•
Role of sulphide inclusions in pitting and crevice
corrosion of stainless steels
A. J. Sedriks
The role of sulphide inclusions in the pitting
and crevice corrosion of stainless steels is
reviewed. It is noted that manganese sul-
. phides, particularly those containing a
central oxide core, are the most favourable
sites for pit initiation. Replacing the manga-
nese in the sulphide by chromium renders
pit initiation more difficult. However, as the
severity of the environment increases,
pitting occurs at the less active inclusions.
It is concluded that changing the composition
of sulphides can give a useful, if somewhat
limited, improvement in pitting resistance
and in crevice -corrosion resistance.
Further studies are needed to define the
mechanism by which molybdenum, or n10lyb-
denum and nitrogen in combination, improve
pitting and crevice -corrosion resistance in
the presence of sulphide inclusions.
IMR/114
It is now widely recognized that the microstruc-
ture of stainless steels can play an important part
in determining pitting resistance. Phases such as
a-ferrite, 0, X,and a', the strengthening precipi-
tates in .precipitation -hardening stainless steels,
sensitized grain boundaries, welds, and metal sul-
phides and oxides can all have an effect on pitting
resistance.!
Recently, much attention has been paid to con-
trolling the composition of sulphide inclusions to
render them less effective as pit -initiation sites.
From the commercial viewpoint the incentive has
been one of cost saving by developing sulphide-
controlled, less alloyed stainless steels with a
pitting resistance equivalent to that of more highly
alloyed materials. Basic research on pitting, how-
ever, has been split between approaches in which
pitting has been regarded as inclusion related and
attempts to develop pitting mechanisms by con-
sidering the breakdown of defect -free passive
films. Of these attempts, a number of theories
have been proposed to explain the initiation of pits
in perfect surfaces (i.e. surfaces not containing
physical defects such as inclusions or composi-
tional heterogeneities). In these theories, pit
initiation is considered to be the result of certain
interactions between discrete species in the en-
vironment (e.g. chloride ions) and the passive
surface. There are kinetic theories in which the
breakdown of passivity is explained in terms of
the competitive adsorption between chloride ions
The author is Head of the Environmental Effects
Branch, Naval Research Laboratory, Washington,
DC, USA.
International
and oxygen, and thermodynamic theories in whic.h
the pitting potential is considered as that potentIal
at which the chloride ion is in equilibrium with
the oxide. (For a review and discussion of these
and other theories, the reader should consult
Refs.2 and 3.) The further development of such
theories is important to obtain a fundamental
understanding of the conditions under which pitting
can develop in the absence of surface defects.
However, conlmercial1y produced stainless steels
contain numerous inclusions, second phases, and
regions of compositional hete~ogeneit.Y'. ~nd. there
have been many reports in WhIChthe InItIatIon. o.f
pitting is identified with stru~tural he~ero.geneItIes
at the surface particularly wIth sulphIde Inclu-
sions. It is th~ purpose in this paper to review
this literature with a view to identifying the state
of present knowledge and the questions that remain
to be answered.
SULPHUR AND MANGANESE IN STAINLESS
STEELS
Sulphur is present in stainless steels as an im-
purity (0.03 max.) or as an intentional addition,
%
usually at a level of O. 3'10to improve machinabi-
lity (e.g. in Type 303). Since the solid solubility of
sulphur in stainless steels is less than O. 01% at
room temperature, it is usually present as a sul-
phide. The sulphides are predominantly manga-
nese sulphides (see Fig. 1), but they may also
contain chromium, iron, and other elements, and
may be physically associated with oxides.
The production of low-sulphur stainless steels
does not present a problem in argon-oxygen de-
carburization (AOD), a technique for producing
stainless steels that is widely used in the USA.
Sulphur contents as low as 0.002% can readily be
obtained with the AOD practice. However, it is re-
ported4 that sulphur contents as low as 0.002%
can cause a lack of penetration, at typical heat in-
puts, in welding Type 304 sheet of thicknesses
greater than 1.65 mm. Resulphurization to levels
of 0.005-0.01'10 is often carried out to ensure
adequate weld penetration in regular grades such
as Type 304.
The AISI 300 series of standard grades is
specified as having a maximum of 2% manganese
and 0.03% sulphur. In AOD -produced stainless
steel, desulphurization is achieved with a basic
slag (stirred by an argon gas stream). One of the
roles of manganese is to tie up the residual sul-
phur as manganese sulphide. Because of the much
lower sulphur contents attainable with modern
AOD practice, the amount of manganese needed to
tie up the residual sulphur is significantly less
than was needed in the past for the higher -sulphur
Metals Reviews, 1983, Vol. 28, NO.5 295
296 Sedriks: Sulphide inclusions and corrosion of stainless steels

