7 References
1. C. Bresseleers et al.: EUR 6203, 1978, Luxemburg, Commission of
the European Communities.
2. J . K. Stanley: Journal of Materials 5 (1970) 957-971.
3. H . J. Grabke, A . Schnaas: Alloy 800, pp. 195-208, Amsterdam.
North Holland Publishing Comuanv.
4. J . M. Harrison, J . F. Noryon, R.=T.Derricott, J . B. Marriott: Werkstoffe u. Korrosion 30 (1979) 785-794.
W 2186
OO43-2822/81/111 l-O478$02.50/0
Material
Mean linear
Youngs moduli Refercoefficient of
ences
thermal expansion
E x 10MPa
x 10-iK
MnS
18.1
8.0
0.58
5.0
5.0 + 8.8
8.4
9.4
,41203
SOz
3A1,03 x 2Si02
CaO x A120z
MgO x A1,03
TiN
Carbon steel (RT)
Austenitic steel (RT)
Martensitic steel
(850 -+ RT)
12.5
14.6
11.5
27.6
32.3
-20.7
20
171
171
[71
[71
[71
[71
[71
[81
[81
21.2
[71
39.6
14
479
Inclusions
Stress concentration
estimated
experimental
theoretically
FeS
Si02
1.75
1.41-1.57
AW?
complex
silicates
1.31
-
1.58-1.7
1.4 -1.55
1.29-1.4
IW?llnll
Fe H2S -+ Fe(HzS)dds
Fe(H2S),d, -+ FeH2S2+ 2e
FeH2S2+-+ Fe2+ H2S
480
Passive Film
IMeZ+
PH7
Stet1
2 Pitting corrosion
Sulfide inclusions and especially mixed sulfide-oxide inclusions [l, 21 are the most privileged sites for pit nucleation i n
commercial steels.
The nucleation of corrosion pits at sulfide inclusions is
differently interpreted in the relevant literature.
Taking into consideration that, as a rule, in the presence of
sulfides the corrosion attack starts within the region between
the sulfide inclusion and the passive metal, the supposition of
Tronstad [20] can still be regarded as valid. He has assumed
that the breakdown of the passive film at the boundary of
certain inclusions occurs since there may be differences
between the thermal expansion of the two adjacent species, or
differences in the adhesion of the film resulting in crevice formation.
More recently, Brooksbank and Andrews [21] have suggested that voids may be created between MnS inclusions and
steel matrix because the sulfide contracts more in volume at
cooling than does martensite o r ferrite.
A different interpretation has been proposed for stainless
steels by Wranglkn [22] and Eklund [23].
Wrangle'n suggests that owing to the relatively high electronic conductivity of sulfide inclusions compared to that of
the surrounding oxide film, chloride ions are adsorbed on. the
surface of sulfide inclusions. Adsorbed chloride ions facilitate
the anodic dissolution of sulfide inclusions. Therefore, the
steel surface becomes exposed and attacked. According to this
viewpoint, the above process can be considered as microcrevice corrosion.
Eklund [23] claims, on the other hand, that because the
sulfides are electronic conductors, they can be polarized to a
potential at which stainless steel assumes the passive state. A t
this potential the sulfides are unstable thermodynamically and
tend to dissolve. When such a dissolution takes place, virgin
metal is exposed to the environment. Eklund suggests that
since the electronic conductivity is relatively low, dissolution
takes place preferentially at the boundary between the sulfide
and the matrix; and for this reason a small crevice develops.
According to our point of view, the mechanism of pit nucleation at sulfide inclusions is as follows: A t sites on the metal
surface, where nonmetallic inclusions are present, the film is
inhomogeneous, either chemically or physically. Presumably,
at the metal-inclusion interface the oxide film is defective,
stressed and susceptible to failure by localized attack. Through
such a defective oxide film iron ions are assumed to pass more
easily than through a more perfect film. A t these defective
spots there occurs a critical agglomeration of chloride ions,
and this happens already at a potential slightly less positive
than the pitting potential, while pit nucleation takes place at a
more noble potential [24]. The local agglomeration of chloride
ions leads to the formation of microstains (islets on the passive
film). These microstains, 50-100 A in thickness, probably contain iron chloride o r - in the case of stainless steels - a mixture
of iron and chromium chlorides. D u e to hydrolysis and a high
CI- concentration, there occurs a local acidification of the
electrolyte, and this leads to dissolution of the passive film
which had already been weakened by the exit of iron ions at
these sites. Therefore, the aggressive environment has now
IN CL
IN
MeCL,+lz-I
Cc
1 H,O-MefOH)z+zHf*Ze
c LpH7
rn
Pit
Salt
layer
Fig. 2. The model of MnS effect on the pit formation and develop-
ment
Abb. 2. Model1 fur die Wirkung von MnS bei der Lochkeimbildung
und beim Lochwachstum
free access to the metal surface. The pit develops when the
electrolyte within it acidifies to such an extent that repassivation cannot occur. The presence of H2S additionally prevents
steel from repassivation.
