Stress Corrosion Cracking of 18Mn-4Cr Generator Rotor Endretaining Ring Steel

N.Mukhopadhyay1 and U. K. Chatterjee2

General Manager, BHEL, Hyderabad, and 2Professor, IIT Kharagpur
1
Corporate R&D Division, BHEL, Hyderabad 500593, India, and
2
Department of Metallurgical & Materials Engineering, IIT Kharagpur 721302, India
Correspondence: ukc@metal.iitkgp.ernet.in
1

ABSTRACT
Stress corrosion cracking of 18Mn-4Cr generator rotor end-retaining ring steel in a 50 ppm chloride containing
water was investigated using constant load technique. Both as-received and thermo-mechanically treated
0
0
fabricated materials were used. In the latter, the stress relieving temperature was varied from 350 C to 500 C,
and the susceptibility to cracking was found to decrease with increasing temperature, accompanied by a change
in the mode of cracking from transgranular to intergranular. The as-received material showed a mixed mode of
cracking, predominantly intergranular. The propensity to cracking increased with anodic polarization and
decreased with cathodic polarization indicating the process to be electrochemical in nature. However, the
initiation of cracks appeared to have taken place by the chemically controlled dissolution of water soluble
carbides.
INTRODUCTION
18Mn-4Cr austenitic steel has virtually been the standard material for the rotor end-retaining rings in power
generation plants during the period of 1960-1980, before it was replaced by the 18Mn-18Cr variety. A good
number of cases of failure of the 18Mn-4Cr steel ring by stress corrosion cracking (SCC) led to a switchover to
the higher chromium variety. The cases of failure have been documented in the report of EPRI Workshop on
Retaining Rings [1]. Investigations by Speidel [2] have shown that nitrate has the most deleterious effect on the
strength properties of this steel followed by water and hydrogen. The sources of humidity have been identified [3]
as imperfectly dried hydrogen, leakages from water-fed stator winding, oil in the hydrogen-tightness circuit and
moisture condensation during shut downs, storage and transportation of the rings. However, no light was thrown
on the mechanism of SCC or any possible effect of stress-relieving temperature, an essential step in the
fabrication of the end-retaining ring, on SCC. The present study was undertaken with these considerations in
view.
Microstructural characterization and electrochemical tests under potentiostatic conditions had been performed
earlier to study the localized corrosion behaviour of this material in the as-received as well as in stress relieved
condition, and the results were reported in a previous publication [4]. The results of the present study have been
discussed on the basis of these previously published results.
EXPERIMENTAL
A right circular cylindrical ring forging was used in the as-received (designated A.R.) and thermo-mechanically
treated conditions. The chemical composition of the steel was:0.52 C, 0.01 S, 0.02 P, 18.98 Mn, 3.87 Cr, o.035
Al. 0.05 V, 0.15 Ni, 1.04 Si, balance Fe. The thermo-mechanical treatment route was in line with the fabrication
0
and heat treatment method generally followed for the end-retaining rings viz. solution annealing at 1040 C,
water quenching, cold working to 15% reduction in area, stress relieving at different temperatures, followed by
furnace cooling. The deformation operation was carried out by pulling the bars of rounded cross section in an
0
0
0
MTS universal testing machine. The temperatures for stress relieving were chosen as 350 C, 400 C, 450 C and
5000C, and the corresponding samples are designated as M4, M5, M6 and M7, respectively.
Tensile specimens of 50 mm gage length and 3 mm diameter were prepared from both as-received and thermomechanically treated steel. Stress corrosion tests were performed in a 50 ppm chloride solution by constant load
technique using a Mayes Unisteel stress corrosion testing device having a lever ratio of 30:1. The tests were
carried out at 80% of the 0.2% YS of the material under free corroding as well as under polarization conditions
using a Wenkin potentiostat. Fractographic studies were performed with a Jeol-JSM5800 scanning electron
microscope.