MnS
~Cr5SS ~ + ~ MnS ::-
Cr5SS

60 0....
Mn //
Cr / "
I
o
/
40 I
I
I
I

I
I
20 9
/

.... / ....
0 ~
_---0 ----6----- -6----
-f!:>-.:-- ---....../:).
Fe
I

1 Manganese sulphide inclusions in commer-
cially produced Type 304 stainless stee l;
(courtesy of INCO)
stainless steels produced by the old double -slag
electric-arc process. However, the manganese
content of, for example, Type 316 AOD heats, is
still maintained at about 1. 8CJoto ensure the solu-
bility of nitrogen and to decrease the nickel
alloying addition. Also, stainless steel scrap,
which is often used in the melt charge, contains
significant levels of manganese. Hence, the lower-
ing of the manganese level in large production
heats may be accompanied by a cost penalty (i.e.
higher nicke 1 leve Is and less scrap in the melt
charge) and lower strength (Le. lower levels of
nitrogen in solid solution).
Despite these drawbacks, there has been a
significant commercial effort in Europe to develop
low-manganese stainless steels with a higher
pitting resistance. 5,6
COMPOSITION OF SULPHIDES IN STAINLESS
STEELS
Most of the studies of the composition and struc-
ture of metal sulphides in stainless steels have
been carried out on the 'free-machining' or 'resul-
phurized' grades such as Type 416 (martensitic),
Type 430F (ferritic), and Type 303 (austenitic).
The composition- structure relationships derived
for these resulphurized grades have provided
significant insight into this topic for all stainless
steels.
0.2 0.5 I 2 5 10 20
Mn/S RATIO IN METAL
2 Effect of Mn/S ratio on composition and type
of sulphide found in as-cast Type 303
(18. 5Cr-12Ni) stainless steel; after Ref. 14
In earlier studies7-13 it was recognized that,
while plain carbon stee Is contain manganese and
iron sulphides, the introduction of chromium into a
steel causes chromium to be contained in the
sulphide. At the chromium levels present in stain-
less steels, the sulphides usually contain some
chromium. Generally, as the manganese content
of the sulphide decreases, the chromium content
increases. This effect is shown for Type 303 in
Fig.2 (Ref. 14),for Type 416 in Figs. 3 (Ref. 13)
!lnd 4 (Ref. 15), and for Types 304 and 316 and
alloy 904L in Table 1 (Ref. 16). The iron content
of the metallic sulphide remains at 1-2% and
does not vary with the chromium and manganese
contents (see Fig. 2). (The compositions of the
alloys shown in Fig.2 are listed in Table 2.) It
will be shown below that sulphides rich in
chromium are much more corrosion resistant
than sulphides rich in manganese.
For the AlSI standard resulphurized Types
416, 430F, and 303, maximum manganese contents
are 1.25,1.25,and 2. 00%, respectively, and the
minimum sulphur content is O. 15% for all three
grades. Within the composition ranges possible
with these specifications, one could expect a wide
variation in sulphide composition and, as is shown
below, pitting resistance. The same could be said
about regular grades such as the popular Types
304, 316,410,and 430,for which manganese and

