WEAR

Wear186-187(1995)291-298

The erosion-corrosion

of alloys under oxidizing-sulphidizing at high temperature

conditions

F.H. Stott, M.P. Jordan, S. Lekatos, M.M. Stack, G.C. Wood

Corrosion and Protection Centre, University of Manchester Instituie of Science and Technology, Manchester, UK

Abstract A whirling-arm erosion-corrosion rig has been designed and constructed to allow studies under gaseous conditions of high-sulphur, lowoxygen activities at high temperatures; these environments are pertinent in processes such as gasification of coal and catalytic cracking of oil. The system can operate at particle impact velocities up to 30 m s- , particle impact fluxes up to 1 g cm- s- and temperatures up to 800 C. The particles are carried to the specimen chamber in a stream of nitrogen and mixed with hydrogen, hydrogen sulphide and, if necessary, water vapour to attain the required sulphur and oxygen activities. In this paper, results are presented for two commercial austenitic hightemperature alloys, 310 stainless steel and Alloy 8OOHT,during impact erosion by 25 pm alumina particles at velocities of lo-25 m s- and particlefluxesin theranges0.06-0.16 g cmm2 SKand0.38-0.95 g crn- ~-~ at 500 C. The gaseous environment resulted in the development of sulphide scales on the alloys during exposures in the absence of the erodent particles. The erosion-corrosion damage was determined in terms of mean thickness-change measurements obtained every 5 h and overall metal-recession rates obtained by cross-sectional examination at the end of the 35 h or 70 h exposure periods. The results are discussed in terms of the synergistic interactions of growth of metal sulphides and removal of such phases by the impacting particles.
Keywords: Alloys;

Erosion; Corrosion; Oxidation; Sulphidation; High temperature

1. Introduction The synergistic interaction of mechanical damage due to impact of metallic surfaces by fast-moving particles and chemical degradation due to high-temperature gaseous corrosion is not well understood. Under some conditions, corrosion may enhance the rate of erosion damage while, under other conditions, erosion may enhance the rate of corrosion. However, particularly for relatively low impact velocities by relatively small particles, the formation of a corrosion-product scale can give some protection to a metallic component against erosion damage. These interactions have led to the introduction of terms such as erosion-enhanced oxidation [ 11, erosion+orrosion-dominated behaviour [ 21 and corrosion-dominated behaviour [ 2,3]. During the past 10 years, considerable advances have been made in understanding the synergism between impact erosion and high-temperature gaseous corrosion, in which formation of an oxide scale is the usual mode of corrosion (e.g. [ l81) . Emphasis has ben placed on oxidation in air or oxygen since many industrial processes operate under conditions where alloys for metallic components are selected on the basis that they develop a slow-growing oxide scale for protection against further oxidation.
0043-1648/95/$09.50 0 1995 Elsevier Science S.A. All rights reserved SSDIOO43-1648(95)07149-O

However, there are several modern industrial processes in which components are exposed to environments of highsulphur, low-oxygen contents under potentially erosive conditions; these include systems to convert coal into a gaseous product to drive a gas turbine and catalytic cracker systems in the petrochemical industry. Under such conditions, a protective, slow-growing oxide scale may not be able to be established, or only with difficulty, or be maintained for long periods, and much less protective sulphide scales may be able to develop. Such scales on conventional iron-andiron-nickelbase high-temperature alloys are much less protective than the corresponding oxides and grow at faster rates, resulting in much more rapid rates of metal loss, even if erosion plays no role. Indeed, in some coal-conversion systems, the temperatures of metallic components have to be kept relatively low (below 600 C) , to prevent excessive sulphidation. The aim of the present research has been to design and build an erosion-corrosion rig capable of operating at high temperatures in gaseous environments that have high sulphur partial pressures and low oxygen partial pressures, in order to carry out basic studies of the interactions of oxidation/ sulphidation and particle erosion. The present paper describes the rig and includes the results from some of the initial studies on the degradation under particle-impact conditions of two

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standard commercial high-temperature alloys, 3 10 stainless steel and Alloy 800HT, at 500 C in an oxidizing/sulphidizing gaseous environment that was essentially sulphidizing to these materials.

