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Jacobson, Nathan S.

Publications and source records attributed to Jacobson, Nathan S..

106 records · Page 6

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗

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.↗

Thermodynamic properties of some metal oxide-zirconia systems

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Jacobson, Nathan S.↗

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗

Sodium sulfate - Deposition and dissolution of silica

The hot-corrosion process for SiO2-protected materials involves deposition of Na2SO4 and dissolution of the protective SiO2 scale. Dew points for Na2SO4 deposition are calculated as a function of pressure, sodium content, and sulfur content. Expected dissolution regimes for SiO2 are calculated as a function of Na2SO4 basicity. Controlled-condition burner-rig tests on quartz verify some of these predicted dissolution regimes. The basicity of Na2SO4 is not always a simple function of P(SO3). Electrochemical measurements of an (Na2O) show that carbon creates basic conditions in Na2SO4, which explains the extensive corrosion of SiO2-protected materials containing carbon, such as SiC.

Jacobson, Nathan 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.↗

Multielement mapping of alpha-SiC by scanning Auger microscopy

Fine second-phase particles, numerous in sintered alpha-SiC, were analyzed by scanning Auger microscopy and conventional techniques. The Auger analysis utilized computer-controlled data acquisition, multielement correlation diagrams, and a high spatial resolution of 100 nm. This procedure enabled construction of false color maps and the detection of fine compositional details within these particles. Carbon, silicon oxide, and boron-rich particles (qualitatively as BN or B4C) predominated. The BN particles, sometimes having a carbon core, are believed to result from reaction between B4C additives and nitrogen sintering atmospheres.

Browning, Ray↗

Materials for engine applications above 3000 deg F: An overview

Materials for future generations of aeropropulsion systems will be required to perform at ever-increasing temperatures and have properties superior to the current state of the art. Improved engine efficiency can reduce specific fuel consumption and thus increase range and reduce operating costs. The ultimate payoff gain is expected to come when materials are developed which can perform without cooling at gas temperatures to 2200 C (4000 F). An overview is presented of materials for applications above 1650 C (3000 F), some pertinent physical property data, and the rationale used: (1) to arrive at recommendations of material systems that qualify for further investigation, and (2) to develop a proposed plan of research. From an analysis of available thermochemical data it was included that such materials systems must be composed of oxide ceramics. The required structural integrity will be achieved by developing these materials into fiber-reinforced ceramic composites.

Shaw, Nancy J.↗

Corrosion of SiC by Molten Salt

Advanced ceramic materials considered for wide range of applications as in gas turbine engines and heat exchangers. In such applications, materials may be in corrosive environments that include molten salts. Very corrosive to alloys. In order to determine extent of problem for ceramic materials, corrosion of SiC by molten salts studied in both jet fuel burners and laboratory furnaces. Surface of silicon carbide corroded by exposure to flame seeded with 4 parts per million of sodium. Strength of silicon carbide decreased by corrosion in flame and tube-furnace tests.

Jacobson, Nathan 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.↗

Mechanism of strength degradation for hot corrosion of alpha-SiC

Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000 percent. This hot corrosion attack reduced room temperature strengths by as much as 50 percent. Strength degradation was proportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is cnsistent ith published values.

Smialek, James L.↗