Oxidation of Metals, Vol. 54, Nos.

3/4, 2000

Effect of Experimental Procedures on the Cyclic, Hot-Corrosion Behavior of NiCoCrAlY-Type Bondcoat Alloys
C. Leyens,* I. G. Wright, and B. A. Pint
Received October 18, 1999; revised February 17, 2000

A simplied test procedure was established to assess the hot-corrosion behavior of MCrAlY-type nickel-base alloys under the inuence of molten sodium sulfate as well as sodium sulfate/potassium sulfate salt blends. Salt-coated specimens were exposed to 1-hr thermal cycles at 950C in owing oxygen for up to 500 cycles. Mass-change data of the specimens revealed a signicant dependence of the corrosion attack not only on the average contaminant ux rate, as expected, but also on the initial amount of salt deposited during each recoating cycle. Furthermore, deposit removal before salt recoating markedly inuenced the corrosion attack of the alloys. This was apparently related to changes in salt chemistry by the dissolution of elements such as Cr from the alloy, which can shift the basicity of the salt and thus affect the extent of attack. Substituting Na for K in sodium sulfate/potassium sulfate salt blends generally resulted in decreased attack. For K-containing salt deposits, increasing the gross amount of alkali compared to sulfur resulted in increased sample weight losses due to scale spallation. In contrast, decreasing the amount of sulfur in such deposits which contained exclusively Na as the alkali resulted in a signicantly reduced corrosion attack compared to stoichiometric sodium sulfate.
KEY WORDS: hot-corrosion testing; NiCoCrAlY-type bond coats; contaminant ux rate; biomass fuels. *DLR-German Aerospace Center, Institute of Materials Research, 51170 Cologne, Germany. Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37830-6156. At the time this work was performed, the author was on sabbatical at Oak Ridge National Laboratory. Author to whom all correspondence should be sent. email: christoph.leyens@dlr.de (Christoph Leyens). 255
0030-770X001000-0255$18.000 2000 Plenum Publishing Corporation

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INTRODUCTION Although new materials for high-temperature applications mainly provide high mechanical strength and creep resistance, it is mandatory to consider their corrosion behavior in the anticipated environment early in their development. Corrosion testing of materials is also of great importance when well-established materials (or material systems including coatings) are to be operated in environments where their behavior is not well known. As the operating conditions for a specic material or material system can be quite complex, the optimum test would be to run the actual component in an existing facility or engine. However, such a test is generally extremely costly and failure of the component may cause signicant damage to the whole operating device; thus, the component test is almost always the last step for a material to demonstrate its suitability for a specic application. Therefore, simplied corrosion tests are extremely useful in research and development activities in order to develop an improved understanding of the corrosion mechanisms and in industrial applications to establish materials behavior in a simulated environment. Unfortunately, no standardized test procedures have yet been established, and most research laboratories, materials manufacturers, and their customers have developed their own tests. Recently, the European Federation of Corrosion started an initiative to develop guidelines and standards for high-temperature corrosion research and testing.1 Although simplied tests cannot (and are not intended to) simulate all aspects of actual operating conditions, standardized testing methods would be a great help in generating comparable data. As for nonstandardized tests, there remains the question how well the results of simplied tests correlate with the more complex service conditions of the real world. The degree of correlation will, in many cases, depend on the sophistication of the test and on the proper control of the relevant test parameters.2 In many cases, reasonable correlation between laboratory tests and service experience has been achieved (for example, Ref. 3). Among laboratory tests, the discontinuous measurement of high-temperature corrosion is widely used (for example, Refs. 4 and 5). The most common methods are: (a) crucible tests, where the specimens are totally or partly immersed in a molten salt; (b) salt-coating tests, where the specimens are coated with salt prior to exposure to high temperatures, or continuously coated in a two-zone furnace arrangement6 ; and (c) burner-rig tests, where the specimens are exposed to a burner into which contaminants can be injected. Because of considerable differences in these test methods, it is not surprising that singular results obtained from one of the above tests methods may differ signicantly and sometimes may not even reect the same performance ranking for a variety of materials. However, even when one particular method is chosen, the results are strongly dependent on the exact