2. Experimental 2.1. Test rig The erosion-corrosion rig has been built to allow tests to be undertaken under moderate particle-loading conditions in gaseous environments of relatively low oxygen concentrations and high sulphur concentrations at temperatures to 800 C. The practical difficulties and safety implications of these requirements have placed considerable restrictions on the design of the equipment. The system was built by Severn Furnaces Ltd of Thornbury, Bristol and consists of three main parts: a particle fluidizer, a gas-mixing device and an erosioncorrosion chamber (Fig. 1) . Particles in a cylindrical Pyrex glass vessel ( 100 mm in diameter) are filled with erodent particles to a depth of 170 mm and fluidized by nitrogen passing through a sintered disc at the bottom of the vessel and by injection of a jet of nitrogen via a vertical tube in the centre of the fluidizer. The particles and gas form a cloud in the upper part of the vessel and are drawn off via a small diameter tube and fed into the main gas stream above the preheater. The nitrogen gas flow rate to the disc and jet nozzle essentially controls the inlet particle loading into the erosion chamber. Excess gas from the fluidizer provides additional cooling to the electrical terminal boxes in the chamber. Flow meters are used to control the inlet composition of the reactive gas (consisting of hydrogen mixed with hydrogen-2% hydrogen sulphide for the present tests). The gas streams are mixed and then fed into

the stream of nitrogen plus erodent particles before entering the erosion chamber via a carbon-block preheater. The latter ensures that the gas and particles attain the temperature of the chamber. In order to minimize corrosion of the components, the outer metal case of the chamber is kept below 100 C while the volume of the hot zone is restricted to the graphite cylinder at the centre. The heating elements in the dead space outside the cylinder are protected from the reactive gases by a nitrogen purge during a test. Up to 10 specimens can be accommodated in the rig, with 5 being located on each side of the central axis of a 200 mm long specimen holder. During a test, the holder is rotated by a motor attached to the drive shaft. This moves the specimens through the stream of erodent particles that enter the chamber at the top. The relative impact velocities of the particles and the specimens are determined by the locations of the specimens with respect to the axis of rotation of the holder and its rotational speed. In these tests, the specimens were oriented so that they impacted the particle stream at an angle of 90. The gases and particles leave via the bottom of the chamber where the former is scrubbed with potassium carbonate to remove hydrogen sulphide and the latter are collected in a catchpot. 2.2. Materials Results are presented for the erosion-corrosion behaviour of two commercial high-temperature alloys: Alloy 8OOHT and 310 stainless steel, with compositions given in Table 1. The impacting face of the specimens was essentially flat and rectangular ( 10 X 8 mm), while grooves in the specimens allowed them to be secured in the holder. The surface that
contacted the erodent particles was ground to a 320 grit finish and ultrasonically cleaned in acetone immediately before a

Speck N2

hoider

Fig. 1. Schematic diagram of the erosion-corrosion

rig.

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Table 1 Chemical compositions of the alloys (wt.%) Fe Bal. Bal. Ni 32.0 20.0 Cr 21.0 25.0 Mn 1.5 1.5 Si 1.0 1.5 Al 0.4 cu 0.75 _ Ti 0.4 C 0.07 0.04

Table 2 Gas flow rates used to attain the two particle loadings Gas Gas flow rate ( cm3 min- ) Loading: 380 g m-3 Hydrogen Hydrogen-2% hydrogen sulphide Nitrogen fluidizer Nitrogen jet Nitrogen + particles leaving the tluidizer 495 105 3000 1000 1500 Loading: 65 g m-3 495 105 2000 600 1100

Fig. 2. Scanning electron micrograph of erodent particles.

