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Fox, Dennis S.

Publications and source records attributed to Fox, Dennis S..

49 records · Page 3

Oxidation kinetics of CVD silicon carbide and silicon nitride

The long-term oxidation behavior of pure, monolithic CVD SiC and Si3N4 is studied, and the isothermal oxidation kinetics of these two materials are obtained for the case of 100 hrs at 1200-1500 C in flowing oxygen. Estimates are made of lifetimes at the various temperatures investigated. Parabolic rate constants for SiC are within an order of magnitude of shorter exposure time values reported in the literature. The resulting silica scales are in the form of cristobalite, with cracks visible after exposure. The oxidation protection afforded by silica for these materials is adequate for long service times under isothermal conditions in 1-atm dry oxygen.

Fox, Dennis S.↗

Reactions of silicon carbide and silicon(IV) oxide at elevated temperatures

The reaction between SiC and SiO2 has been studied in the temperature range 1400-1600 K. A Knudsen cell in conjunction with a vacuum microbalance and a high-temperature mass spectrometer was used for this study. Two systems were studied - 1:1 SiC (2 wt pct excess carbon) and SiO2; and 1:1:1 SiC, carbon, and SiO2. In both cases the excess carbon forms additional SiC within the Knudsen cell and adjusts to the direct reaction of stoichiometric SiC and SiO2 to form SiO(g) and CO(g) in approximately a 3:1 ratio. These results are interpreted in terms of the Si-C-O stability diagram.

Jacobson, Nathan S.↗

Environmental durability of ceramics and ceramic composites

An account is given of the current understanding of the environmental durability of both monolithic ceramics and ceramic-matrix composites, with a view to the prospective development of methods for the characterization, prediction, and improvement of ceramics' environmental durability. Attention is given to the environmental degradation behaviors of SiC, Si3N4, Al2O3, and glass-ceramic matrix compositions. The focus of corrosion prevention in Si-based ceramics such as SiC and Si3N4 is on the high and low sulfur fuel combustion-product effects encountered in heat engine applications of these ceramics; sintering additives and raw material impurities are noted to play a decisive role in ceramics' high temperature environmental response.

Fox, Dennis S.↗

Elevated temperature mechanical behavior of monolithic and SiC whisker-reinforced silicon nitrides

The mechanical behavior of a 30 volume percent SiC whisker reinforced silicon nitride and a similar monolithic silicon nitride were measured at several temperatures. Measurements included strength, fracture toughness, crack growth resistance, dynamic fatigue susceptibility, post oxidation strength, and creep rate. Strength controlling defects were determined with fractographic analysis. The addition of SiC whiskers to silicon nitride did not substantially improve the strength, fracture toughness, or crack growth resistance. However, the fatigue resistance, post oxidation strength, and creep resistance were diminished by the whisker addition.

Salem, Jonathan A.↗

Burner rig hot corrosion of silicon carbide and silicon nitride

A number of commercially available SiC and Si3N4 materials were exposed to 1000 C for 40 h in a high-velocity, pressurized burner rig as a simulation of an aircraft turbine environment. Na impurities (2 ppm) added to the burner flame resulted in molten Na2SO4 deposition, attack of the SiC and Si3N4, and formation of substantial Na2O+x(SiO2) corrosion product. Room-temperature strength of the materials decreased as a result of the formation of corrosion pits in SiC and grain-boundary dissolution and pitting in Si3N4.

Fox, Dennis S.↗

Hot corrosion of silicon carbide and silicon nitride at 1000 C

The sodium sulfate hot corrosion of silicon-based ceramics at 1000 C has been extensively studied. Deposition of the sodium sulfate corrodant from combustion products is discussed in relation to sodium air impurity and sulfur fuel impurity content. Corrosion occurs by the combined processes of oxidation to form protective silica scales and dissolution of these scales to form nonprotective sodium silicates. The chemical corrosion mechanisms are presented in terms of acidic/basic dissolution of oxides in molten salts. The reactions are strongly influenced by the presence of free carbon in the ceramic. Strength reductions have been measured and are attributed to pitting in SiC and grain boundary attack in Si3N4. Initial results of burner corrosion of two ceramic matrix composites are consistent with the models developed for monolithic ceramics.

Fox, Dennis S.↗

The behavior of SiC and Si3N4 ceramics in mixed oxidation/chlorination environments

The behavior of silicon-based ceramics in mixed oxidation/chlorination environments was studied. High pressure mass spectrometry was used to quantitatively identify the reaction products. The quantitative identification of the corrosion products was coupled with thermogravimetric analysis and thermodynamic equilibrium calculations run under similar conditions in order to deduce the mechanism of corrosion. Variations in the behavior of the different silicon-based materials are discussed. Direct evidence of the existence of silicon oxychloride compounds is presented.

