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All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

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.↗
NASA NTRS1977

Interaction of NaCl(g) and HCl(g) with condensed NA2SO4

The interaction of Na2SO4(l) with NaCl(g), HCl(g) and H2O(g) was studied in atmospheric pressure flowing air and oxygen at Na2SO4(l) temperatures of 900 and 1000 C. Thermomicrogravimetric and high pressure mass spectrometric sampling techniques were used. Experimental results establish that previously reported enhanced rates of weight loss of Na2SO4(l) in the presence of NaCl(g) are due to the reaction: Na2SO4(c) + 2HCl(g) = 2NaCl(g) + SO2(g) + H2O(g) + 1/2O2(g) being driven to the right in flowing gas systems. The HCl(g) is the product of hydrolysis of NaCl caused by small but significant amounts of H2O(g) present in the system. Thermochemical calculations are used to show that even with sub-ppm levels of H2O(g) present, significant quantities of HCl(g) are produced.

Stearns, C. A.↗
NASA NTRS1983

Effect of the amount of Na2SO4 on the high temperature corrosion of Udimet-700

The corrosion of Udimet-700, coated with different doses of Na2SO4, was studied in an isothermal thermogravimetric test in the temperature range 900 to 950 C. The weight gain curve is characterized by five distinct stages: an initial period of linear corrosion; an induction period; a period of accelerated corrosion; a period of decelerating corrosion; and a period of parabolic oxidation. The time required for the failure of the alloy increases with an increase in the amount of Na2SO4, reaches a peak and then decreases with further increase in the amount of Na2SO4. For low and intermediate doses (0.3 to 2.0 mg/sq cm), the catastrophic failure of the material occurs by the formation of Na2MoO4 and interaction of the liquid Na2MoO4 with the alloy. For heavy doses, the degradation of the material is due to the formation of large amounts of sulfides.

Misra, A. K.↗
NASA NTRS1984

Effects of SO2 and SO3 on the Na2SO4 induced corrosion of nickel

The effects of SO2 and SO3 in the environment on the hot-corrosion behavior of Ni in the temperature range 750-950 C has been studied. Below the melting point of Na2SO4 (884 C), rapid corrosion takes place by formation of a Na2SO4-NiSO4 melt which can penetrate the porous oxide scale and give rise to sulfide information by coming in contact with the metal. The distribution of the sulfides depends on the SO2 level in the ambient gas. Continued corrosion occurs by a sulfidation-oxidation mechanism. At temperatures above the melting point of Na2SO4, accelerated degradation occurs via dissolution of the surface scale, followed by reprecipitation of the oxide in a nonprotective form.

Misra, A. K.↗
NASA NTRS1977

The effect of NaCl/g/ on the Na2SO4-induced hot corrosion of NiAl

Studies have been performed to examine the effect of NaCl vapor on the Na2SO4-induced hot corrosion of the alumina former NiAl. In the incubation period associated with such hot corrosion, NaCl(g) has been shown to be effective in removing aluminum from below the protective alumina scale and redepositing it as Al2O3 whiskers on the surface of the Na2SO4-coated sample. Similar effects seen in simple oxidation are associated with isothermal rupturing of the protective alumina scale.

Smeggil, J. G.↗
NASA NTRS1984

Deposition of Na2SO4 from salt-seeded combustion gases of a high velocity burner rig

The mechanism of deposition of Na2SO4 was studied under controlled laboratory conditions and the results have been compared to a recently developed comprehensive theory of vapor deposition. Thus Na2SO4, NaCl, NaNO3 and simulated sea salt solutions were injected into the combustor of a nominal Mach 0.3 burner rig burning jet fuel at constant fuel/air ratios. The deposits formed on inert collectors, rotation in the cross flow of the combustion gases, were weighed and analyzed. Collector temperature was uniform and could be varied over a large range by internal air cooling. Deposition rates and dew point temperatures were determined. Supplemental testing included droplet size measurements of the atomized salt solutions. These tests along with thermodynamic and transport calculations were utilized in the interpretation of the deposition results.

Santoro, G. J.↗
NASA NTRS1986

Mechanism of Na2SO4-induced corrosion of molybdenum containing nickel-base superalloys at high temperatures. I - Corrosion in atmospheres containing O2 only. II - Corrosion in O2 + SO2 atmospheres

Kinetics of the Na2SO4-induced corrosion of the molybdenum-containing nickel-base superalloys, B-1900 and Udimet 700, coated with Na2MoO4, has been studied in oxygen atmosphere at temperatures ranging from 750 to 950 C. Because the gas turbine atmosphere always contains some SO2 and SO3, the effect of atmospheric SO2 content on corrosion of Udimet-700 has also been studied. It was found that in the O2 atmosphere the melt in the catastrophic corrosion phase consists of Na2MoO4 plus MoO3, with the onset of the catastrophic corrosion coinciding with the appearance of MoO3. In the presence of low levels of atmospheric SO2 (below 0.24 percent), the melt during catastrophic corrosion contains, in addition to Na2MoO4 and MoO3, some quantities of Na2SO4. At the levels of SO2 above 1 percent, no catastrophic corrosion was observed. At these SO2 levels, internal sulfidation appears to be the primary mode of degradation.

