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478

Szklarska-Smialowska und Lunarska

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.

Werkstoffe und Korrosion 32,478-485 (1981)


5. J. M . Harrison, J . F. Norton: Behaviour of High Temperature
Alloys in Aggressive Environments. D.D. 661-680. Book 266/EUR
6814 The Metals Society, London, i9kO.
6. 0.Van der Biest, J . M . Harrison, J , F, N
~ pp 681-701,
~
~as
above.
7. T. B. Pierce, J . W. McMillan, P. F. Peck, I. G . Jones: Nuclear
Instrumentsand Methods 118 (1974) 115-124,

(Received: 27. 3. 1981)

W 2186

The effect of sulfide inclusions on the susceptibility


of steels to pitting, stress corrosion cracking and
hydrogen embrittlement
EinfluB von Sulfideinschlussen auf die Anfalligkeit von Stahlen fur LochfraB,
SpannungsriBkorrosion und Wasserstoffversprodung
2. Szklarska-Smialowska, E. Lunarska*

Recent opinions on the effect of nonmetallic inclusions, especially


sulfides, on the nucleation of pits, stress corrosion cracks, and hydrogen-induced cracks are reviewed.
The nonmetallic inclusions present in steels as impurities adversely
affect the corrosion resistance of steels. This is true for both the general and local corrosion mechanisms, like pitting corrosion, stress corrosion cracking (SCC), and hydrogen embrittlement (HE).
The effect of nonmetallic inclusions (in particular that of sulfides)
on the pitting corrosion mechanism has been the subject of numerous
investigations. A fairly+aboundantinformation can be found in vast
original literature and in many review articles [1-31. The role of nonmetallic inclusions in SCC is relatively less covered in the pertinent
literature. Since, however, the nucleation of corrosion cracks frequently starts from pits, and pits nucleate at sulfides, the presence of
sulfides is likely to affect the SCC process.
Another corrosion mechanism that leads to a local cracking of a
metal is the hydrogen embrittlement. The presence of nonmetallic
inclusions enhances susceptibility of steel to hydrogen-induced cracking [4].
This review will be concerned with the effect of nonmetallic inclusions on the local corrosion types mentioned.

In einer kritischen Ubersicht werden neuere Ansichten uber den


EinfluB von nichtmetallischen Einschlussen (besonders Sulfiden) auf
die Lochkeimbildung sowie die Entstehung von Spannungskorrosionsrissen und wasserstoffinduzierten Rissen erortert. Die in Stahlen als
Verunreinigungen vorhandenen nichtmetallischen Einschlusse beeintrachtigen die Korrosionbestandigkeit; das gilt sowohl fur die Flachenkorrosion als auch fur ortliche Korrosionsvorgange wie Lochkorrosion, SpannungsriBkorrosion und Wasserstoffversprodung.
Der Einflulj von nichtmetallischen Einschlussen, besonders von Sulfiden auf die Lochkorrosion ist von vielen Autoren untersucht worden, so dalj in der Originalliteratur und in zahlreichen Ubersichtsarbeiten umfassende Informationen verfugbar sind. Die Rolle der nichtmetallischen Einschlusse bei der SpannungsriBkorrosion ist bisher verhaltnismaljig wenig untersucht worden. Da aber Korrosionsrisse haufig von Lochkorrosionsstellen ausgehen, die wieder in der Nahe von
Sulfideinschlussen entstehen, ist anzunehmen, daB Sulfideinschlusse
auch die Spannungsriakorrosion beeinflussen.
Ein weiterer Korrosionsvorgang der zu ortlicher RiRbildung in
Metallen fuhrt, ist die Wasserstoffversprodung. Durch nichtmetallische Einschliisse wird die Anfalligkeit von Stahlen auch fur wasserstoffinduzierte RiRbildung erhoht. Die vorliegende Ubersicht behandelt den Einflulj der nichtmetallischen Einschliisse auf die obengenannten ortlichen Korrosionsvorgange.