Marra, John E.↗

Reactions of silicon-based ceramics in mixed oxidation chlorination environments

The reaction of silicon-based ceramics with 2 percent Cl2/Ar and 1 percent Cl2/1 percent to 20 percent O2/Ar at 950 C was studied with thermogravimetric analysis and high-pressure mass spectrometry. Pure Si, SiO2, several types of SiC, and Si3N4 were examined. The primary corrosion products were SiCl4(g) and SiO2(s) with smaller amounts of volatile silicon oxychlorides. The reactions appear to occur by chlorine penetration of the SiO2 layer, and gas-phase diffusion of the silicon chlorides away from the sample appears to be rate limiting. Pure SiO2 shows very little reaction with Cl2, SiC with excess Si is more reactive than the other materials with Cl2, whereas SiC with excess carbon is more reactive than the other materials with Cl2/O2. Si3N4 shows very little reaction with Cl2. These differences are explained on the basis of thermodynamic and microstructural factors.

Marra, John E.↗

Molten salt corrosion of SiC and Si3N4

Industrial systems such as heat engines and heat exchangers involve harsh environments. The structural materials are subjected to high temperatures as well as corrosive gases and condensed phases. Past experience with metal alloys has shown that these condensed phases can be particularly corrosive and are often the limiting factor in the operation of these systems. In a heat engine the most common condensed corrodent is Na2SO4 whereas in a heat exchanger an oxide slag may be present. The primary emphasis is on Na2SO4 induced corrosion, however, similarities and differences to oxide slag are also discussed. The extensive research on corrosion of metal alloys has led to understanding and controlling corrosion for these materials. Currently silicon based ceramics are prime candidates for the applications discussed. Therefore it is important to understand the effects of condensed phase deposits on this emerging class of high temperature materials. Both the thermodynamic and strength of the ceramic is also examined. Finally some control strategies for corrosion of silicon based ceramics are explored.

Jacobson, Nathan S.↗

Direct mass spectrometric identification of silicon oxychloride compounds

Silicon oxychloride compounds formed during the high temperature reaction of Si and SiC with Cl2/O2 mixtures at 930 and 950 C have been directly observed with an atmospheric pressure mass spectrometer sampling system. Molecules with the formulas Si2OCl6 and Si3OCl8 have been identified. These compounds are very likely formed by a gas phase reaction between the oxygen gas in the system and silicon tetrachloride which is produced by chlorination of the silicon-based material.

Marra, John E.↗

Molten-salt corrosion of silicon nitride. I - Sodium carbonate. II - Sodium sulfate

An experimental study of the corrosion of Si3N4 under thin films of Na2CO3 at 1000 C has been conducted using both pure Si3N4 and Si3N4 with various additives. The reaction mechanism is shown to consist of: (1) the decomposition of Na2CO3 and the formation of Na2SiO3; (2) rapid oxidation; and (3) the formation of a protective silica layer below the silicate. In the second part, the corrosion mechanism of Si3N4 + Na2SO4/O2 at 1000 C was studied for both pure and additive-containing Si3N4. The reaction of Si3N4 + Na2SO4 was found to involve an initial period of slow weight loss (due to Na2SO4 vaporization and oxidation-dissolution) followed by further oxidation or the near termination of the reaction, depending on the Si3N4 additive.

Fox, Dennis S.↗

Hot corrosion of ceramic engine materials

A number of commercially available SiC and Si3N4 materials were exposed to 1000 C in a high velocity, pressurized burner rig as a simulation of a turbine engine environment. Sodium impurities added to the burner flame resulted in molten Na2SO4 deposition, attack of the SiC and Si4N4 and formation of substantial Na2O-x(SiO2) corrosion product. Room temperature strength of the materials decreased. This was a result of the formation of corrosion pits in SiC, and grain boundary dissolution and pitting in Si3N4. Corrosion regimes for such Si-based ceramics have been predicted using thermodynamics and verified in rig tests of SiO2 coupons. Protective mullite coatings are being investigated as a solution to the corrosion problem for SiC and Si3N4. Limited corrosion occurred to cordierite (Mg2Al4Si5O18) but some cracking of the substrate occurred.

Fox, Dennis S.↗

Hot corrosion attack and strength degradation of SiC and Si(sub)3N(sub)4

Thin films of Na2SO4 and Na2CO3 molten salt deposits were used to corrode sintered SiC and Si3N4 at 1000 C. The resulting attack produced pitting and grain boundary etching resulting in strength decreases ranging from 15 to 50 percent. Corrosion pits were the predominant sources of fracture. The degree of strength decrease was found to be roughly correlated with the depth of the pit, as predicted from fracture toughness considerations. Gas evolution and bubble formation were key aspects of pit formation. Many of the observations of furnace exposures held true in a more realistic burner rig test.

Smialek, James L.↗