RESULTS
Stress corrosion cracking was encountered in all the specimens. The time to fracture has increased in
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0
0
specimens stress relieved at 350 C (ca. 540 hr), 400 C (ca. 430 hr) and 450 C (ca. 300 hr), compared to that in
0
the as-received specimens (ca. 150 hr), and has decreased in specimens stress relieved at 500 C (85 hrs). The
0
variation is shown in Table 1. The specimen stress relieved at 500 C was also tested in a chloride solution
deareated by continuous argon purging. No failure was encountered in 470 hrs, showing that the absence of
dissolved oxygen cannot promote cracking.
TABLE 1
Time to Fracture for Specimens in Different Conditions and in Different Media
Type of Specimen

Solution Condition

As-received
SR at 350 C
SR at 400 C
SR at 450 C
SR at 500 C
SR at 500 C
As-received

Average Time to Fracture, hr

50 ppm chloride
- do - do - do - do 50 ppm Cl Argon purged
Cl- free distilled water

150
540
430
300
85
470 NF
2450 NF

SR: Stress Relieved NF: No Failure

Fractrographic examination revealed that the cracking was predominantly intergranular in the as-received
0
condition, predominantly transgranular in specimens stress relieved at 350 C, completely transgranular in
0
specimens stress relieved at 400 C and, and predominantly and exclusively intergranular in specimens stress
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0
relieved at 450 C and 500 C, respectively. Representative fractographs are shown in Figure 1. It may be noted
that the transgranular features include the presence of parallel grooves and saw-tooth steps.

(a)

(c)

(b)

(d)

Figure 1. SEM fractographs for material in (a) As-received, (b) Stress relieved at 350 C, (c) Stress relieved at
400 C, (d) Stressed relieved at 500 C conditions

The effect of polarization on SCC was studied with as-received specimens and also with the specimens stress
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relieved at 350 C and 500 C. The experiments were carried out under OCP (-590 to -605 mV SCE), and anodic
(-400 mV SCE) and cathodic (-920mV SCE) polarization conditions. The results are shown in Table 2. There has
been an acceleration of SCC under anodic polarization, and a decrease under cathodic polarization in all the
cases. It may be noted that under cathodic polarization, the specimens stress relieved at 3500 C did not fail in
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2000 hrs whereas SCC was not suppressed in the specimens stress relieved at 500 C, indicating a high
susceptibility of the alloy in this heat treated condition. Representative fractographs (Figure 2) show that anodic
and cathodic polarization have not altered the mode and basic features of stress corrosion cracks, but the latter
is obliterated by corrosion and corrosion products in the anodically polarized specimens.
TABLE 2
The Effect of Polarization on Time to Fracture
__________________________________________________________________________________
Applied Potential
Average Time to Fracture, hr
As-received
SR at 3500C SR at 500oC
-400 mV (SCE)
O.C.P., -590 to 605 mV (SCE)
- 920 mV (SCE)
SR: Stress Relieved NF: No Failure

65
150
2012(NF)

(a)

340
540
2000(NF)

71
85
1137

(b)

Figure 2. SEM fractographs of (a) As-received, (b) Stress relieved at 500 C, tested under anodic polarization
The as-received material was also tested in chloride-free distilled water. No cracking was encountered in 2450
hrs of exposure (Table 1). The specimen was finally pulled to fracture. A portion of the fractured surface revealed
intergranularity (Figure 3) in a predominantly ductile fracture mode.

Figure 3. SEM fractograph for as-received material tested in chloride-free distilled water
DISCUSSION
The salient observations of the present study are:
1)
2)

The stress relieving temperature has a pronounced effect on the stress corrosion susceptibility. The
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material stress relieved at 500 C has shown the maximum susceptibility.
The mode of cracking is mixed but predominantly intergranular in the as-received condition and in the
material stressed relieved at 4500 C, and exclusively transgranular in the material stress relieved at
5000 C, whereas it is transgranular in the material stress relieved at 3500 C and 4000 C.

3)
4)

Anodic polarization has enhanced the SCC susceptibility, whereas cathodic polarization has reduced it.
There has been evidence of SCC in the as-received material in chloride-free distilled water.