1 Properties of nonmetallic inclusions

erty of nonmetallic inclusions from the standpoint of corrosion


is their ability to deteriorate in aqueous media. The thermal
expansion coefficients and elastic properties may play an
important role in some cases.
Chemical composition of nonmetallic inclusions and their
morphology depend upon both the chemical composition of
steel and the technological process employed.
The most common group of nonmetallic inclusions are sulfides, as sulfur is an impurity generally present in all commer-

The nonmetallic inclusions occurring in steel vary by their


chemical composition and morphology, as well as by their
chemical and physical properties. The most important prop-

z.Szklarska-Smiabwska, Frau Dr. E. Lunarska,


Institute of Physical Chemistry, Polish Academy of Sciences,
P. 0. Box 49, Warszawa 42lPoland.

* Frau Prof. Dr.

OO43-2822/81/111 l-O478$02.50/0

0 Verlag Chemie GmbH, D-6940 Weinheim, 1981

Werkstoffe und Korrosion 32, 478-485 (1981)

The effect of sulfide inclusions

cia1 steels. As this element is hardly soluble in iron and in


ferrous alloys, it precipitates as simple or complex sulfides,
such as FeS, MnS, CaS from the former group, and (Al, Cr,
Mn)S or (Mn, Fe)S from the latter group.
In carbon and low-alloy steels semi-killed with silicon, the
major inclusions are sulfides (primarily the manganese sulfide)
and silicates. The sulfide inclusions occurring in cast steel are
called after Sims [5] Type I MnS. They contain oxygen in solid
solution or in the form of complex oxide inclusions in a sulfide
shell. As a result of hot working a well dispersed array of
moderately deformed particles are produced. The silicates
present in such steel are fairly plastic and can be disintegrated
by rolling.
In steels killed with silicon and aluminum, the sulfides are in
the form of thin films arranged along the boundaries of the
austenite dendrites and grains. They are called Type I1 MnS
[5, 61. These sulfides are more plastic than Type I ones and
during rolling they become arranged in the form of long stringers parallel to the rolling direction. In these steels there also
are complex aluminum and calcium oxides, as well as silicates.
The thermal expansion coefficients of nonmetallic inclusions
are given in Table 1. As can be seen, only MnS exhibits a
much higher value of the thermal expansion coefficient than
the steel matrix. Therefore during cooling the sulfides contract
in volume much more than the surrounding metal, and this
results in the formation of voids between the inclusions and
the metal. Other typical inclusions have the values of the thermal expansion coefficient distinctly lower than for steel. Consequently, stress fields (so called tesselated stresses) build up
around them at cooling. The magnitude of the stress thus produced depends upon many variables: cooling rate, shape, size
and distribution of inclusions, elastic constants of the inclusions related to those of steel, etc.
The nonmetallic inclusions also are responsible for the
occurrence of stresses in the material under load.
According to Eshelby [9], the stress concentration produced
by the presence of a sharp inclusion is roughly equal to the
ratio of the modulus of elasticity of the inclusion and the
matrix.
A comparison made by Finkel et al. [lo] of the theoretical
and the experimental values of the stress concentration occurring around inclusions showed that the shape of an inclusion
Table 1. Youngs moduli and thermal expansion coefficients of nonmetallic inclusions and steel
Tabelle 1. Young-Modul und thermische Ausdehnungskoeffizienten
von nichtmetallischen Einschliissen und Stahl

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

Table 2. Elastic stress concentration in steel near nonmetallic inclusions (101


Tabelle 2. Elastische Spannungskonzentration in der Nahe der nichtmetallischen Einschliisse im Stahl

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

may even be more important that its elastic properties,


Table 2. For instance, sharp-edged Alz03inclusions are more
efficient notches than spherical Si02 or elliptical silicates. The
sulfides present as inclusions in steels after rolling are arranged
in chain form, which lowers their notchlike effect, at least if
the load is applied in the rolling direction.
Sulfides are known to disintegrate in aqueous solutions.
Their
solubility
increases
in
the
order:
TiS < MnS < PbS < MnS < CaS [ l l ] .
In acid solutions, hence also in occluded corrosion cells,
MnS, FeS and CaS dissolve with formation of H2S. In alkaline
solutions, ionic form HS- and S-- overcome the molecular
form of H,S, see Fig. 1 [12]. Many investigators have established an accelerating effect of H2S on the corrosion rate of
iron [13-151, steel [16] and nickel [17]. Jofa et al. (14, 151 have