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testing procedure. The aim of the present paper is to assess the importance of test parameters in the salt-coating test. Effects of salt deposits present on the specimen surface, recoating frequency, removal or retention of the deposits prior to salt recoating, as well as the effect of the salt composition were investigated for cast, model MCrAlY-type bondcoat compositions under cyclic conditions. The salt compositions were selected to include pure sodium sulfate, the baseline contaminant being used in many hot-corrosion studies, and sodiumpotassium sulfate blends, attempting to represent compositions typical of deposits expected from biomass-derived, fuel-combustion products.7 The hot-corrosion scenario under consideration was that described by Bornstein and Allen8 in which salt is delivered to the hot gaspath components by direct impingement, rather than by condensation of vapor species. These authors reported indications that, in large land-based gas turbines, deposits are shed from the compressor periodically and impinge on the surface of turbine components, thus suggesting a route whereby contaminants may experience some residence time on turbine blades operating with surface temperatures nominally higher than the equilibrium condensation temperature of the salts. In contrast to conventional hot-corrosion tests in which Type-I hot corrosion is supposed to occur in an SOx-containing atmosphere, the experiments presented were performed in owing oxygen without SOx addition. In the present study, the sole source of sulfur in the fuel entering the turbine combustor was considered to be associated with the alkali particles passing the lter, a scenario relevant to combustion of biomass-derived fuels.9 The gas atmosphere obtained from combustion of these fuels is essentially sulfur-free, as simulated in the tests. Furthermore, during gas-turbine operation, deposits formed on the compressor are periodically removed by injection of water and, therefore, deposit removal in laboratory tests may also be useful in simulating service conditions. As a result, laboratory tests with intermittent rather than continuous salt delivery were considered appropriate to simulate this behavior. The specimens were tested in 1-hr cycles at 950C up to 500 hr and subsequently characterized by optical and scanning electron microscopy, as well as microprobe and energy dispersive X-ray analysis. EXPERIMENTAL PROCEDURES The alloys used in this study included cast versions of NiCoCrAlY (Ni 22Co18Cr12.5Al0.06Y, in wt.%) and NiCoCrAlYHfSi (Ni20Co18Cr 12.5Al0.55Y0.26Hf0.37Si, in wt.%, composition after Ref. 10) coatings. The alloys were vacuum-induction melted and cast in a water-chilled copper mold. The castings were then annealed at 1250C for 4 hr in quartz ampules. Both alloys exhibited a two-phase microstructure, with discrete regions of

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-phase containing precipitates of -phase, surrounded by (or mixed with) regions of -phase containing precipitates of . Specimens ( 1.5 cmB0.1 0.15 cm) were cut from the castings and polished with SiC paper to 600 grit, such that preferred orientation of the grinding marks was avoided. The test procedure involved 1-hr thermal cycles at 950C performed in an automated test rig in which the specimens were attached to alumina rods by PtRh wire hooks in a vertical tube furnace for 1-hr and cooled to room temperature for 10 min between cycles. Dry oxygen owed continuously into the bottom of the tube furnace during the exposures. With respect to the mode of delivery of contaminants from biomass-derived fuels, these will likely arrive directly in the combustion gas, so that the way in which they impinge on the hot gas-path components has yet to be determined.9 In these tests, all deposits were applied by the periodic coating method. Prior to testing, all specimens were ultrasonically cleaned in acetone and methanol. For hot-corrosion tests, the specimens were coated with water solutions of different salt compositions (Table I). For the biomass fuel-related deposits, the higher K content was simulated by three different KNa ratios (KNa G0, 2, and 15) and the lower sulfur content was approximated by three different sulfur levels (2S(NaCK) G1, 0.4, 0.2). A stoichiometric sulfur content was represented by 2S(NaCK) G1. The salt solutions were prepared using distilled water and high-purity Na2SO4 (Tm G 884C), K2SO4 (Tm G1076C, and dewpoint lower than the melting point), NaOH (Tm G318C), and KOH (Tm G360C). The high basicity of the water solution was neutralized to pH7 using HNO3 . The salt solutions were deposited onto the specimens using a dropper pipette and the water was evaporated by heating the specimens on a hot plate up to about 200C. In order to provide a uniform salt coating at the beginning of the tests, the

Table I. KNa and 2S(NaCK) Ratios for Different Salt Compositions KNa 0 0 0 2 2 2 15 15 15 2S(NaCK) 1 0.4 0.2 1 0.4 0.2 1 0.4 0.2

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Table II. Amount of Salt, Recoating Frequency, Contaminant Flux Rate (CFR), and Washing Procedure of Na2SO4-Coated Cast NiCoCrAlY Designation Sample Sample Sample Sample Sample Sample Sample Sample A B C D E F G H Amount of salt [mg cm2] 1.016J0.062 1.061J0.072 0.262J0.050 0.264J0.043 1.059J0.101 1.051J0.156 4.746J0.383 0.283J0.085 Recoating every 100 100 20 20 20 20 20 100 hr hr hr hr hr hr hr hr CFR [mg cm2 hr 1] 1B102 1B102 1.3B102 1.3B102 5.3B102 5.3B102 23.7B102 0.3B102 Washing before recoating Yes No Yes No Yes No Yes No

