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For the next generation of nuclear reactors, HTGRs specifically, an unlikely air ingress warrants inclusion in the license applications of many international regulators. Much research on oxidation rates of various graphite grades under a number of conditions has been undertaken to address such an event. However, consequences to the reactor result from the microstructural changes to the graphite rather than directly from oxidation. The microstructure is inherent to a graphite's properties and ultimately degradation to the graphite's performance must be determined to establish the safety of reactor design. To understand the oxidation induced microstructural change and its corresponding impact on performance, a thorough understanding of the reaction system is needed. This article provides a thorough review of the graphite-molecular oxygen reaction in terms of kinetics, mass and energy transport, and structural evolution: all three play a significant role in the observed rate of graphite oxidation. These provide the foundations of a microstructurally informed model for the graphite-molecular oxygen reaction system, a model kinetically independent of graphite grade, and capable of describing both the observed and local oxidation rates under a wide range of conditions applicable to air-ingress. [ABSTRACT FROM AUTHOR]

Laser ultrasonic line source methods have been used to study elastic anisotropy in nuclear graphites by measuring shear wave birefringence. Depending on the manufacturing processes used during production, nuclear graphites can exhibit various degrees of material anisotropy related to preferred crystallite orientation and to microcracking. In this study, laser ultrasonic line source measurements of shear wave birefringence on NBG-25 have been performed to assess elastic anisotropy. Laser line sources allow specific polarizations for shear waves to be transmitted – the corresponding wavespeeds can be used to compute bulk, elastic moduli that serve to quantify anisotropy. These modulus values can be interpreted using physical property models based on orientation distribution coefficients and microcrack-modified, single crystal moduli to represent the combined effects of crystallite orientation and microcracking on material anisotropy. Ultrasonic results are compared to and contrasted with measurements of anisotropy based on the coefficient of thermal expansion to show the relationship of results from these techniques. [ABSTRACT FROM AUTHOR]

Abstract: Natural graphite powders were subjected to a series of thermal treatments to improve the anode irreversible capacity loss and capacity retention during long-term cycling of lithium-ion batteries. A baseline thermal treatment in inert Ar or N2 atmosphere was compared to cases with a proprietary additive to the furnace gas. This additive substantially altered the surface chemistry of the uncoated natural graphite powders and resulted in significantly improved long-term cycling performance of the lithium ion batteries over the commercial, carbon-coated natural graphite baseline. Different heat-treatment temperatures were investigated ranging from 950 to 2900°C to achieve the desired long-term cycling performance with a significantly reduced thermal budget. A detailed summary of the characterization data is also presented, which includes X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and temperature-programmed desorption-mass spectroscopy. Characterization data was correlated to the observed capacity fade improvements over the course of long-term cycling at high charge–discharge rates in full lithium-ion cells. It is believed that the long-term performance improvements are a result of forming a more stable solid electrolyte interface (SEI) layer on the anode graphite surfaces, which is directly related to the surface chemistry modifications imparted by the proprietary gas environment during thermal treatment. [Copyright &y& Elsevier]

Abstract: Oxidation resistance in air of three grades of nuclear graphite with different structures was compared using a standard thermogravimetric method. Differences in the oxidation behavior have been identified with respect to both (i) the rate of oxidation in identical conditions and the derived apparent activation energy and pre-exponential factor and (ii) the penetration depth of the oxidant and the development of the oxidized layer. These differences were ascribed to structural differences between the three graphite grades, in particular the grain size and shape of the graphite filler, and the associated textural properties, such as total BET surface area and porosity distribution in the un-oxidized material. It was also found that the amount of strongly bonded surface oxygen complexes measured by thermodesorption significantly exceeds the amount afforded by the low BET surface area, and therefore low temperature oxygen chemisorption is not a reliable method for determining the amount of surface sites (re)active during air oxidation. The relationship between nuclear graphite microstructure and its oxidation resistance demonstrated in this work underlines the importance of performing comprehensive oxidation characterization studies of the new grades of nuclear graphite considered as candidates for very high temperature gas-cooled reactors. [Copyright &y& Elsevier]