Fig. 1. Approximate distribution of H2S, HS- and S z as a


function of pH [12]
Abb. 1. Angenaherte
Verteilung von Schwefelwasserstoff.
Hydrogensulfidion und Sulfidion
in Abhangigkeit vom pH

IW?llnll

found that in the presence of H2S the velocities of both the


anodic and cathodic process are increased. This is thought to
be due to the adsorption on the metal surface of HS- ions
produced by the dissolution of H2S. Acceleration of the dissolution process is ascribed to the catalytic action of transient
(MeHS-),d, complexes. In acid solutions, however, not HSbut H2S is the stable compound. Therefore Antropov and
Panasenko [18] suggest that H2S is acting as a catalyst in acid
solutions and that the anodic process on iron is accompanied
by the formation of a transient complex Fe(H,S),l,I,

Fe H2S -+ Fe(HzS)dds
Fe(H2S),d, -+ FeH2S2+ 2e
FeH2S2+-+ Fe2+ H2S

Crolet [19] studied the anodic dissolution and passivation of


an 18CrlONi stainless steel in H2S04 H F solution with
different H2S additions. The results of these experiments were
compared with those obtained for a similar steel containing
different percentages of sulfur. It was found that the higher
was the H2S content of the solution or the S content of the
steel, the higher dissolution rates and the higher critical passi-

480

Szklarska-Smialowska und Lunarska

Werkstoffe und Korrosion 32,478-485 (1981)

vation potentials were obtained. These results seem to indicate


that in the presence of adsorbed H2S molecules (or H S ions)
on the metal surface, the formation of the passive film is hampered.

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-

Werkstoffe und Korrosion 32, 478-485 (1981)

faces. It is concluded that these effects are associated with the


shape of sulfide inclusions. Namely, in the single-phase material the sulfides occur as stringers parallel to the rolling direction, whereas in the duplex alloy they are of spheroidized
shape and do not nucleate pits. These workers also claim that
the pitting potential depends on the directionality of grinding.
Transverse grinding, which cuts through inclusions, increases
the effective interfacial area and leads to a more active pitting
potential than longitudinal grinding.
Similarly, Scotto et al. [30] observed for two stainless steels
(18Cr9Ni and 17CrllNi2Mo) a higher corrosion reactivity of
the transverse than the longitudinal section. However, the
effect of the shape of inclusions exposed by cutting diminishes
as pH of the bulk electrolyte is decreased or the potential
shifted to more positive values.
The results thus far obtained can be summarized as follows:
1. Complex sulfide-oxide inclusions exhibit the highest susceptibility to pitting corrosion;
2. The ability of the inclusions to nucleate pits depends on the
shape of inclusions;
3. The inclusions induce stresses and generate dislocations in
the surrounding metal;
4. Occasionally, at the early corrosion stage, the metal surrounding inclusions dissolves and microcrevices result;
5. A preferential chloride - ion adsorption and agglomeration
occurs around inclusions.

The effect of sulfide inclusions

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.

4 Hydrogen embrittlement (HE)


From the standpoint of the effect of nonmetallic inclusions
on HE, the following two cases should be distinguished:
1. surface inclusions which may facilitate entry of hydrogen
into steel and thus to induce cracking, and
2. inclusions distributed in the metal bulk, which may play a
role in hydrogen trapping and assist nucleation and development of internal crevices and cracks.

