Status of Chronic Oxidation Studies of Graphite

Contescu, Cristian I.¹  Mee, Robert W.² 

[1] Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States);Univ. of Tennessee, Knoxville, TN (United States)

关键词: kinetic model;    nuclear graphite;    chronic oxidation;    Langmuir-Hinshelwood;    Boltzmann;   

DOI  :  10.2172/1255697
RP-ID  :  ORNL/TM--2016/195
PID  :  OSTI ID: 1255697

学科分类：化学（综合）

美国|英语

来源: SciTech Connect

【 摘 要 】

Graphite will undergo extremely slow, but continuous oxidation by traces of moisture that will be present, albeit at very low levels, in the helium coolant of HTGR. This chronic oxidation may cause degradation of mechanical strength and thermal properties of graphite components if a porous oxidation layer penetrates deep enough in the bulk of graphite components during the lifetime of the reactor. The current research on graphite chronic oxidation is motivated by the acute need to understand the behavior of each graphite grade during prolonged exposure to high temperature chemical attack by moisture. The goal is to provide the elements needed to develop predictive models for long-time oxidation behavior of graphite components in the cooling helium of HTGR. The tasks derived from this goal are: (1) Oxidation rate measurements in order to determine and validate a comprehensive kinetic model suitable for prediction of intrinsic oxidation rates as a function of temperature and oxidant gas composition; (2) Characterization of effective diffusivity of water vapor in the graphite pore system in order to account for the in-pore transport of moisture; and (3) Development and validation of a predictive model for the penetration depth of the oxidized layer, in order to assess the risk of oxidation caused damage of particular graphite grades after prolonged exposure to the environment of helium coolant in HTGR. The most important and most time consuming of these tasks is the measurement of oxidation rates in accelerated oxidation tests (but still under kinetic control) and the development of a reliable kinetic model. This report summarizes the status of chronic oxidation studies on graphite, and then focuses on model development activities, progress of kinetic measurements, validation of results, and improvement of the kinetic models. Analysis of current and past results obtained with three grades of showed that the classical Langmuir-Hinshelwood model cannot reproduce all data collected so far. Starting from here we propose a modification of the LH model to include temperature activation of graphite surface as a Boltzmann activation function. The enhanced Boltzmann-Langmuir-Hinshelwood model (BLH) was tested successfully on three grades of graphite. The model is a robust, comprehensive mathematical function that allows better fitting of experimental results spanning a wide range of temperature and partial pressures of water vapor and hydrogen. However, the model did not fit satisfactorily the data extracted from the old report on graphite H-451 oxidation by water.