Properties of graphitic composites

Abstract

The Pebble Bed Modular Reactor (PBMR) is a high temperature graphite-moderated nuclear reactor that uses helium as a coolant. The triple coated (TRISO) particles contain enriched uranium oxide fuel which is coated with layers of various forms of pyrolytic carbon and silicon carbide. The TRISO particles are further embedded in the matrix of spherical graphite pebbles. The graphite matrix is a composite moulded from a compound containing natural flake graphite (64 wt.%), synthetic graphite (16 wt.%) and a phenolic resin binder (20 wt.%) heated to 1800 °C in inert atmosphere. The graphitic composite provides structural integrity, encasement and act as a moderator material. In this work, low density model graphite composites similar to those used in nuclear applications as encasement material in fuel pebbles were made by uniaxial cold compression moulding. The graphitic composites contained various ratios of natural flake graphite and synthetic graphite at fixed phenolic novolac resin binder content of 20 wt.% (green state). The fabrication process employed entails mixing the graphite powders, followed by addition of methanol phenolic resin solution to the graphite powder mix, drying, grinding, milling and sieving; and finally compression moulding in a stainless steel die at 13 MPa using a hydraulic press. The green moulded disc specimens were then carbonized at 900 °C in nitrogen atmosphere to remove volatiles followed by annealing at 1800 °C in helium atmosphere. The annealing step diminishes structural defects and result in densification of the composites. The microstructure of fabricated graphitic composites was characterized using various techniques. Particle Size Distributions determined using Laser diffraction showed that the inclusion of the binder leads to agglomeration. The composite powders had larger mean particle sizes than the raw graphite powders showing the binding effect of the novolac phenolic resin. X-ray diffraction studies showed that the graphitic composites had a hexagonal crystal structure after annealing. Raman spectroscopy revealed the presence of the structurally disordered phase derived from the resin carbon (indicated by the pronounced D-band in the Raman spectra). XRD and Raman observations were consistent with literature and gave results supporting existing knowledge base. Optical microscopy revealed a flake-like microstructure for composites containing natural graphite and needle-coke like particles for composites containing mainly synthetic graphite. Optical microscopy confirmed that the effect of the manufacturing route employed here was to align the particles in the direction perpendicular to the compression moulding direction. As a result, the graphitic composites exhibited anisotropic property behavior. The bulk density of the composites increased with the increase in the natural graphite content due to compactability of natural flakes in the manufacturing route. Thermogravimetric analysis studies on the composites showed that they were stable in air to 650 °C. Composites containing mainly synthetic graphite were thermally more stable in air compared to their natural graphite counterparts. The linear coefficients of thermal expansion of the composites were measured using thermomechanical analysis (20-600 °C). In the moulding direction, the average CTE (αP) values were in the range (5-9) × 10-6 K-1 and increased with increment in the natural graphite content in the composite. In the direction perpendicular to moulding direction, the average CTE (αN) values were in the range (1.7-2.1) × 10-6 K-1 showing that the expansion was similar or constant in this direction. Therefore an anisotropic expansion ratio, i.e. αP:αN, of about 3 was observed in the composites. This anisotropy is attributable to the alignment of the filler particles in the manufacturing route. The thermal conductivity of the annealed composites were measured in the pressing direction from 100 to 1000 °C and the values ranged from 19 to 30 W m-1 K-1. Anisotropy was also observed as far as strength was concerned. A composite containing 64:16:20 wt.% ratio had the best mechanical properties, high thermal conductivity and slightly high expansion coefficient. This work demonstrates the complimentary properties of the graphite fillers in the composites. It also reports for the first time, data on the effect of variation of the filler graphites on microstructure and properties of model low density compression moulded graphitic composites.