Table 3 Particle fluxes used in the test programme for the two inlet particle loadings Impact velocity (m s- ) Impacting particle flux (g cm- s- ) Loading: 380 g me3 Loading: 65 g m-3 0.16 0.14 0.11 0.09 0.06

test. The erodent particles were 25 p,rn alumina, from Universal Abrasives Ltd. They were angular in shape (Fig. 2). 2.3. Test environments In this paper, the results of tests carried out under two inlet particle loadings (65 g mP3 and 380 g me3) in one gaseous environment at 500 C are reported. The equilibrium partial pressure of sulphur in the mixed gas was lo- * atm and that of oxygen was nominally 1O-35 atm, although it is unlikely that gas-phase equilibrium was attained in these tests, owing to the high gas-flow rates. It had been intended to obtain this environment by mixing hydrogen with hydrogen-2% hydrogen sulphide and water vapour (as is usual for corrosion tests). However, although the hydrogen sulphide content could be attained accurately, it was not possible to control the oxygen content as closely, owing to the trace oxygen concentration in the nitrogen carrier gas. In order to estimate this concentration, several pure metals (nickel, iron chromium, cobalt, aluminium and molybdenum) were exposed to the gas (but containing no hydrogen sulphide) flowing through the rig at 500 C. From the products formed on these test coupons (ie chromium oxide on chromium, aluminium oxide on aluminium, and no oxides on the other metals), it was concluded that the partial pressure of oxygen was between 10P3and 10Wu atm. In view of this, it was decided not to add water vapour to the test gas, but to carry out the experiments in the appropriate hydrogen-hydrogen sulphide gas mixture and rely on oxygen impurities in the nitrogen to provide the required oxygen concentration. The particle loading in the inlet gas to the erosion chamber was controlled by the flow rate of nitrogen and was determined by calibration procedures. The gas flow rates used in the tests for the two particle loadings are given in Table 2. The particle fluxes

25.0 21.2 17.5 13.8 10.0

0.95 0.81 0.67 0.52 0.38

were estimated from knowledge of the inlet particle loading of the gas and the velocities of the specimens as they impact the particles (Table 3). 2.4. Experimental procedures For a test, 10 specimens were fastened into the specimen holder in the chamber, which was sealed and purged with nitrogen at 2 1min- for 45 min before introduction of the mixed hydrogen-hydrogen sulphide gas and the nitrogen stream containing the alumina particles. The preheater and chamber heater were switched on and the system was brought to 500 C over a 2 h period. There was no significant difference between the inlet gas temperature and the temperature of the specimens in the erosion chamber. Following stabilization, the motor was started and the specimens were rotated through the stream of particles at 2388 rev min- , giving the relative specimen velocities specified in Table 3. After 5 h, the motor was switched off and the system was cooled to room temperature over an 8 h period. Thickness-change measurements (which included any thickness increase due to formation of corrosion scale on the back surface of the specimen that was not in contact with the erodent particles) were made, using a digital ball-ended micrometer, accurate to + 1 pm, at 12 locations on each specimen and the average

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determined. The specimens were then returned to the chamber and the process repeated, for a total of 35 h or 70 h. At the end of the test, the specimens were examined in plan by Xray diffraction and analytical scanning electron microscopy. Subsequently, they were mounted and polished in cross-section and the thicknesses of residual metal and of residual scale were measured in at least 24 locations, using an optical microscope, to determine the average values. As there was very little internal corrosion after exposures at 500 C, the residual metal thickness was taken as the distance from the original back surface of the specimen to the metal-scale interface at the side of the specimen exposed to the erodent. The mean metal recession was the difference between the average thickness of the original specimen (determined by micrometer measurements) and the average residual metal thickness. The damaged regions were examined in the analytical scanning electron microscope.

c -20 f t -30 0 I 10 I 20 I 30 Tome, I LO

'a,4

??

50

60

70

Fig. 5. Plot of thickness change against time for specimens of Alloy 800HT during erosion-conosion at 500 C (inlet particle loading, 380 g m- ) at the velocities indicated: 0, corrosion only; A, 17.5 m s-l; X, 10 m SK ; 0.21.2 m s- ; V, 13.8 m s- ; c3,25 m SK .