specimens were preoxidized for 1 hr at 950C (1 cycle) prior to coating, rather than depositing salt on the bare metal surface.11 One set of NiCoCrAlY specimens was recoated with pure Na2SO4 after 20 and 100, 1-hr cycle intervals (recoating frequency), respectively, applying different contaminant ux rates (CFRs) (Table II). In some cases, the specimens were washed carefully in distilled water prior to recoating in order to remove the existing deposits. A second set of NiCoCr AlYHfSi specimens was coated with salts of different KNa ratios and sulfur levels (Table I) at an average CFR of 1.07 mg cm2 hr 1. These specimens were recoated every 100 cycles without deposit removal. All specimens were weighed before and after coating with salt, after washing, and before and after exposure. Mass change of the specimens was calculated taking into account the evaporative mass loss of the PtRh hooks (approximately 2B104 mg cm2 hr 1). Corrosion products were characterized using optical microscopy, a eld-emission gun scanning-electron microscope (FEG-SEM) equipped with energy dispersive X-ray analysis (EDS), and a microprobe. Specimens were sectioned and examined metallographically at the end of the tests. RESULTS AND DISCUSSION Effect of Salt-Deposition Procedure An overview of the data for mass gain vs. number of 1-hr cycles for Na2SO4-coated NiCoCrAlY specimens tested at 950C is given in Fig. 1. The CFR was varied by almost two orders of magnitude between 0.28B102 and 23.73B102 mg cm2 hr 1 and, accordingly, the extent of corrosion attack also differed widely. As expected, the highest mass loss was found for the highest CFR. The mass-change data for most data lie in a scatter band up to 350 1-hr cycles. However, one specimen exposed to the highest

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Fig. 1. Sample mass change vs. number of 1-hr cycles for Na2SO4-coated cast NiCoCrAlY. Specimens were coated with different CFRs at different time intervals. Some specimens were washed to remove salt deposits before recoating with salt. Specimen designation is according to Table II. The arrows indicate the range over which CFR, deposit removal, and recoating frequency affect the hot-corrosion attack of the alloy.

CFR (sample G) and one specimen exposed to a fresh salt coating every 20 hr at an intermediate CFR (sample E) started to lose mass rapidly after 200250, 1-hr cycles, indicating accelerated attack. It should be noted that the data represent sample mass change, i.e., the mass of the deposits that possibly remained on the specimen surface was included in all data points. Detailed comparison of mass-change data before and after sample washing, i.e., with and without deposits included, revealed, however, that the course of the mass-change curves was similar qualitatively, albeit the absolute mass data were, of course, lower when deposits were removed.11 The qualitative inuence on corrosion attack of the three experimental parameters, contaminant ux rate, deposit removal or retention prior to salt recoating, and recoating frequency, is indicated by arrows in Fig. 1. It is evident that, for the set of parameters investigated, the contaminant ux rate (i.e., the amount of salt deposited on the specimen surface per unit time) was the major factor determining the corrosion attack of the NiCoCrAlY

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alloy. The effect of deposit removal became important with intermediate CFRs on the order of 5.3B102 mg cm2 hr 1, whereas, for CFRs G1 1.3B102 mg cm2 hr 1, the effect was relatively minor. Recoating frequency demonstrated some effect on the hot-corrosion attack of NiCoCrAlY. The effect of these parameters will be discussed in more detail below. Contaminant Flux Rate The dependence of specimen mass loss on the contaminant ux rate of Na2SO4-coated cast NiCoCrAlY after 350, 1-hr cycles at 950C is illustrated in Fig. 2. The specimens (samples C, E, and G) were recoated every 20 cycles and the deposits were removed before recoating. Although the CFR varied by a factor of approximately 20, the resulting specimen mass loss

Fig. 2. Mass loss vs. contaminant ux rate of Na2SO4-coated cast NiCoCrAlY after 350, 1-hr cycles at 950C. As expected, lowest corrosion attack was caused by the lowest CFR (a), whereas the highest CFR resulted in severe attack (c). The respective macrographs (ac) indicate that the alumina scale (light gray areas on the surface) was attacked on all specimens. For intermediate and high CFRs the alumina-scale spinel phases (dark specimen areas) were the dominant oxides formed. The specimen edges especially suffered from signicant metal loss due to repeated oxide scale spallation and reformation.

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showed more than two orders of magnitude difference, indicating the inuence of the CFR on the extent of corrosion attack. The greatest attack of cast NiCoCrAlY was experienced with a CFR of 23.73B102 mg cm2 hr 1. The specimen started to lose signicant mass after about 200, 1-hr cycles (Fig. 1) and was heavily corroded after the test period of 350 cycles (Fig. 2c). It should be noted that, for the experimental geometry, i.e., 1.5 cmdiameter coupons, and their vertical suspension in the furnace, approximately 5 mg cm2 was the maximum amount of salt that could be coated without losing salt due to droplet formation and subsequent dripping during heating. The optical macrographs in Fig. 2 also illustrate the signicant increase in attack with increasing CFR. With increasing CFR, spinel phases (dark gray surface areas) were the dominant oxide phases present for CFR G 5.3B102 and 23.7B102 mg cm2 hr 1 after 350, 1-hr cycles, whereas for CFR G1.3B102 mg cm2 hr 1 quite a large portion of the initially formed alumina scale (light gray phase on the surface) was still present. Mass loss of the samples was caused by repeated spallation of the oxide scale (presumably during cooling between cycles) and subsequent regrowth of the oxide scale. The specimen edges especially showed signicant loss of metal as a result of this process. Optical macrographs of the specimens exposed to CFR G1.3B102 mg 2 cm hr 1 (Fig. 3a) and CFR G23.7B102 mg cm2 hr 1 (Fig. 3b) revealed relatively non-uniform attack of the cast NiCoCrAlY alloy. For CFR G 1.3B102 mg cm2 hr 1 the alumina scale was partly intact, although areas of voluminous spinel phases were present, as shown in Fig. 2, indicating degradation of the protective layer. For CFR G23.7B102 mg cm2 hr 1,

