the user to now perform measurements within minutes of setup. With this refinement, it is estimated that the overall standard uncertainty in the absolute determination of dose to water is 1%, making the GPC comparable to a calibrated ionization chamber. This research has received financial support from Sun Nuclear Corporation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The Characterization of Grade PCEA Recycle Graphite Pilot Scale Billets

Here we report the physical properties of a series specimens machined from pilot scale (~ 152 mm diameter x ~305 mm length) grade PCEA recycle billets manufactured by GrafTech. The pilot scale billets were processed with increasing amounts of (unirradiated) graphite (from 20% to 100%) introduced to the formulation with the goal of determining if large fractions of recycle graphite have a deleterious effect on properties. The properties determined include Bulk Density, Electrical Resistivity, Elastic (Young s) Modulus, and Coefficient of Thermal Expansion. Although property variations were observed to be correlated with the recycle fraction, the magnitude of the variations was noted to be small.

36 MATERIALS SCIENCE↗

Ultrasonic and mechanical characterizations of fatigue states of graphite epoxy composite laminates

Eight-ply (0, + or - 45, 0)s laminates of Hercules AS/3501-6 graphite epoxy composite are fabricated using various cure pressures ranging from 0.52 to 0.86 MPa and cure temperatures ranging from 150 C to 200 C. In general, the minimum composite void volume fraction is obtained at a cure temperature of 175 C and a cure pressure of 0.86 MPa, or at 200 C and 0.86 MPa. The ultrasonic attenuation at 4 MHz was found to correlate with the composite void volume fraction. Composite specimens were tested in flexural fatigue. Beyond 10,000 fatigue cycles, the ultrasonic attenuation at 4 MHz was found to increase and the flexural stiffness was found to decrease. The ultrasonic attenuation at 4 MHz of the as-fabricated composite can be correlated with the number of fatigue cycles to failure.

Williams, J. H., Jr.↗

Ultrasonic and mechanical characterizations of fatigue states of graphite epoxy composite laminates

Results of an exploration of the relationship between ultrasonic attenuation and fatigue survivability of graphite fiber epoxy composites fabricated under different cure conditions are reported. A total of 9 27 x 40 cm eight-ply graphite epoxy laminated specimens were formed, and fatigue tests were run on five partial samples at 73.5 N varying at 30 Hz, with tests ending at a 1.27 cm deflection. A pulsed oscillator generated sinusoidal waves and transducers recorded the passage of the ultrasonic waves for display on oscilloscopes. Cure pressures ranged from 0.52-0.85 MPa and cure temperatures were in the 150-200 C interval. Ultrasonic through-transmission at 4 MHz was performed prior to and during fatigue testing. The minimum void volume fraction occurred at 175 C and 0.86 MPa. The flexural stiffness decreased with the number of fatigue cycles past 10,000, when the attenuation also increased. Correlations were found between the 4.0 MHz signal attenuation and the void volume fraction, and between the number of fatigue cycles to failure and the 4.0 MHz signal attenuation.

Williams, J. H., Jr.↗

Update on Activities Related to the Library of Graphite Microstructures

This report provides an overview and update of the ongoing efforts to create a comprehensive library of microstructures for nuclear graphite and carbon-based materials under consideration for nuclear applications. The library includes data on microstructural characterization of unirradiated graphite materials, a guide to the techniques used to analyze graphite (which complements the ASME guidelines and ASTM standards), a summary of characterization data for neutron-irradiated or oxidized material, and a compendium of microstructural information for carbon-based materials. These efforts are being conducted at various length scales for the filler and binder phases in graphite to better understand graphite’s local structure and property relationships. This report is a follow-up to the previous milestone report titled Report on initial development of a database of nuclear graphite characteristics based on microstructural characterization, ORNL/TM/-2023/2992, published in July 2023.The effort to develop the library of microstructures supports the US Department of Energy Office of Advanced Reactor Technologies program objectives of aiding the material selection, licensing, management, and core assessments of a graphite core by documenting the unirradiated microstructure of relevant grades or characterizing the microstructure’s evolution under the reactor environment. Additionally, this project aims to provide (1) information and guidelines for the characterizing of graphite and (2) a protocol to assess a nuclear graphite grade.

36 MATERIALS SCIENCE↗

Stacking fault induced tunnel barrier in platelet graphite nanofiber

A correlation study using image inspection and electrical characterization of platelet graphite nanofiber devices is conducted. Close transmission electron microscopy and diffraction pattern inspection reveal layers with inflection angles appearing in otherwise perfectly stacked graphene platelets, separating nanofibers into two domains. Electrical measurement gives a stability diagram consisting of alternating small-large Coulomb blockade diamonds, suggesting that there are two charging islands coupled together through a tunnel junction. Based on these two findings, we propose that a stacking fault can behave as a tunnel barrier for conducting electrons and is responsible for the observed double-island single electron transistor characteristics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Radiation Characterization Summary: ACRR Polyethylene-Lead-Graphite (PLG) Bucket Located in the Central Cavity on the 32-Inch Pedestal at the Core Centerline (ACRR-PLG-CC-32-cl).