3. Experimental results

3.1. Measurements of erosion-corrosion damage

The average thickness changes (with respect to the original specimen dimensions) as a function of time, measured at 5 h intervals, are plotted in Figs. 3 and 4 for the inlet particle
-300

10
I

20 1

30 I1 Tfme,

LO

50 :

_i___i

60

70

Fig. 6. Plots of thickness change against time for specimens of 310 stainless steel during erosion-corrosion at 500 C (inlet particle loading, 380 g m- 3, at the velocities indicated: 0, corrosion only; A, 17.5 m s-r; X, 10 m s-l; ?? ,21.2ms- ;0,13.8ms- ;0,25ms-

Time,

Fig. 3. Plot of thickness change against time for specimens of Alloy 800HT during erosion-corrosion at 500 C (inlet particle loading, 65 g m-3) at the velocities indicated: 0, corrosion only; A, 17.5 m s-t; X, 10 m s- ; 0, 21.2 m s-l; V, 13.8 m s- ; 0.25 m s- .

Fig. 7. Plots of metal recession as a function of velocity for erosionxorrosion at500C:(a)alloy800HTfor35h(65gm~3);(b)3l0stainlesssteelfor 35h(65gm~3);(c)alloy800HTfor70h(380gm~3);(d)3l0stainless steelfor70h(380gm-3).

Fig. 4. Plot of thickness change against time for specimens of 3 10 stainless steel during erosion-corrosion at 500 C (inlet particle loading, 65 g m- ) at the velocities indicated: 0, corrosion only; A, 17.5 m s- ; X , 10 m SK ; ?? ,21.2ms- ;V,13.8ms- ;0,25ms- .

loading of 65 g m-3 and in Figs. 5 and 6 for that of 380 g mP3, for impact velocities of 10-25 m s- ; a positive value indicates a thickness increase. The corresponding data for corrosion only are included for comparison. The mean values of metal recession, measured after the tests, are plotted as a function of velocity for the various conditions, in Fig. 7.

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However, it should be emphasized that the thickness-change value is the difference between the average value determined for the specimen prior to the test and that determined after each test period, using a micrometer. Since the surfaces of the exposed specimens were often irregular, particularly as material was removed by the particle impacts, there is a significant scatter band associated with each stated value, even using 12 measurements to determine the mean. From observations of the surfaces after the tests and calculations of standard deviations, it is estimated that each value is within a scatter band of between + 2 p,m and f 3 p.m. The metal recession value is the difference between the average thickness value determined for the specimen prior to the test, using a micrometer, and the average thickness of residual metal determined at the end of the test run, using an optical microscope, after mounting in cross-section (ensuring that the specimen was square to the polishing plane) and metallographic preparation. This change in method, even using 24 measurements, inherently must increase the scatter band for each value, particularly as the scale-metal interfaces were sometimes irregular. From examination of these difficulties and from calculation of standard deviations, the scatter bands for the metal recession data are between + 4 Frn and + 6 p.m. It should also be appreciated that the plots given in Fig. 7 are merely convenient methods of presenting the data; they do not represent true relationships since a change in velocity is also accompanied by a change in particle flux (Table 3). In addition, the data for a loading of 65 g mW3are for 35 h total exposure times while those for a loading of 380 g me3 are for 70 h. As described later, the corrosion process was essentially sulphidation, resulting in the relatively large thickness increases being recorded during the corrosion-only exposures, owing to development and growth of relatively rapidly thickening sulphide scales. Although there were some irregularities in the thickness-change data, several trends were apparent following the erosion-corrosion tests. 1. Under a loading of 65 g m- 3 for 3 10 stainless steel (Fig. 4), there was a greater thickness increase after a given time up to 10 h with increasing velocity. This indicates that the particle impacts did not result in substantial removal of scale. Moreover, the trend for the thickness increase to be greater at higher velocities suggests that erosion-enhanced sulphidation may have occurred, although the differences were not much greater than the scatter band for the measurements. After longer times, smaller thickness increases than for the corrosion-only specimen were observed at the higher velocities (21.2 and 25 m s- ), while, by 35 h, the thickness increases for all velocities were less than that for the corrosion-only specimen, indicating a transition to erosion-corrosion-dominated behaviour, involving significant removal of scale by the erosion action.

