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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.
The susceptibility to hot corrosion of four nickel-base superalloys has been studied at 900 and 1000 C in one atmosphere of slowly flowing oxygen. Hot corrosion was induced by coating the samples with known doses of Na2SO4 and oxidizing the coated samples isothermally on a sensitive microbalance. In order of decending susceptibility to hot corrosion, these alloys were ranked: B-1900, 713C, NASA-TRW VIA, IN738. This order corresponds to the order of decreasing molybdenum content of the alloys. Chemical evidence for B-1900 indicates that hot corrosion is instigated by acid fluxing of the protective Al2O3 coating by MoO3.
Studies were conducted to examine the effect of the gaseous corrodents NaCl, HCl, and NaOH on the high temperature oxidation and Na2SO4-induced corrosion behavior of the alumina former NiAl, the chromia former Ni-25 wt.% Cr, elemental Cr, and the superalloy B-1900. Experiments were conducted at 900 and 1050 C in air in the presence and absence of the gaseous corrodents. Effects involving both reaction rates and microstructural changes in oxide morphology were observed due to the presence of these corrodents at levels anticipated to be present in operating industrial and marine gas turbines. The effect of gaseous NaCl, HCl, and possibly NaOH on NiAl in simple oxidation was to remove aluminum from below the protective alumina layer and to simultaneously weaken the adherence of the protective alumina oxide scale to the substrate. The aluminum removed from below the oxide scale was redeposited on its surface as alpha-Al2O3 whiskers. With respect to the chromia formers, gaseous NaCl and HCl promoted breakaway oxidation kinetics and changes in the microstructures of the oxide scales.
The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).
Samples of a cobalt-base alloy, Mar M-509, were subjected to hot corrosion in a Mach-0.3 burner rig. The corrodent was NaCl added as an aqueous solution to the combustion products of a sulfur-containing Jet-A fuel. The metal temperature was fixed at 900 C. The extent of hot corrosion increased by a factor of three as the fuel-to-air mass ratio was increased from 0.033 to 0.050. Because the depositing salt was always Na2SO4, the increased attack appeared to be related to the gas composition.
The mechanisms which lead to the destruction of a normally protective scale during the initial stages of hot corrosion of 14 nickel-base alloys contaminated with Na2SO4 and other condensed deposits were investigated. A continuous reading microbalance was used to record weight changes at temperatures between 900 C and 1000 C at 1 atmosphere pressure of slowly flowing oxygen. The reaction was initiated by raising a preheated furnace around the quartz tube in which the specimen was supported with oxygen flowing. The furnace was raised in a time period of seconds. At 900 C, the system and specimen came to thermal equilibrium in less than one minute. Oxidized specimens were studied using optical and scanning electron metallography and X-ray diffraction techniques. Transmission electron microscopy and electron diffraction spectroscopy were also used to identify the structure of carbides in some of the commercial alloys.
A cobalt-base alloy, Co-25Cr-10Ni-5Ta-3Al-0.5Y (S-57), was subjected to hot corrosion in Mach 0.3 burner-rig combustion gases at maximum alloy temperatures of 900 and 1000 C. Various salt concentrations were injected into the burner: 0.5, 2,5, and 10 parts per million synthetic sea salt and 4 parts per million sodium sulfate (Na2SO4). The extent of corrosion was determined by measuring the maximum depth of corrosion in the alloy, and the corrosion process was studied by metallography, X-ray diffraction, scanning electron microscopy, and electron microprobe analysis. While S-57 was found to possess only moderate oxidation resistance at these temperatures, this alloy resisted significant hot corrosion attack under all but the most severe test conditions. The process of hot corrosion attack under the most severe conditions of this study was primarily sulfidation.
There is increased interest in, and concern about, deposition and corrosion phenomena in combustion systems containing inorganic condensible vapors and particles (salts, ash). To meet the need for a computationally tractable deposition rate theory general enough to embrace multielement/component situations of current and future gas turbine and magnetogasdynamic interest, a multicomponent chemically 'frozen' boundary layer (CFBL) deposition theory is presented and its applicability to the special case of Na2SO4 deposition from seeded laboratory burner combustion products is demonstrated. The coupled effects of Fick (concentration) diffusion and Soret (thermal) diffusion are included, along with explicit corrections for effects of variable properties and free stream turbulence. The present formulation is sufficiently general to include the transport of particles provided they are small enough to be formally treated as heavy molecules. Quantitative criteria developed to delineate the domain of validity of CFBL-rate theory suggest considerable practical promise for the present framework, which is characterized by relatively modest demands for new input information and computer time.