3 Stress corrosion cracking (SCC)


4.1 Inclusions on the steel surface
It has been suggested on numerous occasions that stress
corrosion cracks in stainless steels initiate very often from corrosion pits (31-37). A correlation has been found between
pitting and SCC by comparing the induction times of pitting
for stressed and unstressed steel samples. In the majority of
cases, the induction times of SCC proved to be longer that
those of pitting [36]. This fact is additional evidence that
cracks may develop from corrosion pits. Apparently, the nonmetallic inclusions do not participate directly in the crack
nucleation, but their presence is undesirable and detrimental,
as they give rise to pitting.
On the other hand, when cracks were found to develop from
a seemingly smooth surface, a number of authors demonstrated that cracks nucleated on sulfide inclusions.
Thus, Clarke and Gordon [38] using scanning electron microscopy, examined a 304 Type stainless steel exposed in stressed and unstressed condition to oxygenated water at 288 "C.
They revealed a strong effect of second phase precipitates and
inclusions on crack nucleation. The attack around an included
particle was severe. Initiating from this creviced region around
the particle, intergranular attack took place. Electron microprobe analysis of these particles indicated a large content of
silicon. It was thought therefore, that they were composed of
silicate. It was suspected that sulfides of (Mn, Cr, Fe)S Type
could also play an important role in the nucleation process.
This assumption can be considered as proved because the
authors have actually found an effect of rolling direction on
crack nucleation. Since sulfide inclusions are generally elongated in the rolling direction, the effective crevice depth at the
attacked particle, where it intersects the surface, is a function
of orientation. Hence, the severity of the attack would be
more pronounced in the transverse direction, what is actually
observed.
Likewise Parker [39], studying 3CrMo and 5NiCrMoV
steels, found a close association between the propensity to

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

Werkstoffe und Korrosion 32, 478485 (1981)

0.006

In

p_

:a003
In

Fig. 3. Effect of a potential on


the hydrogen permeation rate

s
m

[431
Abb. 3. EinfluR eines Potentials

auf die Permeationsgeschwindigkeit von Wasserstoff

Iw211151

'3

2
time, hrs

Fig. 5. Dissolution rate


of (Ce, Mn) (0,S) and
a(Mn, Fe)S in water at
60C [47]
Abb. 5.
Auflosungsgeschwindigkeit von (Ce,
Mn) (0, S) und a-(Mn,
Fe)S in Wasser bei 60 "C

come this problem, a surface treatment has been advanced,


which consists in dipping a steel piece into a cold 10% chromic
acid solution [48]. The treatment proved beneficial for steels
of various carbon contents with a sulfur content of 0.019% or
more, and after various heat treatments and finishing processes. The resistance of steel increases on account of the dissolution of MnS inclusions at the surface of steel.
The effect of oxide and silicates, which are another common
Fig. 4. The surface of
low-alloy
high- type of nonmetallic inclusions in steels, is little learnt. These
strength steel after ex- inclusions are less chemically active, and their most likely
posing in 3% NaCI- effect is to produce notches on the surface which may become
solution [44]
important under stress conditions. Mention should. however.
Abb. 4. Oberflache be made that oxides are quite often surrounded by a shell of
von niedriglegiertem sulfide, or they form complex sulfide-oxide inclusions. In this
Stahl
hochfestem
respect, their effect is similar to that of sulfides.
nach Einwirkung von
3%iger HCI-Losung
4.2 Nonmetallic inclusions in the metal bulk
crack. As an example, Fig. 4 shows an inclusion around which
a corrosion pit was formed upon immersion in 3% NaC1. A
As suggested by literature data, the effect of nonmetallic
crack is seen which initiated from the pit [44].
inclusions on hydrogen-induced cracking in steel should be
The major parameters that control the effect of the sulfides considered separately for low-carbon mild steels and for
on HE are related to their morphology, i.e. their size, number, medium- and high-strength steels. The former are hot worked
shape, and distribution, as well as their reactivity with aqueous or normalized, and their structure is ferritic or ferritic-pearlisolutions. Particularly detrimental is the presence of Type I1 tic. The latter are subjected to quenching and tempering or to
MnS inclusions at the steel surface because they favor forma- special thermo-mechanical treatments, and they have a struction of long and deep pits. An effective way to overcome that ture of tempered martensite or bainite.
problem is the addition of shape-control additives, such as Zr,
Ca, Mg or Ti, and especially, rare-earth metals 1451. The reactivity of sulfides in contact with aqueous solutions should also 4.3 Low-carbon mild steels
be taken into account. The presence of Ca or Mg does not
In mild steels charging with hydrogen produces internal creimprove the resistance of steel because of the formation of
vices and blisters. Experimental results indicate that blisters
sulfides much more easily soluble than MnS [46].
Rare-earth metal additions to steel afford particularly good initiate at internal interfaces, at which hydrogen is evolved in
results, as sulfides or sulfide-oxides of these metals are gaseous form. Blisters grow in volume by increasing pressure
formed, which are much more resistant to aqueous solutions of hydrogen gas.
The evolution of hydrogen is particularly easy at interfaces
and assume a desirable spherical shape. Specifically, the addition of about 0.013 to 0.016% cerium to low-carbon steel featured by a low coherence between the matrix and inclusion
results in the formation of uniformly distributed spherical (Ce, which may even be separated by microvoids. A proof of that
Mn) (0,s)inclusions exhibiting a much lower reactivity in is, among others, the formation of hydrogen-induced crevices
aqueous media as compared with iron or manganese sulfides, arranged along the rolling direction, in conformity with the
nonmetallic inclusion system. Even if a tensile stress parallel to
Fig. 5 1471.
Obviously, the best way to reduce sulfide content would be the rolling direction is applied, the trend remains the same.
by decreasing the amount of sulfur in steel. Quite often, how- The stress only affects the crack coalescence normal to the
ever, for technological reasons, the surface layers may become rolling direction [4].
The most important parameters from the viewpoint of the
enriched in sulfides, despite that the overall sulfur content in
the metal is minute. This effect is observed, for instance, in effect of nonmetallic inclusions on hydrogen-induced cracking
wires produced from small ingots with little or no intermediate of mild steels are: the number, size, and shape of inclusions
annealing. Also, a rapid cooling of the ingot results in a certain (these parameters control the extension of the interfacial
enrichment in sulfide inclusions at the surface [46]. To over- boundaries) and their cohesion to the matrix.

