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WEAR

ELSEVIER
Wear 180 (1995) 91-99

Relationship between the effects of velocity and alloy corrosion resistance in erosion-corrosion environments at elevated temperatures
M.M. Stack, J. Chacon-Nava,
Corrosion and Protection Cenhq

F.H. Stott
M60 IQD, UK

UMIST, P.O. Bar 88, Sackville Street, Manchester

Received 16 July 1993; accepted 31 August 1994

Abstract

Erosion<orrosion by either solid particle or liquid impact occurs in a wide variety of industrial environments which range from coal conversion processes to steam turbines in nuclear power generation. The effects of erosion-corrosion depend on properties of the particle, the target and the nature of the corrosion environment. Various regimes of erosion<orrosion interaction have been identified, ranging from erosion-dominated (erosion of the substrate) to corrosion-dominated (erosion of the corrosion product). In studies of erosion-corrosion, the effects of impact velocity are generally not well understood. In some environments in which corrosion occurs, high velocity exponents have been reported, while, in others, the values are close to 1. In addition, the effects of alloy corrosion resistance in environments of different velocities have been puzzling with differences in the exponents reported, as alloy corrosion resistance is increased. This paper considers the effect of velocity for various erosion%orrosion studies from the literature. The effects of alloy corrosion resistance for such results are evaluated. Some general provisos for the interpretation of the effects of velocity will be made for alloys of different corrosion resistance in erosion-corrosion environments. It is shown that relative erosion-corrosion resistance of alloys in one environment cannot be used arbitrarily to predict resistance in other environments, particularly if parameters such as velocity are varied significantly.
Keyword: Erosion; Corrosion; Particle impact; Velocity

1. Introduction

Although much progress has been made in recent years in the understanding of erosion-corrosion mechanisms, there are still areas which are still not fully understood. Erosion+orrosion problems are major factors which affect materials selection in many industrial processes. Environments in which erosion+rrosion occurs by solid particles at elevated temperatures include coal conversion systems, catalytic crackers in oil and gas separation, and gas turbines. In aqueous environments, erosion-corrosion can be caused by either liquid impact (such as in steam turbines in nuclear power plants), or by solid particles entrained in liquid (slurry erosion<orrosion). Hence, erosion-corrosion can either occur by: (i) solid particle impact in gaseous environments. (ii) liquid impact, (iii) solid particle impact in aqueous environments.

The extent of attack in such environments is dependent on a wide range of variables which includes properties of the: (i) particle (velocity, density, hardness, shape, size, corrosiveness), (ii) target (hardness, strain hardening coefficient, corrosion resistance), (iii) corrosion environment - if gaseous: partial pressure, temperature, corrosion rate constants, - if liquid: pH, Cl-, temperature, velocity. Progress in the understanding of erosion<orrosion mechanisms has been aided in recent years as a result of the systematic studies carried out in low particle velocity fluidized-bed environments [l-5]. Such studies were initiated due to the high wastage rates observed in fluidized bed combustors on the heat exchanger tubes at relatively low temperatures. In the subsequent studies, the effects of variables such as temperature, alloy

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M.M. Stack et al. I Wear 180 (1995) 91-99

corrosion rate, velocity, surface pre-treatments and particle size were evaluated. As a result, an understanding of the effects of such variables in these environments is beginning to emerge. The results showed that erosion-corrosion rate had a distinctive pattern with temperature, increasing up to a critical temperature and decreasing with further increases in temperature [l-5]. This curve shifted to higher temperatures with increasing alloy corrosion resistance [2], and higher temperatures and wastage rates with increasing particle velocity [l]. An interesting feature about such results is that some years earlier the same effect of temperature and alloy corrosion resistance had been observed for erosion-corrosion in aqueous environments [6-81. The effects of these erosion-corrosion variables in fluidized-bed environments have lead to the classification of various erosion-corrosion regimes. The transitions between such regimes are best understood by considering the effect of temperature, Fig. 1. At low temperatures, erosion of the alloy substrate is the dominant process. As the temperature is increased, the rate of formation of corrosion product increases. If this layer which forms between successive erosion events is removed after impaction, a temperature is eventually reached where the removal of corrosion product is the dominant wastage mechanism. This is the regime in which corrosion enhances the erosion-corrosion rate, and marks the transition to the erosion<orrosiondominated regime. At this point, the erosion-corrosion rate increases with further increases in temperatures, as the corrosion product is continually removed and reformed. However, at a critical temperature, the corrosion product becomes sufficiently thick and cohesive to resist impaction between these erosion events and, above this temperature, the erosion-corrosion rate decreases with further increases in temperature. The reason for the shift in the curve to higher temperatures with increased corrosion resistance is due to the fact that alloying additions decrease the growth rate of the