This document presents the facility-recommended characterization of the neutron, prompt gamma-ray, and delayed gamma-ray radiation fields in the Annular Core Research Reactor (ACRR) for the polyethylene-lead-graphite (PLG) bucket in the central cavity on the 32-inch pedestal at the core centerline. The designation for this environment is ACRR-PLG-CC-32-cl. The neutron, prompt gamma-ray, and delayed gamma-ray energy spectra, uncertainties, and covariance matrices are presented as well as radial and axial neutron and gamma-ray fluence profiles within the experiment area of the bucket. Recommended constants are given to facilitate the conversion of various dosimetry readings into radiation metrics desired by experimenters. Representative pulse operations are presented with conversion examples. Acknowledgements The authors wish to thank the Annular Core Research Reactor staff and the Radiation Metrology Laboratory staff for their support of this work. Also thanks to David Ames for his assistance in running MCNP on the Sandia parallel machines.

Vehar, David W.↗

Progress Report on Graphite-Salt Intrusion Studies

The document reports on the design, construction, testing and initial operation of the ORNL graphite intrusion system with pressurized molten salts. This technical memorandum is responsive to work package AT-20OR04060203, “Graphite-Salt Studies” —ORNL”, and fulfills Milestone M3AT20OR040602035 “Report on graphite-salt intrusion studies”.The report outlines the procedure of graphite intrusion experiments, which follows the ASTM standard guidance, and the procedures of other characterization measurements of graphite physical properties, also based on ASTM standard methods. A set of 12 graphite grades of various origin and properties went through preliminary characterizations, and six of them were further selected for intrusion experiments with molten FLiNaK. The results are discussed in the context of graphite physical properties and are compared with a several results from literature. The correlation between molten salt impregnation and mercury intrusion, first proposed by MSRE scientists, is discussed in detail. Pending collection of more data, the mercury intrusion porosimetry technique may possibly be used as a rapid method for screening and down selection of graphite grades with extremely low salt intrusion, as required for operation in molten salt reactors. This new system will generate data non only on intrusion behavior, but will also generate a wide range of salt- impregnated graphite samples that will be further analyzed with advanced characterization techniques for better understanding of the effect of salt intrusion on the properties of nuclear graphite. It expected that these results and future results obtained with this system will help advance our understanding of the factors controlling the extent of salt penetration in graphite and of the relationship with intrinsic structural properties of various grades. Together, correlating direct measurements results and graphite structural properties should allow development of a predictable model that could be used for selection and qualification of optimal graphite grades, tailored to design operation conditions and molten salt properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical Characterization and Removal of C-14 from Irradiated Graphite-12010

Quantities of irradiated graphite waste are expected to drastically increase, which indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 (C-14), with a half-life of 5730 years. Study of irradiated graphite from nuclear reactors indicates C-14 is concentrated on the outer 5 mm of the graphite structure. The aim of the research described here is to identify the chemical form of C-14 in irradiated graphite and develop a practical method by which C-14 can be removed. Characterization of pre- and post-irradiation graphite was conducted to determine bond type, functional groups, location and concentration of C-14 and its precursors via the use of surface sensitive characterization techniques. Because most surface C-14 originates from neutron activation of nitrogen, an understanding of nitrogen bonding to graphite may lead to a greater understanding of the formation pathway of C-14. However, no single technique provides a complete picture. Therefore, a portfolio of techniques has been developed, with each technique providing another piece to the puzzle that is the chemical nature of the C-14. Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), and Raman Spectroscopy were used to evaluate the morphological features of graphite samples. The concentration, chemical composition, and bonding characteristics of C-14 and its precursors were determined through X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (SIMS), and Auger and Energy Dispersive X-ray Analysis Spectroscopy (EDX). High-surface-area graphite foam, POCOFoam{sup R}, was exposed to liquid nitrogen and irradiated. Characterization of this material has shown C-14 to C-12 ratios of 0.035. This information was used to optimize the thermal treatment of graphite. Thermal treatment of irradiated graphite as reported by Fachinger et al. (2007) uses naturally adsorbed oxygen complexes to gasify graphite, thus its effectiveness is highly dependent on the availability of adsorbed oxygen compounds. In research presented, the quantity and form of adsorbed oxygen complexes in pre- and post irradiated graphite was studied using SIMS and XPS. SIMS and XPS detected adsorbed oxygen compounds on both irradiated and unirradiated graphite. During thermal treatment graphite samples are heated in the presence of inert argon gas, which carries off gaseous products released during treatment. Experiments were performed at 900 deg. C and 1400 deg. C to evaluate the selective removal of C-14. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of structural defects in nuclear graphite IG-110 and NBG-18

Nuclear graphite IG-110 and NBG-18 were examined using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM) and high resolution transmission electron microscope (HR-TEM) to understand the structure and microstructure of nuclear graphite. The lattice parameter (a), degree of graphitization ( ), crystallite size parallel and perpendicular to c-direction (Lc and L ), anisotropy (B), as well as in-plane crystallite size (La) were calculated and compared based on XRD patterns and Raman spectra. Results indicate that IG-110 has a larger crystallite size and higher degree of graphitization, but lower anisotropy than NBG-18. These differences are attributed to the properties of coke source and manufacturing processes. Additionally, the shape of the pores and crystallized filler particles, the interface between binders and fillers, Mrozowski cracks and nano-cracks, and the defects of disclination were observed and characterized from SEM and HR-TEM images. The similarities and differences in microstructure between IG-110 and NBG-18 are discussed. The results in this work provide useful information to guide selection of nuclear graphite for the design of next generation nuclear plants (NGNP).

99 GENERAL AND MISCELLANEOUS↗

Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)

Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.

Hurwitz, F. I.↗