Abstract: Quasi-elastic neutron scattering was used for characterization of dynamics of molecular hydrogen confined in narrow nanopores of two activated carbon materials: a carbon derived from polyfurfuryl alcohol and an ultramicroporous carbon. Fast, but incomplete ortho–para conversion was observed at 10K, suggesting that scattering originates from the fraction of unconverted ortho isomer which is rotation-hindered because of confinement in nanopores. Hydrogen molecules entrapped in narrow nanopores (<7Å) were immobile below 22–25K. Mobility increased rapidly with temperature above this threshold, which is higher than the melting point of bulk hydrogen (13.9K). Diffusion obeyed fixed-jump length mechanism, indistinguishable between 2D and 3D processes. Thermal activation of diffusion was characterized between ∼22 and 37K, and structure-dependent differences were found between the two carbons. Activation energy of diffusion was higher than that of bulk solid hydrogen. Classical notions of liquid and solid do not longer apply for H2 confined in narrow nanopores. [Copyright &y& Elsevier]

In this work, we present a model for analyzing activated carbon micropore structures based on graphene sheet walls of finite thickness and extent. This is a two-dimensional modification of the widely used infinite slit pore model that assumes graphite-like infinitely extended pore walls. The proposed model has two versions: (1) a strip pore constructed with graphene strip walls that have a finite length L in the x-direction and are infinite in the y-direction. Strip pores are open on both sides in the x-direction; (2) a channel pore, i.e. a strip pore partially closed along one edge by a perpendicularly orientated graphene wall. This more realistic model allows pore termination via both physical pore entrances and pore blockage. The model consequently introduces heterogeneity of the adsorption potential that is reduced near pore entrances and enhanced near the corners of pore walls. These energetically heterogeneous structures fill with adsorbate more gradually than homogeneous pores of the same width. As a result, the calculated adsorption isotherms are smoother and less steep for the finite versus the infinite pore model. In the application of this model for carbon characterization, it is necessary to make an assumption about the pore length. In this work, we made this assumption based on high-resolution scanning transmission electron microscopy (STEM) results. We find the agreement between the experiment and the model significantly better for the finite than for the infinite pore model. [ABSTRACT FROM AUTHOR]

Abstract: The efforts for designing a meaningful and acceptable standard test method for characterization of kinetic parameters of air oxidation of graphite helped identify several practical issues that must be considered for the development of such a test. Using standard size (and shape) specimens, large enough in size to accommodate the inherent local microstructure differences between graphite samples, resulted in non-uniform oxidation profiles and preferential binder oxidation; this was not expected based on the linearity of Arrhenius plots and the (large) values of activation energy. It was found that the transition between the regimes 1 and 2 of graphite oxidation occurs gradually, depending both on the oxidation temperature and rate of oxygen supply. Nevertheless, measuring oxidation rates obtained on standard size samples provides a basis for a meaningful comparison among materials, which may serve as much needed information for predictive models. [Copyright &y& Elsevier]

This work compared the 3D Random Pore Model (3D-RPM) with experimental and characterization data to systematically study the effect of nuclear graphite microstructure and air oxidation temperature. It is well known that oxidation-induced weight loss at elevated temperatures degrades graphite structure and properties; however, a fundamental understanding of the role of graphite microstructure is still unclear. In this work, three diverse grades of nuclear graphite—IG-110, NBG-18, and PCEA—were examined and tested at air oxidation temperatures of 600, 650, 700, and 750 °C following ASTM D7542. The 3D-RPM reproduced the microstructure and temperature dependence of mass loss curves for these grades. For the first time, measurements and modeling were combined to show how bulk density and the amount and spatial distribution of open and closed porosity affects oxidation. IG-110 was less dense and had an open pore network that is finer and more uniformly spread, and showed fastest oxidation. PCEA porosity was less uniform and showed less oxidation, while NBG-18 was more dense, had the least fine and uniform porosity, and showed the slowest oxidation. In general, oxidation proceeds faster if open porosity is more uniformly distributed and can incrementally access closed pore surface area with more ease. [Display omitted] • 3D microstructural model reproduced the oxidation mass loss of three grades at four different oxidation temperatures. • In the microstructure, the amount of open and closed pores and their proximity to each other are important factors. • Intrinsic reactivity of high-purity graphite is independent of grade and follows expected temperature scaling. • Even in kinetic regime oxidation, there can be a density gradient due to spatial distribution of porosity and sample size. [ABSTRACT FROM AUTHOR]