Fig. 3. Optical micrographs of cast NiCoCrAlY specimens after 350, 1-hr cycles at 950C. (a) For CFR G1.3B102 mg cm2 hr 1 main parts of the specimen surface were covered with a relatively thin alumina scale, but in some spots voluminous spinel formed. (b) For CFR G23.7B102 mg cm2 hr 1 massive oxidation along the phase boundaries underneath the voluminous, porous oxide scale occurred in many spots.

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Fig. 4. Secondary-electron SEM images of the spinel-rich part of the oxide scale formed on NiCoCrAlY coated with Na2SO4 revealed crack formation of the specimen surface (a) and through the oxide scale parallel to the surface (b). The oxide scales typically consisted of a mixture of alumina and spinel phases, but microprobe analysis revealed that chromia also had formed.

voluminous oxide scales containing primarily spinel phase were formed. Nonuniform attack of the alloy led to the formation of an oxide network underneath the oxide scale in several locations on the specimens, indicating signicant internal degradation. As mentioned before, when it formed, voluminous oxide scale spalled readily during cycling. The SEM micrograph in Fig. 4a shows a plan view of the oxide scale typical of NiCoCrAlY specimens exposed to Na2SO4 . The oxide scale was extensively cracked and part of the scale had spalled during thermal cycling. A cross section through the oxide scale revealed massive crack formation in the scale (Fig. 4b). Although such crack formation could occur during metallographic preparation, the rounded appearance of some crack tips suggested that most cracking actually occurred during testing. Crack formation parallel to the specimen surface facilitated loss of part of the oxide scale. The oxide scale was porous as a result of dissolution and reformation during salt attack. In some areas, metallic -phase seemed to be incorporated into the oxide scale. Microprobe analysis of this -phase revealed that all the Al had been leached out during the molten-salt attack. Deposit Removal or Retention Before Salt Recoating According to the mass-change data summarized in Fig. 1, removal or retention of deposits before salt recoating had a signicant effect on the corrosion attack of the NiCoCrAlY alloy. For a given recoating frequency,

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Fig. 5. Inuence of deposit removal before salt recoating on specimen mass loss for (a) CFR G 1B102 mg cm2 hr 1, recoated every 100 cycles; (b) CFR G1.3B102 mg cm2 hr 1, recoated every 20 cycles; and (c) CFR G5.3B102 mg cm2 hr 1, recoated every 20 cycles.

the mass loss of the specimens clearly depended on deposit removal or retention (Fig. 5). At lower CFRs, the effect was less pronounced, but still measurable (Fig. 5a,b), than for higher CFRs (Fig. 5c). For CFR G 5.3B102 mg cm2 hr 1, deposit removal resulted in a signicant increase of mass loss (by about one order of magnitude) compared to the specimen on which the deposits were retained. Based on the current understanding of the mechanisms of hot-corrosion under salt deposits, uxing of the alumina scale by a molten salt is strongly dependent on the oxide-ion activity (aO 2) of the salt melt.12 Basic and acidic uxing are associated with a high and low oxide ion activity, respectively, thus any shift in the salt oxide ion activity will potentially increase the solubility of the alumina scale.13 Although Cr2O3 is also soluble in fused Na2SO4 ,14 dissolution of Cr has been reported to effectively buffer the salt basicity near the level where alumina solubility is minimum and so effectively retard accelerated attack of alumina scales.13,15 Similarly, chromate fuel additives are known to effectively combat hot corrosion in many practical applications. In the present study, the yellow color of the deposits that were removed from the NiCoCrAlY specimens indicated the presence of sodium chromate (Na2CrO4), i.e., Cr was leached out of the substrates by the molten salt. In the case of salt deposition without deposit removal before recoating, the fresh salt was blended with the salt that was already present on the surface for several cycles and that already contained a certain amount of Cr. The basicity of fresh salt presumably would be less changed due to the presence of the Cr buffer, compared to samples exposed to a

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fresh salt on a deposit-free surface. Accordingly, specimens repeatedly exposed to fresh salts were found to suffer stronger corrosion attack than the unwashed specimens, which resulted in marked scale spallation (Fig. 5c). For the lower CFRs this effect was reduced, presumably since the initial amount of salt was much lower and the Cr supply from the substrate would be expected to be sufcient to rapidly buffer the salt basicity even in the case of a cleaned surface exposed to fresh salt. This mechanism will be discussed in more detail below. Recoating Frequency While the effects of the contaminant ux rate and deposit removal or retention on the hot-corrosion attack of cast NiCoCrAlY could be relatively well described by either the macroscopic appearance of the specimens or mass-change data obtained by thermal cyclic testing alone, additional metallographic examinations were necessary to characterize the inuence of recoating frequency. For either deposit removal or retention, mass-change data for recoating frequencies of 20 and 100 cycles revealed only small differences, even for CFRs ranging from 0.1 to 1.1B102 mg cm2 hr 1. Figure 6