Under a loading of 65 g mm3 for Alloy 800HT (Fig. 3), the significantly larger thickness increases that occurred after a given time up to 10 h for velocities of 10 and 13.8 m s- , compared with that for corrosion only, were also consistent with erosion-enhanced sulphidation. Again, the thickness increases, particularly for the higher velocities, after 35 h were significantly less than those observed after corrosion only, suggesting a transition to erosion-corrosion-dominant behaviour. Under a loading of 380 g m -3, the erosion damage was significantly greater than under the lower loading. Apart from a slightly larger increase during the initial 10 h at 10 m s- , the thickness increases recorded for 3 10 stainless steel were always less than those for the corrosiononly specimen (Fig. 6). Indeed, overall thickness losses were eventually recorded for all velocities, with the extent increasing with increasing velocity, as expected for erosion-corrosion-dominated behaviour. Under a loading of 380 g m-3, similar damage trends to those for 310 stainless steel were observed for Alloy 800HT (Fig. 5) ; however, the thickness change at 10 m SKwas always positive and, indeed, was slightly greater than that for the corrosion-only specimen, even after 70 h. Under a loading of 65 g mP3, any differences in the mean metal-recession values as a function of impact velocity for either alloy were within experimental scatter of the measurement method. All values were less than 6 brn (Fig. 7). However, there were much greater effects of velocity under a loading of 380 g mP3, with a rapid increase to metal-recession values of about 30 pm after 70hat25ms- . 3.2. Examination of the sur$aces after the tests In the absence of erosion, both alloys formed sulphide scales (Fig. 8 (a) ) , about 10 pm thick for Alloy 800HT and 12 p,rn thick for 310 stainless steel after 35 h, with no evidence for any oxides. These consisted essentially of an outer porous layer of (FeNi),& and an inner, more compact, layer of iron-chromium-rich sulphides, probably FeCr$,, as expected for such materials (Fig. 9(a)). There was some evidence for spallation of pieces of the outer layer after the first two 5 h cycles, but not after longer periods. Following the erosion-corrosion tests, under a loading of 65 g rne3, there were some obvious changes in the surface morphologies of the specimens. The very fine sulphide crystals observed in the absence of erosion (Fig. 8(a) ) were no longer apparent and typical craters, consistent with 90impact damage, were evident under both low-velocity (Fig. 8 (b) ) and higher-velocity conditions (Fig. 8 (c) ) . Nonetheless, there were significant sulphide scales retained on the surfaces. At the lower velocities ( 10 m s-r), the scales on both alloys were much more irregular in thickness than in the absence of erosion (Fig. 9(b) ) , but the mean values were very similar (about 10 Km for Alloy 800HT and I5 km for 310 stainless

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4. Discussion

Fig. 8. Scanning electron micrographs of the surface of 310 stainless steel after exposure for 35 h in the erosion-corrosion rig at 500 C (inlet particle loading, 65 g m-l): (a) corrosion only; (b) velocity 10 m s- ; (c) velocity 25 ms- .

Fig. 9. Scanning electron micrographs in cross section of the scales developed on the alloys during exposure for 35 h at 500 C (inlet particle loading, 65 g mem3):(a) alloy 8OOHT, corrosion only; (b) alloy 8OOHTat10 m s- ; (c) alloy 800HTat 25 m s-l; (d) 310 stainless steel at 25 m SK .

steel). At 25 m SK , the residual scales were also very irregular (Figs. 9(c) and (d) ), but the mean thicknesses were somewhat reduced (5-9 p,m for both alloys). It was also apparent that the residual scale at the higher velocities was mainly iron-chromium-rich sulphide, with not much of the porous outer layer of (FeNi)& being retained. There was no evidence for loss of scale by spallation in these tests. Also, remnants of erodent particles were never detected in the specimen surfaces. After tests at the higher particle loading of 380 g rnd3, apart from Alloy 8OOHT exposed at 10 m s- , the residual scales retained on the specimens were very thin, consistent with the considerably increased rate of damage and metal loss compared with the results at the lower loading. The mean scale thickness was less than l-2 p,rn in all cases. X-ray analysis revealed that these scales were an iron-chromiumrich sulphide, probably Fe Cr,$, on both alloys. There was no indication of any remaining (FeNi) $& phase.