Werkstoffe und Korrosion 32, 478-485 (1981)

The effect of sulfide inclusions

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

on the sulfides. This observation was explained by a difference


in tesselated stresses set up around inclusions during quenching. Oxides have lower thermal expansion coefficients than
steel (Table 1), which results in increased, thermal stresses
around these inclusions and easier hydrogen-induced cracking.
MnS characterized by a higher thermal expansion coefficient
compared to steel does not form such stress fields. Presumably, around sulfide inclusions even some narrow microvoids
develop which, acting as hydrogen traps, may lower the
amount of the diffusible hydrogen in the surrounding matrix
and thus to improve the resistance of steel to hydrogeninduced cracking. That this can actually take place has been
shown by the results of studies by Thompson et al. [57]carried
out with high-strength nickel alloys. It has been established
that materials containing hardening-phase particles or deliberately introduced T h o z particles, which exhibit a low coherence
to the matrix, are less sensitive to HE than materials in which
such particles are tightly bound to the matrix.
The magnitude of stresses set up around the nonmetallic
inclusions in a loaded steel depends upon the ratio of the
elastic constants of the inclusions and the matrix, as well as
upon the size, shape and distribution density of the inclusions
(Table 2). Accordingly, depending upon the kind of the inclusions, they may act as internal notches and reduce the resistance of steel to HE, or they may act as hydrogen traps,
thereby improving the resistance of steel to HE.
In a study by French et al. [58], internal cracks were found
to form at large oxide-sulfide inclusions during tensile tests of
a hydrogen-precharged pearlitic steel, whereas in a similar and
similarly treated steel which contained only a small amount of
sulfide inclusions, no such cracking was observed. The ductility of the first steel was drastically reduced by cathodic charging with hydrogen, whilst that of the second steel was hardly
affected.
There is scarce information in the literature on the effect of
A
individual inclusion types on HE in medium- and high-strength
steels. A reason for that is, among others, that the effect of
hydrogen is now mostly studied on notched specimens or on
those provided with a pre-crack. In such tests the hydrogeninduced crack propagation is not controlled by the presence of
nonmetallic inclusions (except for cases of a large accumulation of inclusions or their specific arrangement in the steel
HDcmS/OOg
item).
diffusible hydrogen
The nonmetallic inclusions, however, even if present in
Fig. 6. Results of constant strain cracking test (E = 0.5%) [S2]
minor quantities, may control the process of hydrogenAbb. 6. Ergebnisse des RiRversuchs bei konstanter Dehnung ( E =
induced cracking in smooth specimens. This has actually been
O,S%)
proved for a high-strength steel containing about 0.9% C [59].
Fractographic observations of notched specimens subjected to
4.4 Medium- and high-strength steels
constant load during cathodic charging with hydrogen in a
saturated solution of Ca(OH)2 with 0.1 M Na2S did not reveal
Hydrogen dissolved in the metal diffuses to sites of inclusions on the fracture surface. On the other hand, on the
increased tensile stress [54]. Increased hydrogen concentration fracture surface of smooth specimens (Fig, 7 a), numerous
at these sites, assisted by stress fields, is thought to bring about nonmetallic inclusions (probably oxides) were actually
a local decohesion of the crystal lattice and lead to the forma- observed, despite that the contamination of the steel with
tion of an internal crack [55]. This may primarily occur at inclusions was very low (from nil to few inclusions occurred in
the field of view of an optical microscope at a 100 x magnificainterfacial boundaries.
It should be emphasized that only the diffusible hydrogen tion on both longitudinal and transverse microsections). These
(dissolved in the lattice) is responsible for the above type of specimens were probably ruptured as a result of coalescence of
HE.
internal cracks formed around inclusions (Fig. 7 b). Under
The effect of nonmetallic inclusions on the internal crack severe hydrogen charging conditions used in the above study,
formation in a high-strength steel during cathodic charging the test specimens failed after a few hours of exposure at a
with high-fugacity hydrogen in 1 N H2S04 SeO, was investi- load of 80% of the ultimate tensile strength. It cannot, howgated by Ciszewski et al. [%I. In the quenched unloaded steel, ever, be excluded that in specimens with a less favorable
the cracks used to develop on the oxidic inclusions (oxides, arrangement of inclusions, and after a long exposure, even a
silicates, aluminosilicates), but no crack initiation was noted weak hydrogen source might produce failure.