Fig. 6. Effect of recoating frequency on the corrosion attack of cast NiCoCrAlY coated with Na2SO4 and exposed at 950C for 350, 1-hr cycles. (a), (b), (c), and (d) macrographs of specimens recoated every 100 and 20 cycles with CFR G1B102 and 1.3B102 mg cm2 hr1, respectively. The deposits were removed by washing or retained before salt recoating. Although massloss data revealed a fairly minor (but measurable) effect of deposit removal or retention, appearance of the specimens was signicantly different.

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summarizes the mass-loss data as a function of recoating frequency for deposit removal and retention using the specimens subjected to CFRs of 1B102 and 1.3B102 mg cm2 hr 1 for comparison. Despite the small differences in mass loss among the specimens, their macroscopic appearance was signicantly different. Whereas large parts of the specimens recoated every 20 cycles contained alumina (light gray phases in Fig. 6c and d), the oxide scale on specimens coated every 100 cycles contained mainly spinel phases (dark gray phases in Fig. 6a and b), rather than alumina. As spinel phases tended to spall more easily than alumina, it was concluded that the mass-change data for these specimens was the net result of mass gain by voluminous oxide scale formation and mass loss from subsequent spallation. Therefore, mass-change data alone were obviously an insufcient measure for determining the extent of corrosion attack of cast NiCoCrAlY, in these cases. It is of note that the effective mass gain and mass loss for 20 and 100 cycle recoating frequencies, respectively, measured for specimens from which the deposits were not removed from the surface (Fig. 6) was reversed when the deposits were removed. This was a direct result of the loss of oxide scale during deposit washing. Figure 7ad shows representative cross sections of the respective specimens illustrated in Fig. 6ad. For similar CFRs, the increased severity of attack when a larger amount of salt was initially present on the specimens recoated every 100 cycles (approximately 1.0B102 mg cm2 hr 1 vs. 0.26B102 mg cm2 hr 1 for those recoated every 20 cycles) is clearly evident. This is presumably due to the longer time of continuous contact of the salt with the specimen surface before removal by evaporation during 100-cycle recoating tests, allowing dissolution of the protective scale and attack of the substrate (see below for a discussion on evaporation). In the case of the specimens recoated every 20 cycles, the shorter contact time with the molten salt presumably resulted in diminished dissolution of scale, so that a protective scale reformed after the salt had evaporated. The cause of the increased severity of attack of the specimens, which were not washed prior to recoating, is not obvious. Based on the present results, a 20-hr salt-recoating frequency and an average contaminant ux rate of the order of 1.0B102 mg cm2 hr 1 with deposit removal before recoating was considered to provide the most consistent results regarding correlation between mass-change data and actual corrosion attack of the specimens. However, the 20-hr salt-recoating procedure was very labor intensive. Therefore, for the sake of a reasonable specimen throughput (100, 1-hr cycles per week) in the laboratory, a simplied test procedure involving 1.0 mg cm2 of salt, recoated every 100 hr without deposit removal before recoating, was chosen.

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Fig. 7. Optical micrographs of cast NiCoCrAlY specimens tested under different experimental parameters. The cross sections indicate signicant effect of the contaminant ux rate, recoating frequency, and deposit removal or retention upon hot-corrosion attack.

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Effect of Salt Evaporation Comparison of mass-change data associated with recoating and deposit removal revealed that, for small amounts of salt coated onto the specimens, mass loss by washing before recoating was fairly small (Fig. 8a). It should be noted that mass loss, in general, included not only salt deposits, but also loss of oxide during washing; however, this was found to be marginal in the case of CFR G1.3B102 mg cm2 hr 1. For larger amounts of salt deposited on the surface (Fig. 8b), the absolute amount of salt present on the surface before washing was much higher, indicating that the salt had not completely evaporated within a period of 20, 1-hr cycles. However, after about 200 overall cycles, the mass loss after deposit removal started to increase. This disproportionally high mass loss of the specimen was associated with partial loss of the oxide scale in addition to the mass loss due to deposit removal during washing. Increasing amount of oxide loss during washing was correlated with the onset of accelerated specimen mass loss (compare Fig. 8b with Fig. 1). As a result of rapid scale growth and continuing attack by

Fig. 8. Relative mass change vs. number of 1-hr cycles for two NiCoCrAlY specimens Na2SO4-coated at different CFRs. Different sets of data points were taken after different numbers of cycles. For example, between 280 and 300 cycles, data was recorded after 281, 283, 285, 290, 295, and 300 hr. Mass loss of the specimens was partly a result of salt evaporation during exposure (refer to text for details).