Table 1 Composition of sulphide inclusions in various stainless steels, wt-<>to

Composition of
Steel composition sulphide inclusion
Steel C Mn S Cr Mo Ni Cu Cr Mn S

Type 304 0.037 1.49 0.012 18.3 0.02 9.2 3 63 34

Type 304* 0.040 0.15 0.012 18.5 0.01 10.0 39 24 37
Type 316 0.035 1.62 0.019 17.3 2.7 11.6 2 63 35
Type 316* 0.036 0.16 0.013 17.7 2.6 11.9 44 19 37
904L 0.020 1.64 0.017 19.9 4.4 24.7 1.5 5 62 33
904L* 0.022 0.12 0.014 20.0 4.4 25.1 1.5 57 8 35

*Low-manganese variant.

International Metals Reviews, 1983, Vol. 28, No.5

 Sedriks: Sulphide inclusions and corrosion of stainless steels 297
70 Table 2 Chemical composition of steels in Fig. 2,
wt-/'o
~ I 60
Total

"3 .- Mn C 8i Mn 8 Cr Ni Mn/8
Z
Q 50
•
(J) 0.022 0.53 0.06 0.32 18.29 12.08 0.2
::>
-.J
u 40 , 0.022 0.61 0.28 0.32 18.45 12.15 0.9
~ 0

LL • 0.025 0.64 0.53 0.27 18.42 11.99 2.0

0 0
•
f--
z
30 • 0 0.032 0.61 0.79 0.30 18.48 12.06 2.6
w
f--
z 20 • '" 0 0.035 0.66 1.73 0.28 18.51 12.06 6.2
0 /
u 16.6
0.035 0.65 3.66 0.22 18.72 11.98
-.J
10
~
w ~cr+Fe
~
0
0 /.0 2.0 3.0 manganese content to increase, with increasing
MANGANESE CONTENT OF STEEL, wt_% annealing temperature. These changes are thought
to arise from desegregation in the cast structure
3 Composition of sulphide inclusions in as-cast and the attainment of equilibrium, mutual diffusion
Type 416 (13Cr-O. 38) stainless steel;after of chromium and manganese taking place between
Ref. 13 the sulphides and the stainless steel matrix.14
Similar changes in the chromium and manganese
sulphur contents are specified only by maximum contents of the sulphides in cast Type 303 can be
values (Mn = 2.0 max. and S = 0.03 %
max. for %
detected after certain processing steps, as shown
Types 304 and 316, and Mn = 1. 0/'0 max. and S = in Fig. 6.14 These changes are caused by the
%
0.03 max. for Types 410 and 430). thermal treatments associated with the processing
steps: heating to a forging temperature of 1250°C,
Variations in sulphide content can occur as a annealing at 1100cC after hot rolling, and annealing
result of heat treatment of castings having Mn/S at 1100cC after cold rolling.
ratios in the range 0.9-6.2.14 The variations in
the chromium and manganese contents of sulphides Another sulphide which may be present in
in cast Type 303 as a function of heat treatment stainless steels is titanium sulphide. Titanium is
are shown in Fig. 5.14 It may be seen that in cast generally a stabilizing addition to stainless
alloys with very low manganese contents (Mn = steels. 1 In a study of a resulphurized, low -inter-
O.06%) and with high manganese contents (Mn = stitial, 18Cr - 2Mo, ferritic stainless steel
3. 66%) the composition of the sulphide is not containing various amounts of titanium, 17 the re-
sensitive to heat treatment. However, at inter- lationships between chromium, manganese, and
mediate manganese contents the chromium content titanium contents in sulphides were identified
of the sulphides is found to decrease, and the (Fig. 7). The diagram shown in Fig. 7 is only tenta-
tive, the low-manganese, low-titanium corner
remaining to be fully explored.17 An area may
20
exist there in which only chromium sulphides will
be precipitated .
•
Niobium and tantalum, which are also used as
stabilizing additions to stainless steels, 1 also
eft. form sulphides which have been described as 'in..:.
I
+-' 15 soluble in acids' 18 (see Table 3). Similarly, ex-
~ tracted cerium oxysulphide (Ce, Mn)(O, S), formed
v>
w in low-carbon steel by adding mischmetal (a mix-
0
:r: ture mainly of cerium and lanthanum)to the melt,
a..
-.J has been reported to be insoluble in water at
=>
(J) 60cC .19 Further identification of sulphides found
10
~ in alloys such as Type 347 (stabilized by niobium
~ and tantalum additions) and alloys 6X and 904L (to
2 which mischmetal may be added to improve hot
~
0 workability and retard a-precipitation) may be of
0::
J: interest.
U
5
Other sulphides described as 'insoluble in
acids,18 are those of molybdenum, vanadium,
tungsten, and' zirconium (see Table 3). Of these,
molybdenum is a very common addition to pitting-
resistant grades, and some insight into its role in
0.5 1.0 1.5 2.0 sulphide formation would be desirable. Vanadium
.MANGANESE IN STEEL,wt-%
is a less common addition, but it is found in cer-
tain proprietary stainless steels such as the
4 Chromium content of in situ sulphides of Japanese grade 8CR-3.20 Tungsten and zirconium
Type 416 (13Cr--O. 38) stainless steel· as are not intentional additions to stainless steels,
function of manganese content; after Ref. 15 but may be found in nickel.alloys.