The preliminary design and a demonstration of the feasibility of fabricating submodules of an automotive Stirling engine recuperator for waste heat recovery at 370 C are described. Sinterable silicon nitride (Sialon) tubing and plates were fabricated by extrusion and hydrostatic pressing, respectively, suitable for demonstrating a potential method of constructing ceramic recuperator-type heat exchangers. These components were fired in nitrogen atmosphere to 1800 C without significant scale formation so that they can be used in the as-fired condition. A refractory glass composition (Al2O3 x 4.5 CaO.MgO x 11SiO2) was used to join and seal component parts by a brazing technique which formed strong recuperator submodules capable of withstanding repeated thermal cycling to 1370 C. The corrosion resistance of these materials to Na2SO4 + NaCl carbon mixtures was also assessed in atmospheres of air, hydrogen and CO2-N2-H2O mixtures at both 870 C and 1370 C for times to 1000 hours. No significant reaction was observed under any of these test conditions.
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.
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.
The conversion to Na2SO4 of NaCl deposited on oxide substrates was studied as a function of temperature, in air with various SO2 and H2O partial pressures. The substrate was either a pure oxide or an oxide scale growing on a metal specimen. The progress of the reaction was observed using the SEM-EDAX technique to monitor morphological effects and, as far as possible, establish the rate of the process. The physical characteristics of the interaction between salt and substrate were also examined with particular reference to physical damage to the underlying oxide, especially when this is a scale on a metal specimen. An effort was also made to establish the conditions under which liquid phases may form and the mechanisms by which they form.
The importance of coatings for hot section airfoils has increased with the drive for more cost-effective use of fuel in a wide variety of gas turbine engines. Minor additions of silicon have been found to appreciably increase the oxidation resistance of plasma-sprayed NiCoCrAlY coatings on a single crystal nickel-base superalloy. Increasing the chromium content of MCrAlY coatings substantially increases the resistance to acidic (Na2SO4-SO3) hot corrosion at temperatures of about 1300 F (704 C) but gives no significant improvement beyond contemporary coatings in the range of 1600 F (871 C). Surface enrichment of MCrAlY coatings with silicon also gives large increases in resistance to acidic hot corrosion in the 1300 F region. The resistance to the thermal stress-induced spalling of zirconia-based thermal barrier coatings has been improved by lowering coating stresses with segmented structures and by controlling the substrate temperature during coating fabrication.
A simple engineering correlation scheme is developed to predict the variable property effects on dilute species laminar forced convection mass transfer applicable to all vapor molecules or Brownian diffusing small particle, covering the surface to mainstream temperature ratio of 0.25 T sub W/T sub e 4. The accuracy of the correlation is checked against rigorous numerical forced convection laminar boundary layer calculations of flat plate and stagnation point flows of air containing trace species of Na, NaCl, NaOH, Na2SO4, K, KCl, KOH, or K2SO4 vapor species or their clusters. For the cases reported here the correlation had an average absolute error of only 1 percent (maximum 13 percent) as compared to an average absolute error of 18 percent (maximum 54 percent) one would have made by using the constant-property results.
Sodium chloride is deposited on the surface of alumina substrates and exposed to air containing 1% SO2 at temperatures between 500 C and 700 C. In all cases the sodium chloride was converted to sodium sulfate. The volatilization of sodium chloride from the original salt particles was responsible for the development of a uniform coating of sodium sulfate on the alumina substrate. At temperatures above 625 C, a liquid NaCl-Na2SO4 autectic was formed on the substrate. The mechanisms for these reactions are given. One of the main roles of NaCl in low temperature hot corrosion lies in enabling a corrosive liquid to form.
The computer program based on multicomponent chemically frozen boundary layer (CFBL) theory for calculating vapor and/or small particle deposition rates is documented. A specific application to perimter-averaged Na2SO4 deposition rate calculations on a cylindrical collector is demonstrated. The manual includes a typical program input and output for users.
Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000%. This hot corrosion attack reduced room temperature strengths by as much as 50%. Strength degradation was porportional 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 consistent with published values.
The hot corrosion of sintered alpha-SiC by thin films of Na2SO4 and Na2CO3 was studied at 1000 C in controlled gas atmospheres. Under all conditions, corrosion led to 10 to 20 times the amount of SiO2 formed in pure oxidation after a 48-h exposure. In addition, small amounts of sodium silicate formed. Melts of Na2SO4/SO3 caused uniform pitting of the SiC substrate; Na2CO3/CO2 melts caused localized pitting and grain-boundary attack. In all cases, the protective SiO2 layer dissolved to form silicate, leading to corrosion. In the sulfate case, free carbon in the SiC promotes this process. In all cases the presence of liquid films is responsible for rapid transport rates and the subsequent rapid reaction.