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Fig. 9. Mass change vs. number of 1-hr cycles for two Ni CoCrAlY specimens Na2SO4-coated at different CFRs. Mass gain was attributed to the amount of salt added, whereas mass loss was mainly due to salt evaporation and loss of oxide scale during cleaning.

fresh salt, the mechanical integrity of the oxide scale was signicantly affected after longer times of exposure. Once part of the oxide scale spalled, the next salt coating was deposited on either a thinner oxide scale or bare metal (depending on the type of spallation), thus further facilitating attack. A more detailed analysis of the evaporation behavior of the salt deposits is given in Fig. 9. The relative mass change of the specimens denotes the mass of the specimen during exposure in relation to its starting mass, including the fresh salt coating. It should be noted, of course, that the specimen mass was affected by superposition of mass gain as a result of corrosion and mass loss caused by salt evaporation and possibly oxide spallation. It is apparent from Fig. 9 that sodium sulfate evaporated from the NiCoCrAlY specimens at an almost linear rate, as observed for both CFR G1.3B102 mg cm2 hr 1 and CFR G5.3B102 mg cm2 hr 1. The data were determined at different times between different overall numbers of cycles. Deviation from linear behavior was observed at higher numbers of cycles and, to somewhat greater extent, for the higher CFRs. For higher numbers of cycles, side effects like oxide spallation and accelerated scale regrowth during the 20 cycle periods accounted for the deviation from the

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linear behavior. For CFR G5.3B102 mg cm2 hr 1 and more clearly, for CFR G23.7B102 mg cm2 hr 1 (not shown here), droplet formation and subsequent loss by dripping caused disproportionally high mass loss after the rst few cycles (Fig. 9b), but once the excess salt was lost, a linear evaporation rate was reestablished (Fig. 9b), data points for 280300 hr). It should be emphasized that these data did not accurately reect the salt evaporation behavior, because they included side effects related to oxide spallation. This was clearly indicated by the signicant scatter of the data after 20 cycles, ranging from about zero to 40% relative mass change (Fig. 9). A more accurate determination of the salt evaporation rate would demand a very corrosion-resistant alloy, which forms a slow-growing welladherent oxide scale. Because of the signicant attack of the NiCoCrAlY alloy associated with scale spallation after extended exposure times, the evaporation rate was calculated from only a few data points. From these data, the evaporation rate for pure sodium sulfate at 950C in owing oxygen was calculated to be of the order of 0.01 mg cm2 hr 1. However, the salt evaporation rate was signicantly dependent on the alloy chemistry,13,16 and the alloy composition, in turn, affected the deposit chemistry and, therefore, its vapor pressure.

Effect of Salt Composition In order to assess the extent of corrosive attack likely to occur in the presence of contaminants typical of combustion products of biomassderived fuels, cast NiCoCrAlYHfSi was exposed to different salt compositions representing KNa ratios of 0, 2, and 15, as well as different sulfur levels. The simplied test procedure mentioned above was used involving an average CFR of 1.0B102 mg cm2 hr 1, with specimens coated every 100 hr without deposit removal before recoating. As expected, the mass change vs. number of 1-hr cycles curves showed a signicant effect of salt composition on the corrosion behavior (Fig. 10). Pure sodium sulfate, as a baseline contaminant, caused the most severe attack of all salt blends tested. Repeated spallation of the oxide scale after a short period of initial mass gain resulted in signicant mass loss after 500, 1-hr cycles. Salt blends were all less aggressive than sodium sulfate alone and, surprisingly, the two sodium sulfate blends with a sulfur decit demonstrated the largest differences in mass change compared to stoichiometric sodium sulfate. A more detailed description of the data is given in Figs. 11 and 12, in which sample mass change is summarized as a function of the KNa ratio (Fig. 11) and sulfur content in the salt (Fig. 12).

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Fig. 10. Mass change vs. number of 1-hr cycles at 950C of cast NiCoCrAlYHfSi coated with different salt compositions. Salt blends were selected to represent contaminants relevant to biomass-derived fuel combustion products. Pure sodium sulfate (lled circles) was included as a baseline deposit widely used in hot-corrosion studies.

For a given sulfur level in the salts, substituting K for Na generally resulted in decreased mass loss of the specimens (Fig. 11ac). For a stoichiometric sulfur level, the addition of potassium of the order of KNa G2 resulted in formation of an oxide scale with a signicantly decreased tendency to spall; further increasing the amount of potassium to KNa G15 decreased the attack more signicantly. These results are in good agreement with earlier ndings for a cast NiCoCrAlY alloy, which demonstrated a signicant dependence of hot-corrosion attack on KNa ratio.7 However, unlike NiCoCrAlYHfSi, cast NiCoCrAlY gained mass during testing up to 500, 1-hr cycles, indicating improved scale adherence over that of the Hfand Si-modied version. For a given KNa ratio, reducing the sulfur level of the sodiumpotassium salt blends seemed to slightly increase the hot-corrosion attack of cast NiCoCrAlYHfSi, at least in terms of their tendency to promote scale spallation (Fig. 12b,c). However, whereas changing the sulfur level in the salt mixtures showed little effect on overall weight change for the Na-containing salt, increased attack (based on mass gain) was measured with decreasing sulfur level, as shown in Fig. 12a. Although the extent of corrosion attack of cast NiCoCrAlYHfSi was reduced when the relative amount of Na in the salt was decreased, metallographic investigations of the specimens still revealed intense corrosion

