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Stearns, C. A.

Publications and source records attributed to Stearns, C. A..

At least 37 records · Page 2

Chemical processes involved in the initiation of hot corrosion of B-1900 and NASA-TRW VIA

Sodium surface-induced hot corrosion of B-1900 and NASA-TRW VIA alloys at 900 C has been studied, with special attention to the chemical reactions during and immediately after the induction period. Thermogravimetric tests were run and data were obtained by chemical analysis of water soluble metal salts and of residual sulfate. Surface analyses of hot corroded samples were obtained by spectroscopic techniques (ESCA). A chemical mechanism for elucidating Na2SO4-induced hot corrosion is proposed indicating that hot corrosion is initiated by basic fluxing of the protective Al2O3 scale. The sequential, catastrophic corrosion results from molybdenum content. The self-sustaining feature is a consequence of the cyclic nature of the acidic fluxing. It is believed that the mechanism is applicable not only to laboratory results, but also to the practical problem of hot corrosion encountered in gas turbine engines.

Fryburg, G. C.↗

The chemistry of sodium chloride involvement in processes related to hot corrosion

Sodium chloride is one of the primary contaminants that enter gas turbine engines and contribute, either directly or indirectly, to the hot corrosion degradation of hot-gas-path components. The paper surveys the results of laboratory experiments along with thermodynamic and mass transport calculations, intended for elucidating the behavior of sodium chloride in combustion environments. It is shown that besides being a source of sodium for the formation of corrosive liquid Na2SO4, the NaCl itself contributes in other indirect ways to the material degradation associated with the high-temperature environmental attack. In addition, the experimental results lend credence to the conceptual scheme presented schematically (behavior of NaCl in a turbine engine combustion gas environment) and resolve conflicting aspects of relevant NaCl misconceptions.

Stearns, C. A.↗

Mass spectrometric investigation of the vaporization of sodium and potassium chromates: Preliminary results

Knudsen cell mass spectrometry was used to study the vaporization of sodium and potassium chromates. For both salts, the vaporization proceeds predominately by the reactions M2CrO4(c)=2M(g)+5/4O2(g)+1/2 Cr203(s) and M2CrO4(c)=M2CrO4(g) where M = Na or K. The distribution of the ions M(+), O2(+) and M2CrO4(+) in the measured mass spectrum was found to depend on the material used for the Knudsen cell, even for materials such as platinum and gold. In the case of sodium chromate, the decomposition reaction appears to be less important than the molecular vaporization reaction. A preliminary value of 72 kcal/mole at 1141 K was measured for the heat of the molecular vaporization reaction for sodium chromate. In the case of potassium chromate, it has not been possible to conclude which mode of vaporization dominates. For potassium chromate a value of 101 kcal/mole at 1173 K was obtained for the heat of the molecular vaporization reaction.

Stearns, C. A.↗

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.

Kohl, F. J.↗

The chemistry of sodium chloride involvement in processes related to hot corrosion

Thermodynamic and mass transport calculations, and laboratory experiments elucidating the behavior of sodium chloride in combustion environments, in the deposition process, and in reactions with certain oxides on the surfaces of superalloys are summarized. It was found that some of the ingested salt is separated out of the air stream by the compressor. However, sodium chloride does pass from the compressor to the combustor where numerous chemical reactions take place. Here some of the salt is vaporized to yield gaseous sodium chloride molecules. Hydrogen and oxygen atoms present in the combustion products react with some sodium chloride to yield other gaseous species such as sodium, and a fraction of the salt remains as particulates. Both the gas phase and condensed sodium chloride can lead to sodium sulfate formation by various routes, all of which involve reaction with sulfur oxides and oxygen. In addition to contributing to the formation of sodium sulfate, the sodium chloride can contribute to corrosion directly.

Stearns, C. A.↗

Combustion of solid carbon rods in zero and normal gravity

In order to investigate the mechanism of carbon combustion, spectroscopic carbon rods were resistance ignited and burned in an oxygen environment in normal and zero gravity. Direct mass spectrometric sampling was used in the normal gravity tests to obtain concentration profiles of CO2, CO, and O2 as a function of distance from the carbon surface. The experimental concentrations were compared to those predicted by a stagnant film model. Zero gravity droptower tests were conducted in order to assess the effect of convection on the normal gravity combustion process. The ratio of flame diameter to rod diameter as a function of time for oxygen pressures of 5, 10, 15, and 20 psia was obtained for three different diameter rods. It was found that this ratio was inversely proportional to both the oxygen pressure and the rod diameter.

Spuckler, C. M.↗

Chemical processes involved in the initiation of hot corrosion of B-1900 and NASA-TRW VIA

Sodium sulfate induced hot corrosion of B-1900 and NASA-TRW VIA at 900 C was studied with special emphasis on the chemical reactions occurring during and immediately after the induction period. Thermogravimetric tests were run for set periods of time after which the samples were washed with water and water soluable metal salts and/or residual sulfates were analyzed chemically. Element distributions within the oxide layer were obtained from electron microprobe X-ray micrographs. A third set of samples were subjected to surface analysis by X-ray photoelectron spectroscopy. Evolution of SO2 was monitored throughout many of the hot corrosion tests. Results are interpreted in terms of acid-base fluxing mechanisms.