corrosion product formed, and hence the so-called critical scale thickness required to effect the transition to corrosion-dominated behaviour must be attained at higher temperatures. Increases in velocity increases the impact energy, and the overall efficiency of the erosion event. Hence, the critical thickness needed to effect the transition to corrosion-dominated behaviour is also attained at successively higher temperatures as velocity is increased. The effects of velocity in solid particle erosion are well established. The generalized relationship which relates erosion (mass loss/mass impacting particles) to velocity is given by the following equation: E=Kvf(B) (I)

h Fig. 1. Schematic corrosion regimes

lb

>
Temperature
the erosion-

diagram of the transitions through as a function of temperature.

where e = erosion, k = constant, v = velocity, it = exponent and 0= impact angle. The velocity exponents which are usually reported for the erosion of metals vary between 2 and 3 [9,10]. For ceramics, the dependence of erosion on velocity is less clear, with high exponents being reported in some environments, and models for erosion of brittle materials have been developed to account for this observation [11,12]. The velocity dependency for ceramics is determined by the mode of fracture, whether ductile or brittle. In the ductile regime where the ceramic is not significantly eroded, the exponents are low [13]. Above a critical velocity, the erosion increases considerably and the velocity exponents are much higher, closer to 3. It has been pointed out that extending this ductile regime to higher velocities will result in a lower velocity dependence on the extent of erosion [13]. For example, if the hardness of the target tends to that of the particle, the velocity exponent may decrease. A similar situation may occur if the particle geometry is changed from angular to rounded, or if the particle size is decreased significantly. In erosion-corrosion, however, the effects of velocity are complicated by the fact that erosion conditions determine the extent of corrosion on the surface. For example, the extent of scale growth rate is dependent on the time between impacts which may itself be a function of the velocity. In addition, the effects of velocity in the various regimes are not well understood. A wide range of exponents has been reported in erosion-corrosion environments, ranging from 1 to 5 [l-5,14,15]. In addition, there is no general consensus on why exponents should be high in one environment and low in another. Attempts to evaluate velocity exponents do not consider that the exponent may change according to the erosion-corrosion regime. Generally, exponents tend to be evaluated over the whole velocity spectrum, despite apparent transitions through erosion-corrosion regimes. One of the more interesting results from the erosion-corrosion literature, Fig. 2, has been the effect of

MM. Stack et al. 1 Wear 180 (1995) 91-99

93

sion-corrosion behaviour is that in many of such studies, the effects of velocity have been of less interest than for example temperature, and, at the most, five data points are available for statistical analysis. However, since there are at least three erosion-corrosion regimes, a considerably greater number of data points is necessary before convincing evidence can be presented of the potential of exponents to identify the various erosion-corrosion regimes in a single study. However, this is not to say that the early studies cannot be used to identify trends in the variation of the exponent in different erosion<orrosion regimes, and in this work an attempt has been made to identify such trends.
2.2. Effect of temperature

TcmpWatur*

Fig. 2. Schematic diagram of the variation of erosion-corrosion rate with temperature for two alloys of different corrosion resistances (corrosion rate of Alloy I> Alloy 2).