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Fig. 11. Mass change vs. number of 1-hr cycles at 950C of cast NiCoCrAlYHfSi coated with different salt compositions. Data were identical with those of Fig. 10, but plotted separately for different sulfur levels [2S(NaCK) G1 is stoichiometric sulfates, whereas 2S(NaCK)F1 represents S decit relative to alkali].

Fig. 12. Mass change vs. number of 1-hr cycles at 950C of cast NiCoCrAlYHfSi coated with different salt compositions. Data were identical with that of Fig. 10, but plotted separately for different KNa ratios.

attack (Fig. 13a,b). The cast alloy was preferentially attacked in all cases and the oxide scales consisted of a mixture of alumina and spinel phases. Microprobe analysis revealed that chromia had also been formed to a certain extent. For lower sulfur levels, the general trend of decreased attack with a reduced amount of Na was identical with that of stoichiometric sulfur content but, again, signicant preferential attack occurred (Fig. 13c,d). Notably, salts with Na as the only alkali did not follow this trend. For a given sulfur level (2S(NaCK) G0.4 and 0.2), mass gain rather than mass

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Fig. 13. Optical micrographs of cross sections through specimens coated with different salt blends after 500, 1-hr cycles at 950C (a) Pure sodium sulfate [KNa G0, 2S(NaCK) G1]; (b) KNa G0, 2S(NaCK) G0.2; (c) KNa G15, 2S(NaCK) G1; and (d) KNa G15, 2S(NaCK) G0.2.

loss was observed after an incubation period (Fig. 12b,c), which was in contrast to stoichiometric sodium sulfate which caused signicant scale spallation. However, mass-gain curves indicated nonprotective oxide scale formation, and postoxidation SEMEDS investigations of the oxide scales revealed that on all NiCoCrAlYHfSi specimens, spinels were the dominant oxide phases in the scale rather than alumina. Therefore, the general hotcorrosion mechanism of alumina-scale uxing appeared to be identical for all salt blends tested in this study. The surfaces of NiCoCrAlYHfSi specimens exhibited notably different appearances (Fig. 14). For sodium sulfate alone, back-scattered SEM micrographs indicated a rough surface topography caused by partly spalled oxide scale and the growth of voluminous spinel clusters (Fig. 14a). In contrast, the K-containing salt blends maintained a relatively smooth surface (Fig. 14b) and spinel clusters were rarely found on the surfaces of these specimens. The present results suggested that the role of sulfur might have been indirect with regard to alloy attack. As mentioned earlier, no additional SOx

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Fig. 14. Back-scattered SEM surface image of cast NiCoCrAlY after 500, 1-hr cycles at 950C deposited with (a) pure sodium sulfate and (b) potassiumsodium salt blend [KNa G15, 2S(NaCK) G0.2]. The oxide scale formed under sodium sulfate alone was much more prone to spallation than under salt blends.

was used for the experiments to simulate the salt impact delivery scenario. Therefore, salt decomposition to Na2O and SOx , as well as evaporation, might have had signicant effect. Increasing the Na2O level in the salt changed its basicity and accordingly the extent of attack of the alumina scale. At this time, no further data on basicity of the different salt blends is available. On the other hand, as a result of a sulfur decit in the deposit simulated in this study, free excess alkali might have been present on the specimen surfaces, resulting in a much higher vapor pressure than that of the respective sulfates at the test temperature of 950C. Therefore, part of the alkali was assumed to evaporate from the surface, thus reducing the amount of alkali available and producing conditions comparable to a reduced contaminant ux rate. However, this expectation was only noticed for the change of corrosion attack for Na-containing salts shown in Fig. 12a. When potassium was added to the salt blends, a similar mechanism was expected, since the vapor pressure of potassium hydroxidenitrate is also higher than that of the sulfate at the test temperature. However, as the mass-change data indicated, the differences of corrosion attack induced by different sulfur levels were not as great as for only Na-containing salts (e.g., Fig.12b,c). These results suggest that K plays a role in either affecting the deposit chemistry itself such that its vapor pressure is not sufciently high to evaporate notable amounts of salt, or that K directly alters the extent of corrosion attack, e.g., by altering the salt basicity. Additional microanalytical investigations and information on the effect of salt composition on its basicity are needed to clarify the potentially important role of potassium

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on the hot-corrosion behavior of MCrAlY-based alloys for applications in biomass-derived fuel-red gas turbines.