Misra, A. K.↗
NASA NTRS1977

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.↗
NASA NTRS1977

Theoretical and experimental studies of the deposition of Na2SO4 from seeded combustion gases

A basic point in the hot corrosion of turbine components is the deposition of sodium sulfate from flames containing sodium and sulfur. An experimental study is described which examines a dew point prediction theory based on the local thermochemical equilibrium (LTCE) method, and a means to calculate the deposition rate is suggested. In addition, a convective diffusion theory, based on the assumption of a chemically frozen boundary layer, utilizing the LTCE results, and imposing the additional effects of mass transport, was also successful in predicting dew points for Na2SO4-seeded combustion gases. A multicomponent mass transfer equation was derived to predict NaSO4 deposition rate via vapor transport at temperatures below the deposition onset temperature.

Kohl, F. J.↗
NASA NTRS1977

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 K2S04 molecules were formed in residence times on the order of 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.↗
NASA NTRS1977

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.↗
NASA NTRS1987

Role of molybdenum in the Na2SO4 induced corrosion of superalloys at high temperature

Sodium sulfate induced corrosion of a molybdenum containing nickel-base superalloy, Udimet 700, was studied in laboratory furnace test and in a high velocity (Mach 0.3) burner rig. Tlhe effect of SO2 content in the atmosphere on the corrosion behavior in the laboratory furnace tests was determined. catastrophic corrosion occursonly when the melt contains MoO3 in addition to Na2SO4 and Na2MoO4. The conditions under which catastrophic corrosion occurs are identified and a mechanism is described to explain the catastrophic corrosion.

Misra, A. K.↗
NASA NTRS1985

Deposition of Na2SO4 from salt-seeded combustion gases of a high velocity burner rig

With a view to developing simulation criteria for the laboratory testing of high-temperature materials for gas turbine engines, the deposition rates of sodium sulfate from sodium salt-seeded combustion gases were determined experimentally using a well instrumented high-velocity burner. In the experiments, Na2SO4, NaCl, NaNO3, and simulated sea salt solutions were injected into the combustor of the Mach 0.3 burner rig operating at constant fuel/air ratios. The deposits formed on an inert rotating collector were then weighed and analyzed. The experimental results are compared to Rosner's vapor diffusion theory. Some additional test results, including droplet size distribution of an atomized salt spray, are used in interpreting the deposition rate data.

Santoro, G. J.↗
NASA NTRS1985

Na2SO4 induced corrosion of nickel at high temperature

Sodium sulfate-induced corrosion of nickel was studied at 900 C as a function of oxygen partial pressure. For high O2 partial pressures, accelerated corrosion during the first few minutes occurred by rapid penetration of the melt along the metal grain boundaries. A mechanism is proposed to explain this phenomenon. Repetitive scale metal detachment was observed for corrosion in lower O2 partial pressures and during the later period of corrosion in higher O2 partial pressures. The effect of preoxidation on the hot corrosion has also been studied. An induction period is observed before the onset of rapid corrosion for the preoxidized samples; the onset of rapid corrosion is associated with sudden cracking of the scale. The length of the induction period for the preoxidized samples is a function of the length of preoxidation, and appears to be related to the structure of the oxide scale after the preoxidation treatment.

Misra, A. K.↗
NASA NTRS1989

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.↗
NASA NTRS1975

Sodium sulfate: Vaporization thermodynamics and role in corrosive flames

Gaseous species over liquid Na2SO4 were identified by the technique of molecular beam mass spectrometry. The heat and entropy of vaporization of the Na2SO4 molecule were measured directly. Comparisons of the experimental entropy with values calculated using various molecular parameters were used to estimate the molecular structure and vibrational frequencies. The thermodynamic properties of gaseous and condensed phase Na2SO4, along with additional pertinent species, were used in a computer program to calculate equilibrium flame compositions and temperatures for representative turbine engine and burner rig flames. Compositions were calculated at various fuel-to-oxidant ratios with additions of sulfur to the fuel and the components of sea salt to the intake air. Temperatures for condensation of Na2SO4 were obtained as a function of sulfur and sea salt concentrations.

Kohl, F. J.↗
NASA NTRS1979

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.↗
NASA NTRS1981

Investigation into the role of NaCl deposited on oxide and metal substrates in the initiation of hot corrosion

Morphological aspects of the conversion to Na2SO4 of NaCl deposits over the temperature range 500-700 C, in air with added SO2 and H2O. Progress of the reaction was observed by withdrawing samples at various times and examining them under the scanning electron microscope using EDAX to assess the extent of chloride to sulfate conversion. These initial results show that the conversion to Na2SO4 proceeds directly on the sodium chloride surface as well as on the surrounding substrate due to evaporation of NaCl from the solid particle. The mechanism of this reaction could involve reaction in the vapor to produce Na2SO4 which then deposits, alternatively Na2SO4 could form directly on the substrate surface due to direct reaction there between the vapors NaCl, SO2 and O2.

Birks, N.↗