Silicon carbide (SiC) materials are prime candidates for high temperature heat exchangers for next generation nuclear reactors due to their refractory nature and high thermal conductivity at elevated temperatures. This research has focused on demonstrating the potential of liquid silicon infiltration (LSI) for making SiC to achieve this goal. The major advantage of this method over other ceramic processing techniques is the enhanced capability of making fully dense, high purity SiC materials in complex net shapes.
For successful formation of net shape SiC using LSI techniques, the carbon preform reactivity and pore structure must be controlled to allow the complete infiltration of the porous carbon structure followed by conversion of this carbon to SiC. We have established a procedure for achieving desirable carbon properties by using carbon precursors consisting of two readily available high purity organic materials, crystalline cellulose and phenolic resin. Phenolic resin yields a glassy carbon with low reactivity and porosity, and cellulose carbon is highly reactive and porous. By adjusting the ratio of these two materials in the precursor mixtures, the properties of the carbons produced can be controlled.
We have identified the most favorable carbon precursor composition to be a cellulose:resin mass ratio of 6:4 for LSI formation of SiC. The optimum reaction conditions are a temperature of 1800°C, a pressure of 0.5 Torr of argon, and a time of 120 minutes. The fully dense net shape SiC material produced has a density of 2.96 g cm-3 (about 92% of pure SiC) and a SiC volume fraction of over 0.82.
Kinetics of the LSI SiC formation process were studied by optical microscopy and quantitative digital image analysis. This study identified six reaction stages and provided important understanding of the process. Such knowledge can be used to further refine the LSI technique.
Although the thermal conductivity of pure SiC at elevated temperatures is very high, thermal conductivities of most commercial SiC materials are much lower due to phonon scattering by impurities (e.g., sintering aids located at the grain boundaries of these materials). The thermal conductivity of our SiC was determined using the laser flash method and it is 214 W/mK at 373 K and 64 W/mK at 1273 K. These values are very close to those of pure SiC and are much higher than those of SiC materials made by industrial processes. Thus, SiC made by our LSI process is an ideally suited material for use in high temperature heat exchanger applications.
Electron probe microanalysis (EPMA) and Auger electron spectroscopy (AES) were used to study the chemical composition of LSI SiC materials. Optimized low voltage microanalysis conditions for EPMA of SiC were theoretically determined. EPMA and AES measurements indicate that the SiC phase in our materials is slightly carbon rich. Carbon contamination was identified as a possible source of error during EPMA of SiC, and this error was corrected by using high purity SiC standards.
Cellulose and phenolic resin carbons lack the well-defined atomic structures associated with common carbon allotropes. Atomic-scale structure was studied using high resolution transmission electron microscopy (HRTEM), nitrogen gas adsorption and helium gas pycnometry. These studies revealed that cellulose carbon exhibits a very high degree of atomic disorder and angstrom-scale porosity. It has a density of only 93% of that of pure graphite, with primarily sp2 bonding character and a low concentration of graphene clusters. Phenolic resin carbon shows more structural order and substantially less angstrom-scale porosity. Its density is 98% of that of pure graphite, and Fourier transform analysis of its TEM micrographs has revealed high concentrations of sp3 diamond and sp 2 graphene nano-clusters. This is the first time that diamond nano-clusters have been observed in carbons produced from phenolic resin.