SUMMARY AND CONCLUSIONS The hot-corrosion behavior of NiCoCrAlY-type alloys under thermal cycling conditions was found to depend signicantly on the testing procedures. Contaminant ux rate alone, as an average measure of the amount of deposits applied onto the specimens, was not a sufcient predictor of the corrosion attack when the contaminants are not applied continuously during exposure as in, for example, burner-rig tests. For intermittent deposition of contaminants onto the specimens, a signicant dependence of corrosion on recoating frequency was evident. Even when the same average contaminant ux rate was applied, mass-change data revealed that the corrosion attack was less severe for those specimens coated more frequently but with a lower amount of salt in each recoating step. Therefore, it appears that the residence time of the deposit on the surface is an important consideration. Hence, it is suggested that for hot-corrosion tests with intermittent salt deposition, the recoating frequency must be always considered along with the average contaminant ux rate. Furthermore, the effect of deposit removal should be taken into account when data from different corrosion tests are compared. Depending on the contaminant ux rate, deposit removal (washing) before recoating may result in an accelerated attack, because of a change of the basicity of the molten salt compared to deposits, which were present on the surface for longer exposure times. For different KNa ratios and sulfur levels considered to be relevant to combustion products obtained from biomass-derived fuels, signicantly different corrosion attack was observed, showing that seemingly minor changes in the deposit chemistry may cause important differences in the extent of corrosion attack. With increasing K content in the deposits, the amount of corrosion, relative to pure sodium sulfate, seemed to be reduced. Reducing sulfur in the salts relative to their alkali content reduced corrosion for salt deposits containing Na alone, whereas in the presence of potassium, corrosion was slightly increased. The role of K and its possibly synergistic effect with sulfur on the hot-corrosion behavior of candidate coating materials for application in biomass-derived fuel-related gas turbine applications has yet to be determined. As a nal note, it should also be emphasized that, while measurement of specimen weight change is a convenient technique for following trends in laboratory experiments, given all the caveats mentioned regarding effects of

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salt evaporation and scale loss, conrmation of such trends by metallographic measurements is essential. Further, such measurements are necessary to determine the maximum depth of attack required for quantitative comparison of alloy performance. ACKNOWLEDGMENTS Research sponsored by the German Aerospace Center and the U.S. Department of Energy, Assistant Secretary for Energy Efciency and Renewable Energy, Ofce of Industrial Technologies, as part of the Advanced Turbine Systems Program under contract DE-AC05-96OR22464 with Lockheed Martin Energy Research Corporation. P. F. Tortorelli, D. F. Wilson, and J. R. DiStefano at ORNL provided comments on the manuscript. REFERENCES
1. H. J. Grabke and D. B. Meadowcroft, Guidelines for Methods of Testing and Research in High Temperature Corrosion (The Institute of Materials, London, U.K., 1995). 2. P. Hancock, Corros. Sci. 22, 51 (1982). 3. S. R. J. Saunders, Mat. Sci. Technol. 2, 282 (1986). 4. P. Steinmetz, C. Duret, and R. Morbioli, Mater. Sci. Technol. 2, 262 (1986). 5. J. R. Nicholls, in Guidelines for Methods of Testing and Research in High Temperature Corrosion, H. J. Grabke and D. B. Meadowcroft, eds. (The Institute of Materials, London, U.K., 1995), p. 11 6. A. V. Dean, Investigation into the Resistance of Various Ni- and Co-Based Alloys to Sea Salt Corrosion at Elevated Temperatures, National Gas Turbine Establishment, Report (1964). 7. C. Leyens, I. G. Wright, and B. A. Pint, in Elevated Temperature Coatings: Science and Technology III, J. M. Hampikian and N. B. Dahotre, eds. (TMS, Warrendale, PA, 1999), p. 79. 8. N. S. Bornstein and W. P. Allen, Mater. Sci. Forum 251254, 127 (1997). 9. I. G. Wright, C. Leyens, and B. A. Pint, International Gas Turbine and Aeroengine Congress, Mu nchen, Germany, 811 May 2000, paper 2000-GT-0019, submitted. 10. D. K. Gupta and D. S. Duvall, A Silicon and Hafnium Modied Plasma Sprayed MCrAlY Coating for Single Crystal Superalloys (TMS, Warrendale, PA, 1984), p. 711. 11. C. Leyens, I. G. Wright, B. A. Pint, and P. F. Tortorelli, in Cyclic Oxidation of High Temperature Materials, M. Schu tze and W. J. Quadakkers, eds. (The Institute of Materials, London, U.K., 1999), p. 169. 12. R. A. Rapp and Y. S. Zhang, JOM, 47 (1994). 13. J. A. Goebel, F. S. Pettit, and G. W. Goward, Metall. Trans. 4, 261 (1973). 14. Y. S. Zhang, J. Electrochem. Soc. 133, 655 (1986). 15. R. A. Rapp, Mat. Sci. Eng. 87, 319 (1987). 16. C. Leyens, unpublished research (1998).