alloy corrosion resistance on the erosion-corrosion rate versus temperature curve. The ranking order of the erosion<orrosion rate can reverse for alloys of different corrosion resistances as the temperature is increased. In addition, the literature shows that the velocity exponent for alloys of different corrosion resistance is dependent on the conditions [4]. Thus, the relationship between corrosion resistance and velocity needs to be examined in order to ascertain why corrosion rate may alter the velocity exponent in such environments. Hence, this paper considers the effect of velocity in the various erosion+rrosion regimes. The results will be evaluated from a range of erosion-corrosion studies involving solid particles in gaseous media at elevated temperatures. The factors which affect the derivation of the velocity exponents are examined. The effects of alloy corrosion resistance on such exponents are considered, and some general provisos are outlined for interpreting the effect of velocity for alloys of different corrosion resistances in erosion<orrosion environments.

In one of the initial studies [l] of the effect of velocity at a range of temperatures, Fig. 3, the data suggested that the exponent increased with temperature, as the transitions through erosion-dominated to erosioncorrosion-dominated behaviour occurred [4]. The exponent in the corrosion-dominated regime was high, 4.2 at 557 C. (The point at which the erosion rate reduces with increasing temperature is the commencement of the so-called corrosion-dominated regime). The limitations of this study is that it involved only two velocities, and therefore there is no evidence that the velocity dependence follows a power law relationship. However, the high exponent evaluated in the so called corrosion-dominated regime was a very interesting result because it contradicted the results from other studies which suggested that erosion-corrosion rate is much less dependent on velocity in the corrosiondominated regime than in the other erosion-corrosion regimes [3,14,16]. It was subsequently concluded that these two contrary observations were due to the fact that there was probably more than one corrosiondominated regime. It was suggested that the corrosion-

12-

2. Analysis of experimental
velocity in erosion-corrosion

results on effects of environments

2.1. Introduction One of the aims of this paper is to investigate whether velocity exponents can be used to identify an erosion-corrosion regime. To test whether this is the case, the velocity exponents need to be evaluated from the erosion*orrosion literature. The erosion studies which have been included in this paper were carried out in high temperature gaseous environments. The problem with using exponents as evidence of a type of ero-

OL to0

1
700

200

400 500 300 Tcmprrature (%)

600

Fig. 3. Variation of erosion rate with temperature for two velocities [l] (erodent 1 mm alumina).

for carbon steel

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M.M. Stack et al. I Wear 180 (1995) 91-99

dominated regime should be subdivided into two subregimes [4], corrosion-dominated l, where the erosion rate versusvelocity dependence was high and corrosiondominated 2, where the velocity dependence was low. Other studies on the effect of velocity at a range of temperatures have shown that the design of the rig used for the erosion-corrosion tests can have a significant effect on the experimental results, and this has been pointed out in previous work [2]. In some experimental rigs, which have been used to simulate erosion-corrosion in fluidized beds, the velocity was achieved by rotating the specimens through a bed of particles [2]. In others, the vertical drop apparatus [l], the particles impacted a stationary target. The difference between the two methods, was that in the former, the particle flux increased with velocity, whereas in the latter case, the particle velocity was independent of flux. For experiments in which flux was linked to velocity [2], there was a significant difference in the results obtained, Fig. 4, from those of the earlier work, Fig. 3, because the exponents were much higher than those of the previous study, i.e. 5.0 at 300 C. This was attributed to the fact that in this case, the exponent reflected the increase in particle flux in addition to impact energy as the velocity was increased. Such an effect would not have occurred in the previous study where flux was independent of velocity. The results of an early study [14] for the erosion of a low alloy steel (Fe-9Cr-1Mo) at 850 C, Fig. 5, show an interesting pattern of erosion-corrosion rate versus velocity. In this study, the velocities were significantly higher and particle size lower than in the previous studies. It can be seen that the velocity dependence can be divided into a number of regimes. A low exponent, 0.78, was measured for the lower velocity region between 0 and 25 m s- . The intermediate velocities were associated with higher exponents (i.e. 3.3 in the range

1
20

I
40

10

30

so

I
60

I 70

J
80

v0baw 01paw-km mlr


Fig. 5. Effect of velocity on the thickness loss of 9Cr-1Mo steel after erosion at 850 C at 90 impact angles. T=5 h (erodent 128 pm alumina) [14].