'I

484

Szklarska-Smialowska und Lunarska

Werkstoffe und Korrosion 32, 478-485 (1981)

Fig. 7 a and b. The fracture surface of the


smooth sample of high-strength steel ruptured
during hydrogen charging [59]
Abb. 7 a und b. Bruchflache einer glatten, bei
Beladung mit Wasserstoff gebrochenen Probe
von hochfestein Stahl

Summarizing one can say the following:


1. All the nonmetallic inclusions occurring at the metal surface have a detrimental effect o n the resistance of steel to
hydrogen embrittlement. Particularly harmful in this
respect are manganese-containing sulfides, as they release
HIS in dissolving: the compound that promotes hydrogen
entry into metal.
2. Internal nonmetallic inclusions act as nucleation sites for
hydrogen blisters in mild steel and as nucleation sites for
hydrogen-induced cracks in high-strength steels.
3. In medium- and high-strength steels, the nonmetallic inclusions impair the metal plasticity.
4. In high-strength steels, an important property is the thermal expansion coefficient of the inclusion. Inclusions having low thermal expansion coefficients compared to steel
facilitate cracking on account of increased stresses around
the inclusion. Sulfides, which exhibit a higher thermal
expansion coefficient, may, in some cases, favorably affect
the resistance of steel to hydrogen-induced cracking by
trapping hydrogen in microvoids present around the inclusion.

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.