From the relevant thermodynamic phase stability diagrams for the metal-oxygen-sulphur systems pertinent to the relevant alloying elements (iron, nickel and chromium), iron sulphide, nickel sulphide and chromium oxide should be the stable phases with respect to the pure metals in this environment at 500 C (assuming that the gases are at thermodynamic equilibrium). Although such equilibrium is probably not attained in the rig, the control exposure of chromium in the gas (in the absence of hydrogen sulphide) indicates that the oxide is able to develop on the metal. Exposure of both alloys to the gaseous environment in the rig, without any erodent particles, results in the development of sulphide scales on the specimen surfaces. There is no indication that a Cr,O,-rich layer has been established at any stage. This is not unexpected since the rates of nucleation and growth of the oxide are very much slower than those of ironnickel sulphides, enabling growth of the sulphide phases to predominate in the early stages. Hence, these tests have essentially allowed a study of the interactions of simultaneous sulphidation and impact erosion under two particle loadings at velocities of 10-25 m s--l. Under the lower particle loading (65 g me3 in the inlet gas), there is relatively little difference (within the experimental accuracy of the measurements) in the extent of metal recession at the end of the test as a function of impact velocity (Fig. 7). Although there is an apparent increase with increasing velocity for Alloy 8OOHT, this is within the scatter band of the data. For instance, a metal recession of about 5 pm (rather than mean measured value of l-2 pm) would be expected for a scale thickness of 10 pm, as was formed during corrosion only. The mean thickness-change measurements are more significant and do show some small trends (Figs. 3 and 4). Thus, after short times of exposure, there are larger increases in specimen thickness in the presence of erodent particles than during corrosion only for both alloys, consistent with erosionenhanced sulphidation. However, this trend does not persist and the mean thickness continues to increase less rapidly, or actually to decrease, with longer exposure periods under the erosion conditions. The overall thickness increase at the end of the 35 h test period is less than that for corrosion-only exposures in almost every case, with a general trend for this value to be higher at lower impact velocities. Thus, as the scale thickens, there is a tendency towards erosion+orrosiondominated behaviour. The main damage process is removal of the outer sulphide scale. At the highest velocity, the residual scales are somewhat thinner, in the range 5-9 p,rn for the two alloys, than after corrosion only ( 10-12 Fm) . However, the overall thickness-changedata suggest that the rate of scale removal is relatively small which perhaps accounts for the observation that the extent of metal loss is not increased significantly by erosion; the erosion conditions required for significant removal of scale, leading to increased metal reces-

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sion rates, have to be very severe under these corrosion conditions. Under the higher particle loading (380 g mP3), the trends are similar, except that the extent of scale removal is increased considerably. Thus, there is a general trend for an increase in mean thickness in the early stages to be followed by a decrease on further exposure to the erodent particles (Figs. 5 and 6). There is also some correlation between the erosion damage and the impact velocity; the time to commencement of the thickness decrease is reduced and the rate of such a decrease is enhanced with increasing velocity. (The increase in llux that accompanies an increase in velocity may also be a contributory factor in this respect). Overall thickness decreases are observed eventually for almost all cases (except Alloy 800HT at the lowest velocity). The effect of velocity is also shown in the metal-recession plots, with larger increases being recorded with increasing velocity (Fig. 7). There are always thin residual sulphides retained on the surfaces after the tests. Although these may have developed during cooling after the particle stream was shut off (consistent with the damage process being removal of both metal and sulphide by the erodent particles), it is perhaps more likely that they were present at the end of the erosion period (consistent with the damage process being formation and removal of scale only). However, further work is needed to determine the mechanisms of erosion-corrosion damage under such conditions. During the early stages of exposure, there has been some evidence for erosion-enhanced sulphidation. Here, if the scale is damaged or even if pieces are removed from the outer surface by the impacting particles, accelerated scale growth in these affected areas may result in a thicker scale than in the absence of erosion. However, the precise mechanism for such a process is not yet fully understood [ 11. It is also interesting that the mean thickness change against time plots follow very closely the trends predicted for erosion-corrosion, as discussed by Wright et. al. [9]. In simplistic terms, for a scale (such as an oxide or a sulphide) that grows by a diffusion-controlled process, the growth follows a parabolic relationship with time i.e. the rate of scale thickening decreases with increasing thickness, y. If the scale is impacted by erodent particles and material is removed from its outer surface at a linear rate, the overall rate of scale thickening follows a relationship of the type: dy K -=-k dt Y where K is the parabolic sulphidation rate constant and k is the linear erosion rate constant. Hence, in a situation where the scale thickens by sulphidation and thins by erosion, in the early stages, an increase in scale thickness, and thus in overall specimen thickness, should occur; however, eventually, the sulphidation rate should be just fast enough to balance the rate of scale removal. Thereafter, the thickness of scale remains constant (and equal