Abstract: Aberration corrected scanning transmission electron microscopy was used to demonstrate the feasibility of imaging individual Pd atoms that are highly dispersed throughout the volume of activated carbon fibers. Simultaneous acquisition of high-angle annular dark-field and bright-field images allows correlation of the location of single Pd atoms with microstructural features of the carbon host material. Sub-Ångström imaging conditions revealed that 18wt% of the total Pd content is dispersed as single Pd atoms in three re-occurring local structural arrangements. The identified structural configurations may represent effective storage sites for molecular hydrogen through Kubas complex formation as discussed in detail in the preceding article [Carbon XX (2011), page XXX]. [Copyright &y& Elsevier]

Abstract: Palladium-doped activated carbon fibers are being evaluated as candidate materials for enhanced hydrogen storage at near ambient conditions. Pd-doped fibers were spun using a Pd salt mixed with an isotropic pitch precursor. Experimental techniques such as in situ X-ray analysis, thermogravimetric studies, scanning transmission electron microscopy and gas adsorption were employed to understand how processing conditions for the production of Pd-doped activated carbon fibers affect the microstructure, pore development, and dispersion of metal particles throughout the fibers. The results showed that PdO phase is present in the stabilized fibers and that this oxide phase is stable up to about 250°C. The oxide phase transforms into Pd metal with increasing heat treatment temperature, going through the formation of an intermediate carbide phase. Sintering of Pd particles was observed with heat treatment at temperatures over 750°C. It was also found that pore development during physical activation with CO2 was not significantly affected by the presence of Pd particles within the fibers. [Copyright &y& Elsevier]

Beginning with Chicago Pile I, graphite has been used as a moderator material in nuclear power stations and is considered a potential material for use in future Generation IV advanced reactors. The microstructure of graphite is responsible for much of its mechanical and thermo-physical properties, and how it responds to irradiation. To understand graphite microstructure, it is necessary to understand its porosity at the macro- and micro-scales; and to understand its porosity, it is necessary to characterize the morphological connectivity of the void content and the two main phases of graphite: filler and binder. Here, using several microscopy and analytical techniques, a detailed examination of the heterogeneity, microstructure and pore structure of different graphite grades and their binder and filler phases is presented. Significant differences were found between coarser and finer nuclear grades. Coarse grades have a more diverse range of filler particles, pores and thermal cracks. Finer grades have a more well-defined pore size distribution, fewer variations of filler particles sizes and do not contain as many large thermal cracks. Fine grades tend to have a well-connected network of pores whereas coarser grades contain a larger content of closed porosity. The framework developed within this work can be applied and used to assess the various graphite grades that would down-select materials for specific use in graphite moderated reactor designs. [Display omitted] • Microstructural characterization techniques were combined to understand the phases of graphite. • A comparison of the most common microstructural techniques used to characterize nuclear graphite is provided. • The porosity analysis demonstrates a significant difference between different graphite grades caused by the grain size and raw materials. [ABSTRACT FROM AUTHOR]

Abstract: Potassium-doped activated carbon was prepared by mixing potassium salt with polyfurfuryl alcohol precursor followed by carbonization and activation. Several experimental techniques, such as thermogravimetric analysis, gas adsorption, X-ray diffraction and Raman scattering spectroscopy were employed to understand the effects of potassium on the texture and pore structures of the activated carbon, which ultimately affects the hydrogen adsorption properties. After doping with potassium, the activated carbon exhibits higher surface area, higher micropore volume, and enhanced hydrogen adsorption capacity. Understanding of how alkali metals affect surface area and micropore development in activated carbon may help to clarify the hydrogen adsorption mechanism and improve the design of suitable carbon-based hydrogen storage materials. [Copyright &y& Elsevier]