15. Z . A . Jofa, V . V . Batrakov, Ba Cho Ngok: Zashchita Metallov. 1


(1965) 55.
16. H. Holtan, H. Sigurdsson: Werkstoffe u. Korrosion 28 (1977) 47.5.
17. M. Kesten: Corrosion 32 (1976) 94.
18. L. J. Antropov, V . F. Panasenko: Itogi Nauki i Techniki. Ser.
Korrozia i Zaschita ot Korrozii, v.4 MVNITI. 46 (1974).
19. J. L. Crolef, L. Seraphin, R. Tricor: Mttaux. Corrosion, Industrie
N. 616 (1976).
20. L. Tronstad, J. Sejsted: J. Iron and Steel Inst. 127 (1933) 425.
21. D . Brooksbank, K. W . Andrews: J. Iron and Steel Inst. 206 (1968)
595.
22. G. Wrangltn: Corr. Sci. 14 (1974) 331.
23. G. S. Eklund: J. Electr. SOC.121 (1974) 461.
24. M. Janik-Czachor, A. Szummer, Z. Szklarska-L<miabwska:Corr.
Sci. 15 (1975) 775.
25. H . W . Pickering, R. P. Frankenthal: The U.R. Evans International Conf. on Localized Corrosion, NACE 3, p. 261 (1971).
26. P. Forchhammer, H . J. Engell: Werkstoffe u. Korrosion 20 (1961)
1.
27. 0. V. Kasparova, Ja. M . Kolotyrkiri: Zashchita Metallov. 11
(1975) 553.
28. P. Poyet, A. Desesrret: Mem. Sc. Rev. Met. 72 (1975) 133.
29. P. E. Manning, D. J. Duquette, W . F. Savage: Corrosion 35
(1979) 151.
30. V . Scotto, G . Ventura, E. Traverso: Corr. Sci. 19 (1979) 237.
31. F. W . Hirth, R. Naumann, H . Speckhardt: Werkstoffe u. Korrosion 24 (1973) 349.
32. H. Pickering, F. H. Beck, M . G . Fontana: Corrosion 18 (1962)
230.
33. J. S. McCollough, J. C. Scully: Corr. Sci. 9 (1969) 651.
34. A. A . Seys, M. J . Brabers, A . A . Van Haute: Corrosion 30 (1974)
47.
35. J. G. Parker: Britt. Corr. J . 8 (1973) 124.
36. Z. Szklarska-Smiabwska, J . Gust: C o n . Sci. 19 (1979) 753.
37. R. L. Shamakian, A . R. Troiano, R. F. Hehemann: Corrosion 36
(1980) 279.
38. W. L. Clarke, G. M . Gordon: Corrosion 29 (1973) 1.
39. J. G. Parker: Brit. Corr. J. 13 (1978) 75.
40. J . M. Silocock, P. R. Swann: in Environment-Sensitive Fracture
of Engineering Materials, Ed. by 2. A . Foroulis, Conference
Proc., Met. SOC.of AIME (1979).
41. B. D. Craig: Corrosion 34 (1978) 282.
42. P. H. Pumphrey: Corrosion 36 (1980)537.
43. V . Malyshev, J. Stepanov, V . Troshchenko: Proc. III Intern. Conference Razrabotka Mer Zashchity ot Korrozii, Warszawa,
1980, p. 140.
44. E. Sitko, Ph. D. Theses: Institute of Phys. Chern. Warszawa,
1980.
45. T. J. Baker: in Sulfide Inclusions in Steels, American SOC.for
Metals, N. 6 Materials/Metalworking Technology Ser., p. 135
(1975).
46. G. Wranglin: ibid., p. 361.
47. Harko Shimada, Joshiaki Sakakibara, Hideya Okada: Corrosion
33 (1977) 196.

Werkstoffe und Korrosion 32, 485-488 (1981)


48. D. Twigg, R. H. Bingham: Corrosion 34 (1978) 365.
49. A . Ikeda, J . Morita, F. Terasuki, M. Takeyama: Proc. I1 Intern.
Congr. Hydrogen in Metals, Paris, May 1977, 4 A 7 .
50. J . C. M . Farrar, R . E. Dolby: in Sulfide Inclusions in Steels,
American SOC.for Metals, N. 6 Materials/ Metalworking Technology Ser., p. 252 (1975).
51. B. E. Wilde, C. D. Kim, E. H. Phelps: Corrosion 36 (1980) 625.
52. W . F. Savage: in Sulfide Inclusions in Steels. American SOC.for
Metals, N. 6, Materials/Metalworking Technology Ser.. p. 233
(1975).
53. A. Joshi: Corrosion 34 (1978) 47.
54. J . C. M . Li, R. A. Oriani, L. S. Darken: 2. Phys. Chem. (N.F.)
49 (1966) 271.