to K/k) while, overall, there is a linear rate of decrease in the total thickness of the specimen. Both particle flux and impact velocity are important parameters in influencing this type of erosion+orrosion behaviour. The velocity determines the impact energy and, thus, the extent of damage on each impact while the particle flux determines the number of impacts on the specimen surface in a given time and the time interval between successive impacts on a given spot. The flux can have consequences in terms of the time available for regrowth of scale to replace that removed by previous impacts or for any damage sustained on a previous impact to be repaired, e.g. by an annealing process. Hence, if removal of material follows an accumulation of damage, e.g. a fatigue process, particle flux is likely to be a more important parameter at high temperatures than at low temperatures. Although the above discussion is based on very simple assumptions and ignores many of the factors that complicate the actual erosion+orrosion behaviour, such as the dependence of the erosion rate constant on the oxidation rate constant, the effects of erosion on the mechanisms of growth of the residual scale, the changing composition of the scale as the outer regions are removed, the possibility of removal of complete pieces of scale, etc, it provides a basis to account for the observed erosion-corrosion behaviour. Future research using this rig will address some of these mechanistic features in much more detail. It will particularly compare the erosion characteristics during sulphidation/erosion with those during oxidation/erosion, emphasising the adhesion/ cohesion characteristics of the different scales and the inherent erosion resistance of their surfaces. An important difference between exposures in sulphidizing gases and those in oxidizing gases for these two alloys is that both develop relatively fast-growing iron-nickel-base sulphide scales in the former environment and much slower growing Cr,O,rich scales in the latter environment; there are considerable differences between these two types of scale in terms of adhesion/cohesion with the substrate, growth rates and the ability of the surface to resist multiple impact by erodent particles. For instance, it is generally considered that, as the sulphides developed on such alloys have relatively low melting points (in the region of 700-1000 C, depending on composition), they can deform more easily and may resist the particle impacts more effectively than the higher melting point oxide scales that may be more susceptible to failure by spallation under such conditions.

5. Conclusions 1. An erosion<orrosion rig has been designed and constructed to allow study of the interactions of impacts by solid particles and sulphidation/oxidation in gaseous environments of high-sulphur, low-oxygen activities at high temperatures.

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Preliminary tests have been carried out on two commercial austentic alloys at 500 C in an essentially sulphidizing environment, using 25 km alumina erodent particles, at velocities of 1O-25 m s - . Tests at a relatively low particle loading (giving particle fluxes in the region of 0.06-O. 16 g cm- s- ) resulted in some erosion-enhanced sulphidation during the early stages followed by a slight tendency for erosioncorrosion-dominated behaviour in the later stages. However, increases in the overall rates of metal loss due to erosion by the impacting particles, compared with those recorded for corrosion only, were within the experimental errors of the damage measurements. 4. Tests at a higher particle loading (giving particle fluxes in the region of 0.38-0.95 g cm-* SK ) resulted in very significant overall rates of metal loss, which increased with increasing impact velocity. The relationships between the extent of damage (as thickness-change measurements) determined by and exposure time approximately followed those expected for erosion-corrosion-dominated behaviour.

Acknowledgements

The authors are grateful to Commission of European Community for support under the Joule Programme and the Shell International Petroleum Company for a grant towards the costs of the erosion+orrosion rig.
References
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NACE, Houston, TX, 1989. [5] D.J. Stephenson, J.R. Nicholls and P. Hancock, Corros. Sci., 23 (1985) 1181. [6] F.H. Stott, S.W. Green and G.C. Wood, Mater. Sci. Eng., A121 (1989)
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1045. [8] M.M. Stack and F.H. Stott, J. Phys. IV, 3 ( 1993) 687. [9] LG. Wright, V. Nagarajan and J. Stringer, Oxid. Met., 25 (1986) 175.