The cracking mode, intergranular or transgranular, is generally dictated by an initiation of cracks at grain
boundary or at grain interior. The initiation of cracking involves localized dissolution at imperfections such as a
second phase precipitate, emergent dislocations on active slip planes, inclusions, grain boundaries and so on,
and the dissolution is mostly assisted by the formation of local corrosion cells. The pit thus formed acts as a
stress-raiser and a site for aggravated electrochemical attack. The 18Mn-4Cr retaining ring material contains
undissolved pre-existing carbides in the solutionized matrix. In a previous publication [4], it has been shown that
some of these carbides are soluble in water, both with and without chloride ions, giving rise to the formation of
pits or grooves. The attack at the grain boundary triple points where carbide thickening is maximum is prominent
under all polarization conditions even at a high cathodic potential of 1400 mV, which emphasizes the fact that
the dissolution of the carbides is chemically controlled. The dissolution of grain boundary precipitates gives rise
to intergranular initiation and that at grain interior to transgranular initiation of cracks. A mixture of both is found in
the as-received material because of the prevalence of carbides at both the regions. However, as suggested by
Scully [5], an intergranular initiation can also give rise to a transgranular propagation.
The association of pitting or grooving with crack initiation has been highlighted in several publications [6-8].
Some of these have stressed upon the role of corrosion products in forming a crevice condition that actually
confines the further corrosion attack along narrower fronts forming tunnels into the metal matrix. The presence of
such corrosion products as mounds and selective attack at grain boundaries and slip steps underneath these
mounds in this material was reported earlier [4] and is reproduced in Figure 4. These are most likely insoluble
oxides of Fe and Mn formed subsequent to the dissolution of carbides. Similarly, a pit formed as a result of
carbide dissolution can also sustain the dissolution reaction along a narrow front. The rapid propagation of
crevice corrosion or of a pit in the presence of chloride is widely known [9].
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The fracture mode in the material stress relieved at 350 C and 400 C are predominantly transgranular. The
presence of some amount of intergranularity in the former is considered to be mainly due to the presence of
chains of prior carbides in the microstructure along which some new grains that have grown during the solution
treatment of the as-received material. However, most of these carbides are present in the grain interior sites that
remain obscured by the slip lines produced on cold working in this work-hardenable alloy. It may be mentioned
here that the precipitation of any fresh carbide particles is unlikely at these stress- relieving temperatures.

(a)
(b)
Figure 4. Mounds observed in specimens stress relieved at 500 C after an exposure in undeareated chloride
solution at a potential of 1200 mV (SCE); (a) a cluster of mounds, 80X, (b) selective attack at grain boundaries
and slip bands underneath a mound, 400X
The transgranular fracture has shown the evidence of corrosion tunneling and saw-tooth steps. Corrosion
tunneling is a result of several slip steps intersecting the surface exposed to a cracking environment [5]. In the
present alloy, the dissolution of soluble carbides precipitated along the slip planes may be ascribed a role in
tunnel formation. The fine saw-tooth steps are indicative of fracture arising out of the joining of a number of
microcracks in a single grain. When the microcracks are sufficiently close to each other, then the metal ligaments
separating them undergo plastic deformation, and these micrcracks colalesce to form a large crack [5]. The
formation of this transgranular feature can be attributed to the presence of a large number of carbide particles in
the grain interior where microcracks will initiate through the process of dislocation build-up.
The presence of a predominant and an exclusive intergranular fracture in the specimens stress relieved
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respectively at 450 C and 500 C is an indication of a shift of heterogeneities from grain interior to grain
boundaries, and the identifiable factor is the extensive carbide precipitation at the grain boundaries.