Kinetics and mechanism of crack growth

485

55. R. A . Oriani: in Stress Corrosion Cracking and Hydrogen


Embrittlement of Iron Base Alloys NACE-5 Ed. By R. W .
Staehle, J . Hochmann, R. D. McCrighr, J . E. Surer. p. 351
(1977).
56. A . Ciszewski, T. Radomski, M. Smiabwski: ibid.. p. 671.
57. A . W . Thompson: Mat. Sci. Engng. I4 (1974) 253.
58. J . E. French, P. F. Weinrich, C. W. Weaver: Scripta Met. 13
(1979) 285.
59. 2. Szkiarska-Smiabwska, E. tunarska, W . Raczy&ki, M. Dabrowska: Unpublished results, 1979.

W 2174

(Received: 6. 5. 1981)

Kinetics and mechanism of crack growth during


stress corrosion cracking of zirconium alloys
Kinetik und Mechanismus des RiBwachstumswahrend der SpannungsriOkorrosion von
Zirkoniumlegierungen
L. M. Komissarenko, V. A. Marichev*

Using the electroresistivity method the influence was investigated of


the anodic and cathodic polarization on the crack growth rate during
stress corrosion cracking (SCC) of Zr alloys in aqueous and nonaqueous electrolytes. The ambiguous effect of the cathodic polarization on
CGR was observed. The role of local dissolution and hydrogen
embrittlement by SCC of Zr alloys has been discussed in terms of the
previously developed method of identification of the SCC mechanism.

Unter Verwendung der elektrischen Widerstandsmethode wird der


EinfluR anodischer und kathodischer Polarisation auf die Geschwindigkeit des RiBwachstums bei der SpannungsriBkorrosion von ZrLegierungen in waRrigen und nichtwaRrigen Elcktrolyten untersucht.
Dabei zeigt die kathodische Polarisation eine doppelte Wirkung auf
das RiBwachstum. Die Rolle der ortlichen Aufltisung und der Wasserstoffversprodung wiihrend der SpannungsriRkorrosion von Zr-Legierungen wird aufgrund einer fruher entwickelten Methode zur Bestimmung des Spannungskorrosionsmechanismus erortert.

At present there is no universally adopted view of the


stress corrosion mechanism of zirconium alloys. Local anodic
dissolution, hydrogen embrittlement (HE), or the decrease of
strength as a consequence of adsorption are discussed as possible mechanisms [l-31. As well as for other engineering materials, the role of this or that process occurring during the SCC
of Zr alloys is usually considered on the basis of indirect data
(such as the decrease of plasticity during hydrogen absorption,
the increase in dissolution velocity of the freshly generated
surface at the crack tip, hydrogen absorption during crack
propagation, microstructure of the fracture surface etc.).
These data are not contradictory to the assumptions of H E or
local dissolution during SCC but do not confirm these assumptions.
To determine the part of local dissolution and hydrogen
embrittlement in subcritical crack growth during SCC of Zr

alloys a theoretical and methodical approach developed earlier


for high-strength steels [4] has been used for the present investigation. This approach makes use of the ambiguous effect of
cathodic polarization on the crack growth during SCC of highstrength steels. Experimentally, this means that the same
cathodic polarization either accelerates the growth of cracks
(at crack growth rates (CGR) below critical CGR) o r has an
accelerating effect (above critical CGR). Such an approach
involves the thermodynamic possibility of a simultaneous and
parallel occurrence of anodic dissolution and hydrogen embrittlement at the crack tip. Each of these processes is determined
by the composition of the material and of the electrolyte. by
the potential and by the CGR. These parameters determine
the properties of the metal in the crack tip which approach the
properties of the juvenile surface. The protective films on the
metal in the crack tip increase hydrogen overvoltage, and are
the effective barriers for the hydrogen penetration into the
metal. At low CGRs the protective films inhibit the critical
hydrogen concentration in the metal in front of the crack tip.
Cathodic polarization, therefore, by promoting electrochemi-

* Institute of Physical Chemistry of the Academy of Sciences of the


USSR, Leninskii prospekt, 31, Moscow. 117171KJSSR.

0 Verlag Chemie GmbH, D-6940 Weinheim, 1981

0043-2822/81/1111-0485$02.50/0