.ominor i Turbulent
flow flOU

-I-

rogimo I I I I I I I i I

rOglm0

VC

Plow Velocity
rate

Fig. 6. Schematic diagram of the variation of erosion-corrosion with velocity in aqueous erosion-corrosion conditions [6].

Rmporolure

( C)

Fig. 4. Variation of wastage with temperature for AI.51 347 [2] after erosion-corrosion in a fluid&d bed environment (erodent 180 pm alumina).

25-35 m s-l), and, subsequently, the exponent decreased at the higher velocities above 35 m SK . Such a variation in the exponents derived was evidence of transitions through several erosion-corrosion regimes, as velocity was increased. These results were interesting because such a pattern has also been seen for erosion in aqueous media, Fig. 6. Hence, this shows that the transitions between erosion-corrosion regimes, observed at elevated temperatures for erosion by solid particles are analogous to those for erosion-corrosion in aqueous environments. The exponents derived for two sets of studies involving as-received steels also showed some interesting trends, Figs. 7-8 [3,17]. The tests were carried out in laboratory simulated fluidized-bed environments. For the erosion of a 722M24T steel at 500 C, it was shown that at

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95

2.3. Effect of alloy corrosion resistance The effect of velocity for alloys of different corrosion resistance was outlined in two different studies, at elevated temperatures in dry oxidizing environments. In both studies, erosion was achieved by the impact of alumina particles. The effect of velocity was considered for two alloys at 500 C, for velocities ranging between 1 and 2.5 m SK , and involving 170 pm alumina particles [18], Fig. 9. The results in this study showed that the exponent evaluated for the less corrosion resistant 410 steel (12% Cr), was higher than that reported for the more corrosion resistant 316 stainless steel (18% Cr-10% Ni), although there some evidence of a reversal in this behaviour at the lower velocities. The effects of alloy corrosion resistance and temperature were evaluated in a recent study [19]. The erodent used for the tests was 580 pm alumina, and the specimens were rotated vertically through a laboratory simulated fluidized bed environment which has been described elsewhere [5]. The exposure time was 24 h. Two alloys of different corrosion resistance, mild steel and 310 stainless steel, were tested at temperatures of 300 C and 600 C, Figs. 10-12. The results showed a recorded weight gain for both alloys after exposure at both temperatures of 300 C and 600 C in the velocity range l-2 m s- . (It was not possible to ascertain the relative contributions of oxidation and erodent deposition to this value; obviously deposition was less significant at the higher temperatures as the weight gain for the mild steel increased by a factor of 10 as the temperature was increased to 600 C). It was interesting that the weight loss versus velocity dependence between l-2 m s-l was greater for the 310 stainless steel than for the mild steel at 600 C, Fig. 10(b), indicating that a transition in the erosioncorrosion regime occurred at lower velocities for 310
??

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Log

voloci

ty

Fig. 7. Effect of velocity on the wastage of 722M24T at 500 C [17].

VI

0.2 i-

-I

0.1

0.2 velocity

0.3

0.4

0.5

Log

Fig. 8. Effect of velocity on the weight loss of Incoloy 8OOH in fluidized-bed environments at 500 C [3] (erodent 200 pm silica).

the lower velocities, the exponents were less than 1, Fig. 7. Such results were consistent with the earlier results, Fig. 5, which reported low exponents in the high temperature corrosion-dominated regimes. It was interesting that for other work, Fig. 8, low exponents were also reported for this regime. At the high velocities, Figs. 7-8, the exponents increased significantly. This was due to a transition in the erosion-corrosion regime in addition to the flux/velocity dependence for these tests, outlined earlier. It is worth noting that when a transition between two erosion<orrosion regimes occurs, the exponents derived over the whole velocity range reflect an amalgam of both regimes, which is not surprising. However, this sometimes tends to be ignored by investigators evaluating exponents. In addition, the value of the correlation coefficient can give an indication of transitions between erosion-corrosion regimes. A low correlation coefficient over the total velocity range indicates a transition between several regimes. In general, the higher the correlation coefficient, the more likely the exponent should apply to only one regime.