From all these observations and analysis it emerges out that the soluble carbide, which assists in pit or groove
initiation, may also help in crack propagation by providing an easy path and also by the formation of occluded
cells at these sites. This latter process is electrochemical in nature. The fact that anodic polarization enhances
cracking and cathodic polarization retards it bears testimony to the role of electrochemical processes in the SCC
of this alloy. This is further fortified by the observation that cathodic polarization has drastically slowed down the
process of crack propagation in the samples stress relieved at 5000 C having massive precipitation at the grain
boundaries.
However, the soluble component of the carbide may not carry out the progress of the crack front exclusively. The
electrochemical couple formed by the presence of insoluble cathodic carbides and the adjacent areas
impoverished due to carbide precipitation can also be viewed as contributing to crack propagation. Microcrack
coalescence as discussed earlier is also a contributing factor.
The evidence of SCC crack formation in chloride-free distilled water also supports the chemical dissolution of
soluble carbides. Even if the water is chloride-free beyond a measurable limit, chloride is still there in some trace
amount, and a rapid mass transport phenomenon by diffusion and migration [6,10] can be assumed to occur
leading to the concentration of chloride ions at the crack tip region. However, in such a case the rate of cracking
will obviously be much slower that has been manifested in the large increase in time to failure.
The 18Mn-18Cr variety that has been developed as a new material for retaining ring has been reported [11] to be
resistant to SCC in the conventional environments. This new steel contains very low carbon (0.05 wt%) and high
chromium. The stoichiometric imbalance apparently prevents the formation of complex carbides involving
manganese in this alloy. However, the increased fracture toughness value of the new alloy is also a contributory
factor in resisting the propagation of cracks.
CONCLUSIONS
1.
2.

3.

The susceptibility of 18Mn-4Cr alloy to SCC in chloride medium decreases with increasing stress relief
temperature, and thus the SCC susceptibility can be directly correlated to the extent of carbide
precipitation.
When the stress relief operation is not associated with fresh carbide precipitation, the SCC mode is
predominantly transgranular. With progressive carbide precipitation at the grain boundaries the fracture
becomes exclusively intergranular. The as-received material has shown a mixed mode of fracture that is
predominantly intergranular.
The initiation of SCC cracks can be attributed to the chemically controlled dissolution of soluble
carbides. However, since anodic polarization has hastened the failure process while cathodic
polarization has delayed it, the crack propagation appears to be essentially electrochemical in nature.

REFERENCES
1.

Viswanathan, R., Retaining Ring Failures, Proceedings of the EPRI Workshop on Retaining Rings for
Electrical Generators, USA, Paper No. 2, ( i982)
2. Speidel, M. O., Preventing Failures of Retaining Rings, ibid, Paper No. 1, (1982)
3. Lehnen, C., Alsthoms Experience with 18Mn-4Cr and Trend towards 18Mn-18Cr, ibid, (1982)
4. Mukhopadhyay, N. and Chatterjee, U.K., The effect of microstructure on the localized corrosion
behaviour of a high strength Mn-Cr austenitic steel, Trans. Indian Inst of Metals, 50, 49-58 (1997)
5. Scully, J. C., Fractographic aspects of stress corrosion cracking, The Theory of Stress Corrosion
Cracking in Alloys, Ed. J.C. Scully, NATO Publication, 127-147, (1971)
6. Oldfield, J. W., Test techniques for pitting and crevice corrosion resistance of stainless steels and nickel
base alloys in chloride-containing environments, International Metals Reviews, 32, 3, 153-170,(1987)
7. Hanninen,
H.E.,
Influence
of
Metallurgical
Variables
on
Environment-Sensitive
Cracking of Austenitic Alloys, Int. Met. Rev., 3, 85-136, (1979)
8. Nielsen, N.A., J of Materials, 5, 794, (1970)
nd
9. Corrosion Engineering (2 Edition), M. J. Fontana, McGraw Hill, (1987)
10. Pourbaix, A., Localized corrosion: behaviour and protection mechanism, Corrosion Chemistry within
Pits, Crevices and Cracks, HMSO Books, London, Ed. A. Turnbull, 1-16, (1987)
11. Scarlin, R.B., Albrecht, J., and Speidel, M.O., Corrosion in Power Generating Equipment, Eds. M.O.
Speidel and A. Atrens, Plenum Press, p. 427 (1984)