International Metals Reviews, 1983, Vol. 28, NO.5

298 Sedriks: Sulphide inclusions and corrosion of stainless steels

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International Metals Reviews, 1983, Vol. 28, No.5

 Sedriks: Sulphide inclusions and corrosion of stainless steels 299

Table 3 Heats of formation and solubilities of sulphides of importance in steel

metallurgy, listed in order of increasing (negative) heats of formation

H-G-, kcal mol-1

Element Sulphide of S at 25°C Solubility product pKs

Cu Cu2S -20.6 48
Pb PbS -37.9 28
Fe FeS -38.2 17
Ni Ni3S2 -39.2 20
W WS2 -39.6 Insoluble in acids
Sn SnS -40.5 26
Mo M02S3 -46.2 Insoluble in acids
Cr Cr7SS -50 Sparingly soluble in acids
Nb Nb4S7 -61.8 Insoluble in acids
Zn ZnS -63.6 25
Mn MnS -64.4 13
Ti TiS -67.4 Insoluble in acids
Ta TaS2 -70.9 Insoluble in acids
Be BeS -71. 3 Easily soluble
Al Al2S3 -73.0 Easily soluble
Zr ZrS2 -83.0 Insoluble in acids
V V2S3 -91.0 Insoluble in acids
Mg MgS -98.4 Easily soluble
Ba BaS -121. 4 Easily soluble
Sr SrS -123.5 Easily soluble
Ca CaS -125.4 Easily soluble
Ce CeS -133.4 No data available*

*Cerium oxysulphide is known to be insoluble in water.

1.8 CHEMICAL BEHAVIOUR OF SULPHIDES

1.6 The potential-pH diagram calculated for the
MnS-H20-CI- system is shown in Fig. 8.21 The
1.4
diagram is applicable only to relatively concen-
trated solutions (e.g. 0.1 M Mn species); it may be
~ 1.2
somewhat different for more dilute solutions.
°I
+J However, it is useful in defining the dissolution
~ behaviour of MnS. For example, it shows that MnS
W 1.0
U> can exist between pH 4.8 and 13. 8. At pH values
w
z less than 4. 8, MnS dissolves to form H2S and
<{ 0.8
(!) various manganese ions. However, even in the pH
z range 4.8-13.8, the highest potential at which
<{
'~ 0.6 MnS can exist is about -100 mV (at pH 5). At
more noble potentials, MnS dissolves to sulphur.
0.4
The potential-pH diagram calculated for the
0.2
(Mno.gFeo.1)S-H2G-Cl- system is shown in
Cr-Ti-S
Fig. 9.21 This diagram suggests that the introduc-
o tion of iron in solid solution within the MnS de-
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 creases the domain over which the metallic
sulphide is stable. In view of the importance of
TITANIUM Jwt-o/o chromium sulphide in improving the pitting re-
sistance of stainless steels, the acquisition of
7 Influence of manganese and titanium contents thermodynamic data and similar equilibrium cal-
of 18Cr-2. 3Mo-O. 2S stainless steel on culations for systems involving that. sulphide
sulphide composition; after Ref. 17 would be useful. Chromium sulphide is described