300 t

-r-316 .. I.. 410

A
8

Velocity, m d
Fig. 9. Effect of velocity on the erosion+orrosion of 410 and 316 stainless steel in fluidized bed environments after exposure at 500 C for 100 h [18] (erodent 170 pm alumina).

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MM. Stack et al. / Wear 180 (1995) 91-99

91

Mild steel
30 Weight loss (mg cm-21

0 (a)

Velocity (m e-l)

310 Steel
Weight lore (ma cm-21
7
20
??

, ,

6OOC

10
,

I ,

3ooc

0 (b)

Velocity (m r-1)

Fig. 12. Variation of weight loss with velocity at 300 C and 600 C, after erosion in a fluidized bed environment (erodent 580 pm alumina): (a) mild steel; (b) stainless steel.

The reasons why exponents should be high in the erosion~orrosion-dominated and corrosion-dominated 1 regimes are not fully understood. One explanation is that the erosion constant K changes in the different regimes, and the velocity exponents derived reflect this change. Such an effect can be analyzed as follows. If in the derivation of the exponent, K, and K2 are the erosion constants of the scale formed after erosion at o1 and uuzrespectively:

impacted can vary significantly. In addition, the resistance of the oxide to erosion can also change, depending on the relative cohesion of the layer formed during erosion [S]. For example, thin oxides which have poor cohesion may be less erosion resistant than thick adherent oxides. If the erosion resistance of the surface impacted decreases as velocity increases, it indicates that K,>K,. If this is the case, then the calculated n will be less than the figure evaluated than if it were assumed that K,=K,. It is interesting that the velocity dependence through the erosion<orrosion regimes shows that the exponent is low in the corrosion-dominated 2 regime (= l), increases to higher values in the corrosion-dominated 1 regime, commences to decrease in the erosioncorrosion-dominated regime, and is approximately 2 to 2.5 in the erosion-dominated regime. The reason why the exponent should increase and subsequently decrease within the intermediate regimes is not certain. However, if the erosion-corrosion process within regimes could be considered in terms of a series of microtransitions, suchvariations in the exponent derived could be explained. For example, the erosion resistance of the scale formed in the corrosion-dominated 1 regime will undoubtedly be a function of temperature, and should increase until the onset of corrosiondominated 2 behaviour. Since the erosion constant is denoted by the values of K in Eq. (2), it would be expected that the exponent would reflect this variation within the regime. Similarly, the erosion resistance of the transient scale formed in the erosion-corrosiondominated regime would be expected to vary within the regime, and this would also affect the exponent derived. Other factors which may affect the derivation of the exponent are the differential growth rates of the oxides in the various erosion-corrosion regimes. Parabolic oxide growth behaviour is likely to occur in the high temperature corrosion-dominated regime. However, it is likely that the oxide growth kinetics will be linear in the erosion<orrosion-dominated regime, and hence, transitions between oxidation growth kinetics may also cause a variation in the exponent evaluated. 3.2. Relationship
corrosion between effects of velocity and alloy resistance

(2)

In the evaluation of the exponent, K2 is always assumed to be equal to K1. However, if a transition through an erosion<orrosion regime occurs, this should not be the case because the erosion resistance of the surface

The dependence of erosion<orrosion rate on velocity, for alloys of different corrosion resistance, changed in different conditions, Figs. 9,10-12. This was a surprising observation, but, on closer inspection of the effects of velocity described earlier, there may be some justification for such behaviour. Fig. 13 is a schematic diagram of the transitions through the erosion-corrosion regimes as a function of velocity. Clearly, increases in corrosion resistance or particle erosivity will shift the corrosion-