Fryburg, G. C.↗

Volatile products from the interaction of KCl/g/ with Cr2O3 and LaCrO3 in oxidizing environments

Based on cooled target collection methods and high pressure mass spectrometer sampling, oxidative vaporization rates and emanating volatile products were evaluated for interactions of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments. It was found that: (1) increased rates of oxidative vaporization upon exposure to the reactants are exhibited by chromia and fresh lanthanum chromite samples, and (2) these increased rates result from the heterogeneous formation of complex molecules such as KCl sub 1,2,3CrO3 and KOH sub 1,2CrO3. No increased rates were observed for lanthanum chromite subjected to prolonged oxidative vaporization.

Kohl, F. J.↗

Interaction of NaCl/g/ and HCl/g/ with condensed Na2SO4

Na2SO4(l)-NaCl(g) interactions were studied at a total pressure of one atmosphere of air or oxygen for various temperatures of Na2SO4(l) and for various partial pressures of NaCl(g) and H2O(g). Mass spectrometric sampling techniques were used to identify and monitor gas phase species. Continuous recording thermomicrogravimetric measurements were conducted to determine condensed phase weight change rates. Experimental measurements were supplemented with thermodynamic calculations. Numerous experiments were performed at sample temperatures of 900 and 1000 C with 300 ppm NaCl(g). In these experiments, the reproducibility of the Na2SO4 vaporization weight loss rate and initial weight gain upon addition of NaCl(g) were found to be satisfactory. It was found that the addition of NaCl(g) to air flowing over Na2SO4(l) at 900 and 1000 C enhances the rate of weight loss of the Na2SO4(l). This enhancement increases when H2O(g) is also added to the air flow.

Stearns, C. A.↗

Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous Na2SO4 or K2SO4 molecules were formed in residence times on the order of 1 msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

Fryburg, G. C.↗

High temperature environmental effects on metals

The current status of knowledge and ability to predict high-temperature environmental attack of metals is reviewed with particular reference to the gas turbine engine. Environmental attack is caused by high temperatures, combustion products, and impurities. A schematic representation of life-limiting factors of turbine components shows that environmental attack can lead to very early failures. Attention is given to high-temperature oxidation with prevailing modes of oxidation attack, and to hot corrosion and other impurity effects. Erosion attack results from the direct mechanical removal of component material by impact of hard substances like ash, sand, or dirt. Solutions to hot-corrosion problems can be found semiempirically by using improved alloys or ceramics, protective surface coatings, additives to the engine environment, and air/fuel cleanup to eliminate detrimental impurities.

Grisaffe, S. J.↗

A high pressure modulated molecular beam mass spectrometric sampling system

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Stearns, C. A.↗

Investigation of the formation of gaseous sodium sulfate in a doped methane-oxygen flame

Na2SO4(g) formation was measured at atmospheric pressure in CH4-O2 flames, with high pressure, free-jet expansion, mass spectrometric sampling used to identify and measure reaction products. Measured composition profiles of reaction products for a doped 9.5 mole ratio O2/CH4 flame are presented. Weight percentages of reactants were 4.7 CH4, 89.0 O2, 3.5 H2O, 2.0 SO2 and 0.35 NaCl.

Stearns, C. A.↗

Mechanism of beneficial effect of tantalum in hot corrosion of nickel-base superalloys

X-ray diffraction and electron microprobe analyses were used to examine a prominent NaTaO3 pattern formed in a number of nickel-base superalloys. It is found that a beneficial effect of tantalum with respect to hot corrosion attack arises from the ability of Ta2O5 to tie up Na2O and prevent the formation of a molten Na2MoO4 phase.

Fryburg, G. C.↗

Theoretical and experimental studies of the deposition of Na2So4 from seeded combustion gases

Flames in a Mach 0.3 atmospheric pressure laboratory burner rig were doped with sea salt, NaS04, and NaCl, respectively, in an effort to validate theoretical dew point predictions made by a local thermochemical equilibrium (LTCE) method of predicting condensation temperatures of sodium sulfate in flame environments. Deposits were collected on cylindrical platinum targets placed in the combustion products, and the deposition was studied as a function of collector temperature. Experimental deposition onset temperatures checked within experimental error with LTCE-predicted temperatures. A multicomponent mass transfer equation was developed to predict the rate of deposition of Na2SO4(c) via vapor transport at temperatures below the deposition onset temperature. Agreement between maximum deposition rates predicted by this chemically frozen boundary layer (CFBL) theory and those obtained in the seeded laboratory burner experiments is good.

Kohl, F. J.↗

Gaseous sodium sulfate formation in flames and flowing gas environments

Formation of Na2SO4(g) in flames and hot flowing gas systems was studied by high pressure, free-jet expansion, modulated molecular beam mass spectrometric sampling. Fuel-lean CH4-O2 flames doped with SO2, H2O and NaCl yielded the gaseous Na2SO4 molecule in residence times of less than one millisecond. Intermediate species NaSO2(g) and NaSO3(g) were also observed and measured. Composition profiles were obtained for all reaction products. Non-flame flowing gas experiments showed that Na2SO4 and NaSO3 gaseous molecules were formed at 1140 C in mixtures of O2, H2O(g), SO2 and and NaCl(g). Experimental results are compared with calculated equilibrium thermodynamic predictions.

Stearns, C. A.↗