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Title: SILICON CARBIDE CERAMICS FOR COMPACT HEAT EXCHANGERS

Abstract

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 high 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 which allows complete conversion of the 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 chemical reactivity and porosity while the 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 massmore » 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{sup -3} (about 92% of pure SiC) and a SiC volume fraction of over 0.82. Kinetics of the LSI SiC formation process was studied by optical microscopy and quantitative digital image analysis. This study identified six reaction stages and provided important understanding of the process. 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. This SiC made by our LSI process meets the thermal properties required for use in high temperature heat exchanger. 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 sp2 graphene nano-clusters. This is the first time that diamond nano-clusters have been observed in carbons produced from phenolic resin. AC and DC electrical measurements were made to follow the thermal conversion of microcrystalline cellulose to carbon. This study identifies five regions of electrical conductivity that can be directly correlated to the chemical decomposition and microstructural evolution during carbonization. In Region I, a decrease in overall AC conductivity occurs due to the initial loss of the polar groups from cellulose molecules. In Region II, the AC conductivity starts to increase with heat treatment temperature due to the formation and growth of conducting carbon clusters. In Region III, a further increase of AC conductivity with increasing heat treatment temperature is observed. In addition, the AC conductivity demonstrates a non-linear frequency dependency due to electron hopping, interfacial polarization, and onset of a percolation threshold. In Region IV, the DC conductivity continues to increase with heat treatment due to the growth and percolation of carbon clusters. Finally in Region V, the DC conductivity reaches a plateau with increasing heat treatment temperature as the system reaches a fully percolated state. Thermophysical properties of carbon materials derived from microcrystalline cellulose have been measured under vacuum and compared with earlier measurements conducted under nitrogen to better understand the influence of porosity, composition, and atmosphere effects. The effective thermal conductivity in vacuum is lower than that observed in nitrogen primarily due to the conductivity of nitrogen gas.« less

Authors:
;
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
950101
Report Number(s):
DOE/ID/14676-3
TRN: US0902106
DOE Contract Number:  
FC07-05ID14676
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 22 GENERAL STUDIES OF NUCLEAR REACTORS; CERAMICS; ELECTRIC CONDUCTIVITY; HEAT EXCHANGERS; REACTORS; RESINS; CELLULOSE; CASTING MOLDS; FLUID INJECTION; LIQUID METALS; PORE STRUCTURE; SILICON CARBIDES; THERMAL CONDUCTIVITY; SYNTHESIS

Citation Formats

NAGLE, DENNIS, and ZHANG, DAJIE. SILICON CARBIDE CERAMICS FOR COMPACT HEAT EXCHANGERS. United States: N. p., 2009. Web. doi:10.2172/950101.
NAGLE, DENNIS, & ZHANG, DAJIE. SILICON CARBIDE CERAMICS FOR COMPACT HEAT EXCHANGERS. United States. https://doi.org/10.2172/950101
NAGLE, DENNIS, and ZHANG, DAJIE. Thu . "SILICON CARBIDE CERAMICS FOR COMPACT HEAT EXCHANGERS". United States. https://doi.org/10.2172/950101. https://www.osti.gov/servlets/purl/950101.
@article{osti_950101,
title = {SILICON CARBIDE CERAMICS FOR COMPACT HEAT EXCHANGERS},
author = {NAGLE, DENNIS and ZHANG, DAJIE},
abstractNote = {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 high 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 which allows complete conversion of the 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 chemical reactivity and porosity while the 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{sup -3} (about 92% of pure SiC) and a SiC volume fraction of over 0.82. Kinetics of the LSI SiC formation process was studied by optical microscopy and quantitative digital image analysis. This study identified six reaction stages and provided important understanding of the process. 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. This SiC made by our LSI process meets the thermal properties required for use in high temperature heat exchanger. 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 sp2 graphene nano-clusters. This is the first time that diamond nano-clusters have been observed in carbons produced from phenolic resin. AC and DC electrical measurements were made to follow the thermal conversion of microcrystalline cellulose to carbon. This study identifies five regions of electrical conductivity that can be directly correlated to the chemical decomposition and microstructural evolution during carbonization. In Region I, a decrease in overall AC conductivity occurs due to the initial loss of the polar groups from cellulose molecules. In Region II, the AC conductivity starts to increase with heat treatment temperature due to the formation and growth of conducting carbon clusters. In Region III, a further increase of AC conductivity with increasing heat treatment temperature is observed. In addition, the AC conductivity demonstrates a non-linear frequency dependency due to electron hopping, interfacial polarization, and onset of a percolation threshold. In Region IV, the DC conductivity continues to increase with heat treatment due to the growth and percolation of carbon clusters. Finally in Region V, the DC conductivity reaches a plateau with increasing heat treatment temperature as the system reaches a fully percolated state. Thermophysical properties of carbon materials derived from microcrystalline cellulose have been measured under vacuum and compared with earlier measurements conducted under nitrogen to better understand the influence of porosity, composition, and atmosphere effects. The effective thermal conductivity in vacuum is lower than that observed in nitrogen primarily due to the conductivity of nitrogen gas.},
doi = {10.2172/950101},
url = {https://www.osti.gov/biblio/950101}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2009},
month = {3}
}