Fig. 2. gives a schematic representation of the pit nucleation
and development process in a sulfide-containing stainless
steel.
It should be noted that the corrosion process in a pit occurs
in the active state of the metal. Therefore evolution of hydrogen gas from pits is frequently observed [25, 261. As it will be
discussed later, a part of hydrogen enters the metal and produces hydrogen embrittlement in some cases. Likewise, for
ferritic steels in chloride-free solutions, the local corrosion
occurs on nonmetallic inclusions. This has been observed by
Kasparova and Kolotyrkin who have studied corrosion of 17
and 28% Cr steels in 1 N H2SO4[27].
Recently a number of papers have appeared which show
more or less clearly that the shape of nonmetallic inclusions
plays a significant role in pit nucleation. For example, Payet
and Desestret [28] have paid considerable attention to the
effect of the shape of inclusions. For a given type of inclusions,
spheroidized particles are less susceptible to corrosion than
elongated and plastically deformed ones. It is concluded that
depending upon the amount of cold work and heat treatment,
which affect the coherence between alloy matrix and inclusions, the susceptibility of steel to pitting may vary quite considerably.
According to Manning et al. [29], who have studied pitting
in single and duplex-phase 304 L stainless steel, the singlephase materials show pits at the austenite-sulfide interfaces,
whereas in the duplex-phase materials pits initiate at 61y inter-
481
SCC in high purity water and the presence of certain nonmetallic inclusions.
Silcock and S w a m [40] studied nucleation of transgranular
stress corrosion cracks in Type 316 steel in 42% MgCI2 at
150C. They found that nucleation at inclusions (MnS was the
most potent factor in this sense) occurred preferentially in
surface orientation corresponding to the edge dislocation
emergence indicating that slip was important. The nucleating
particles were several p in diameter and were usually but not
always attacked by stress corrosion. In many cases decohesion
occurred under the action of the applied stress along the inclusion matrix interface.
Even though on numerous occasions one cannot be positive
whether stress corrosion cracks develop owing to the anodic
process of metal dissolution, or due to the penetrating hydrogen, nonmetallic inclusions are detrimental in either case.
The disintegration of sulfides upon immersion in acid solutions or during cathodic polarization results in an increased
absorption of hydrogen by the steel in the vicinity of a sulfide
inclusion. This is because hydrogen sulfide is generated which
promotes hydrogen entry into steel. At a high content of sulfides and their favorable arrangement this effect may be of
significance for the total amount of hydrogen absorbed by the
metal bulk. Craig [41] estimates that the presence of elongated
sulfides may sixfold increase the amount of hydrogen absorbed
by steel compared with spherical or spheroidized sulfides, the
overall sulfide content being the same. Pumphrey [42] has
found that the permeation rate of hydrogen through mild steel
during corrosion in acids increases with sulfur content, especially when sulfides are longitudinally arranged in the membrane examined.
At high pH values the dissolution rate of sulfides is reduced.
Nevertheless, charging of steel with hydrogen may occasionally occur both in natural solutions and under anodic polarization conditions. If local corrosion occurs with the formation of
pits, and pits nucleate at sulfide inclusions, acidic environment
sets up in the pit and, as a consequence, the metal dissolves
with evolution of H2 and the sulfide dissolves with H2S evolution. Accordingly, absorption of hydrogen by steel may occur
inside of the pit, despite that the steel is in its passive condition.
Malyshev et al. [43] have shown that the permeation rate of
hydrogen through a high-strength Cr-Ni-Mo steel immersed in
a 3% NaCl solution increases when an anodic potential is
applied, Fig. 3. Similar results were obtained by Sitko for a
low-alloy high-strength steel [44].