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M.M. Stack et al. I Wear 180 (1995) 91-99

Fig. 13. Schematic diagram of the anticipated transitions between the erosion<orrosion regimes as a function of velocity.

dominated behaviour (where velocity dependence varies between 2-3) is achieved by the most corrosion resistant alloy, Alloy 2 at a lower velocity than for Alloy 1. A similar pattern to the above would be expected if the effect of velocity were assessed for the same alloy at a range of temperatures (Fig. 12), since increasing corrosion resistance by increasing alloying additions is analogous to reducing the erosion+orrosion temperature. This pattern shows that the apparent inconsistencies in the velocity exponent for alloys of different corrosion resistance can be related to the different velocity dependence in the various erosion-corrosion regimes. These observations also suggest that it may be erroneous to assume that the velocity exponent observed for alloys of different corrosion resistance remains unchanged even if the severity of erosion-corrosion conditions is varied. Hence, caution must be used in extrapolating velocity effects in one set of erosion-corrosion conditions to other conditions for alloys of different corrosion resistances. The results also show, Figs. 11 and 12, that the ranking order of erosion-corrosion rates of alloys of different corrosion resistances can reverse in different velocity conditions. This has important consequences for materials selection in erosion-corrosion environments. The relative erosion*orrosion resistance of alloys in one environment cannot be used arbitrarily to predict resistance in other environments, particularly if parameters such as velocity are varied significantly.

F! Velocity

V3

4. Concluding

remarks

Fig. 14. Schematic diagram of the effect of alloy corrosion resistance on the variation of erosionxorrosion rate with velocity. Corrosion rate of Alloy I> Alloy 2.

dominated regime to lower velocities, and, if the corrosion rate of the environment increases, or the particle impact energy decreases, the corrosion-dominated regime will shift to higher velocities. Hence, increasing the temperature will shift this curve to higher velocities, as the transition to erosion-dominated behaviour is achieved at higher velocities. (An analogy can be made between this behaviour and the effect of velocity in Figs. l-2, where increases in velocity shifts the so-called corrosion-dominated regimes to higher temperatures) Fig. 14 is a schematic diagram of the effect of velocity for alloys of different corrosion resistances, where the corrosion rate of Alloy 1> Alloy 2, based on the experimental results reported earlier, Figs. 10-11. It can be seen that in the low velocity range 2)1-V2, the dependence is lowest for the least corrosion resistant alloy, Alloy 1. However, in the higher velocity range Q-V,, this behaviour reverses, as erosion-

(i) The effect of velocity is dependent on the erosion-corrosion regime on the alloy surface. Factors which change this regime, such as temperature or alloy corrosion resistance, will alter the erosion<orrosion versus velocity dependence. (ii) Alloy corrosion resistance has a significant effect on the variation of erosion-corrosion rate with velocity. The ranking order of the exponents for alloys of different corrosion resistance may reverse if the conditions are altered. Hence, velocity exponents cannot be used arbitrarily to predict erosion-corrosion rates of alloys of varying corrosion resistances. (iii) The disparity in exponents reported for the corrosion-dominated regime have justified the subdivision of this regime into corrosion-dominated 1 and corrosion-dominated 2. (iv) In general, the lowest velocity exponents are recorded for the corrosion-dominated 2 regime where erosion is insignificant compared to corrosion. (v) The relationship between erosion-corrosion rate and velocity has a significant implication for materials selection in erosion-corrosion environments. The ranking order of erosion-corrosion resistance of two alloys

M.M. Stack et al. I Wear 180 (1995) 91-99

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of different corrosion resistance can reverse if the velocity is changed significantly. Hence, the relative erosion-corrosion resistance of alloys in one environment cannot be used arbitrarily to predict resistance in other environments, particularly if parameters such as velocity are varied significantly.

Acknowledgements The authors are grateful to CONACYT sponsorship of J. Chacon-Nava.

Mexico for

References
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