International Metals Reviews, 1983, Vol. 28, No.5

 300 Sedriks: Sulphide inclusions and corrosion of stainless steels
NOBLE
1

800 I
_I
HS04\
600 I
400
I
I
W
I I
(/) 200
>
E S
--i 0 Mn;3°4
« "'-
"'-
~ ""-
z -200
w "'"

..-o
a..
-400
H S
2
" ""-" I """" Mn{OH)2
"I
Mn2+
'i"", r'{~)
-600 I
I@
"
'"
~
~
I
(Mno.gFeo.I)S
"-

HS- "'"

I "'" I HS-
-800
I MnS
I
2-
S I

ACTIVE 2 4 6 8 10 12 6 8 10 12
pH pH

8 Potential-pH diagram for MnS-H20~1- 9 Potential-pH diagram for (MnO•9Feo.1)8-

2-
system calculated on basis of O. 1 M for SO 4 , H2o-Cl- system calculated on basis of
CI-, and Mn2+; after Ref. 21 0.09 M Mn2+, O. 01 M Fe2+, 0.1 M SO;-,and
O. 1 M Cl-; after Ref. 21

as 'sparingly soluble in acids' 18 (see Table 3) the threshold velocity of Type 316 stainless steel
and, as will be shown below, it is the sulphide in sea water from "'50 to "'25 ms-1•23 In reducing
present in the pitting-resistant, low-manganese acids, increasing the H2S content can eliminate
stainless steels.5,6 active-passive behaviour, causing a stainless steel
to become active. This is evident from Fig.ll ,24
An important conclusion that emerges from
where it is seen that the active-passive transition
the potential-pH diagrams shown in Figs. 8 and 9
is no longer in evidence when the H2S concentra-
is that manganese sulphide inclusions are active tion reaches 10-2 M. H2S also appears to facilitate
anodic sites at a stainless steel surface in the
presence of aqueous chloride solutions. The cor-
rosion potential of passive stainless steels in
aqueous chloride solutions is often between 0 and 1.0
+200 mV SHE. Since manganese sulphide is an S=
electronic conductor it will be polarized to the
corrosion potential of the passive stainless steel ill
Q
surface. At potentials between 0 and +200 mV :r:
a..
SHE, the sulphide is well outside its domain of ..-I
thermodynamic stability and will tend to dissolve. ~ 0.\
..-I
The potential-ilH diagrams also reveal <.(
~
changes in the chemistry of the corrodent as the o
~
sulphide dissolves. In acid solutions, such as may l.L.
/ be encountered in active pits or crevices, manga- o
nese sulphide will dissolve to form H2S. In neutral ~ 0.01
or alkaline solutions, the HS- and S2- ions replace f=
o
<.(
the molecular form of H2S (see Fig. 10).22 While 0:::
l.L.
it is well known that the presence of H2S in solu-
tion can accelerate the corrosion of copper alloys
and steels, the process is less well defined for
0.00\
stainless steels. Generally, the behaviour of stain- 3 4 5 6 7 8 9 10 II 12 13 14 15
less steels in solutions containing H2S suggests pH
that the H2S makes the formation of passive films
more difficult. For example, in high-velocity 10 Approximate distribution of H2S, HS-, and 82-
erosion-corrosion, the presence of H2S can lower _ as function of pH; after Ref. 22