Under stress conditions, the presence of a pit formed in the
vicinity of a sulfide inclusion gives rise to piling-up of stresses
which favor local accumulation of hydrogen dissolved in the
metal. This may result in nucleation and propagation of a
482
Szklarska-Srnialowskaund Lunarska
0.006
In
p_
:a003
In
s
m
[431
Abb. 3. EinfluR eines Potentials
Iw211151
'3
2
time, hrs
The cohesion between matrix and inclusion can be estimated on the basis of mechanical tests. It has been demonstrated that in steels deoxidized with silicon, the matrix is
weakly bound with elongated silicate inclusions [50]. Consequently, these inclusions may be expected to give rise to generation of hydrogen-induced crevices. In contrast, globular
Type I MnS sulfides are relatively innocuous.
In aluminum-killed steels, Type I1 MnS inclusions are present, which can be easily separated from the matrix during
mechanical testing [50]. The inclusions are likely surrounded
by microvoids because of their considerable contraction at
cooling.
In a recent study on the role of inclusions in the hydrogeninduced cracking of linepipe steels, Wilde et al. [51] have
shown that cracks initiate at elongated manganese sulfide
inclusions. Glassy silicates or massive niobium carbonitride
precipitates can also act as initiation sites.
Savage [52]investigated the effect of the chemical composition and shape of sulfides on the hydrogen-assisted crevice
formation in a HY-80 Type steel witch various additions of
rare-earth elements. In a steel with 10 ppm of rare-earth,
inclusions of (Fe, Mn)S prevailed. In steels with larger contents of rare-earth elements, spheroidized rare-earth sulfides
were present. At the same concentration of diffusible hydrogen, a similar number of cracks was observed in steels with
higher rare-earth additions, cf. Fig. 6 [52].
Joshi [53] gives evidence for the presence of a thin, 150 A
film of (Mn, Fe)S at the grain boundaries in steel containing
0.3-0.4% C and different percentages of Mn and S. ,In tests
conducted in an aqueous H2S solution of pH 3, a lower notch
tensile strength was noted for a steel with higher Mn and S
contents.
483
'I
484
5 References
1. Z . Szklarska-Smiatowska: Corrosion 27 (1971) 223.
2. Z. Szklarska-Smiabwska: Sulfide Inclusions in Steels. American SOC.for Metals N.6 in MaterialsiMetalworking Technology
Ser. p. 380 (1975).
3. Ja. M. Kolotyrkin, L. I. Frejman: Korroziia i Zashchita ot Korrozii;, v.6, Itogi Nauki i Techniki, Moskwa, 1978.
4. M . Smiabwski: in Stress Corrosion Cracking and Hydrogen
Embrittlement of Iron Base Alloys, NACE-5, ed. by R. W .
Staehle, J. Hochmaniz, R. D. McCright and J . E. Slater, p. 405
(1977).
5. C. E. Sims: Trans. AIME 215 (1959) 367.
6. E. M. Moore, J. J . Warga: Mat. Performance 15 (1976) 17.
7. D. Brooksbank, K. W. Andrews: J. Iron and Steel Inst. 210 (1971)
246.
8. E. H. F. Date, J. Iron and Steel Inst. 207 (1969) 998.
9. J . D. Eshelby: Proc. Roy. SOC.(London), A 241 (1957) 376.
10. V . Finkel, 0. Jelesina, V. Fedorov, V. Zraychenko: Metalloved. i
Termicheskaia Obrabotka, N.7, 55 (1971) - russ.
11. L. G. Sillen, A. E. Marfell: Stability Constants, Chemical Soc.,
Spec. Publ. N.17, London (1964).
12. C. B. Hudgins, R. L. McGlasson, P. Mehdizadeh, W . M . Rosborough: Corrosion 22 (1966) 238.
13. V . A. Kuzencov, Z. A . Jofa: Z . Fiz. Chim (russ.) 21 (1947) 201.
14. Z. A . Jqfa, G. N. Tomashova: Z. Fiz. Chim (russ.) 34 (1960)
1036; Z. A . Jofa, Ba Cho Ngok, M. K . Vasileva, ibid. 39 (196.5)
2182.
485
W 2174
(Received: 6. 5. 1981)
0043-2822/81/1111-0485$02.50/0