International Metals Reviews, 1983, Vol. 28, No.5

 Sedriks: Sulphide inclusions and corrosion of stainless steels 301
NOBLE A point which emerges from these results is
that the presence of hydrogen sulphide and its
effects should be considered in attempts to define
the chemical changes occurring in pitting or
.•.0.6 crevice corrosion. Similarly, the initiation pro-
IO-2M cesses of stress-corrosion cracking, corrosion
H2S fatigue, and hydrogen embrittlement may be
0...... IO-3M affected if initiation occurs at actively dissolving
.•0.4 -----~ sulphides producing H2S.
w I
I
(f)
.•.0.2 0
IO-5M MECHANISM OF CORROSION ATTACK ON
> MANGANESE SULPHIDES IN STAINLESS STEELS
-.J
« No H2S
~ 0 The fact that manganese sulphide inclusions act as
z
W initiators of pitting in carbon steels has been
J-
0 known for some 50 years. The early studies found
a.. that sulphides acted as cathodes in the carbon
-0.2
steel surface, stimulating anodic attack in the steel
immediately surrounding them.26 It was noted that
only some sulphide inclusions initiated pitting in
-0.4 this way, and it was suggested that these active in-
0.01 0.1 1.0 10 100 clusions were ones which had crevices at the
ACTIVE sulphide/steel interface. Subsequent studies have
CURRENT DENSITY, rnA cm-2
confirmed the presence of voids at manganese
11 Effect of H2S on anodic polarization behaviour sulphide/steel interfaces formed as a result of the
of 17. 6Cr-9. 7Ni-l. 85Mn-O. 01S-O. 059C greater contraction of the sulphide on cooling.27
austenitic stainless steel in 1.1 M H2S04 + In stainless steels, manganese sulphide is
1. 75 M HF solution; after Ref. 24 anodic with respect to the passive stainless steel
surface. Accordingly, manganese sulphide in a
stainless steel surface directly exposed to a
the breakdown of passive ~ilms on stainless steels. corrodent would be expected to be preferentially
This is suggested by the data shown in Fig. 12,25 attacked in both high - and low -conductivity corro-
where it is seen that the depassivation pH is dents (see Fig. 13).
raised to less acid values as H2S is introduced
into the solution. The effect reverses at about This type of attack forms the basis of the so-
O. 3 ppm of sulphide, and at 32 ppm the depassiva- called 'passivation' treatment of resulphurized
tion pH ceases to be determined by thecomposi- stainless steels, which often consists of immersion
tion of the stainless steel. for 30 min at 50°C in a solution containing 50%

ACTIVE (a) (b)

~I
4

.~ - - - - - Ecorr (MnS)
b
a..
I
a. 3 ~~"~:~:~ "ANODIC
Z 434. .--. NOBLE
o· - - Ecorr (couple) - - - --
~
~
en ;~" ~:"
/t /
. .~.
(f)
CATHODIC
cr: 2
w - - - - - Ecorr (M)
0

I'16Ti "/
CORROSION CORROSION

.---
NSCD •

Metal Metal
0 10-6 10-5 10-4 10-3M [H S]
2
0 0.03 0.3 3 32 ppm S 1 I
HYDROGEN SULPH IDE CONTENT INTERFACE INTERFACE

a high-conductivity corrodent; b low-conduc-

12 Effect of H2S on depassivation pH in 2 M NaCl
tivity corrodent
solution at 23°C of five commercial stainless
steels; after Ref. 25 13 Schematic of expected corrosion profiles at
metal/manganese sulphide interface in
corrodents, assuming mixed control

International Metals Reviews, 1983, Vol. 28, No.5

302 Sedriks: Sulphide inclusions and corrosion
DEFECTIVE
PASSIVE FILM
;/
;/
(0 )
METAL
(c)
(e)
14 Pit nucleation and development at manganese
nitric acid and 2% sodium dichromate .15 The im-
proved pitting resistance after this passivation
treatment is attributed to the removal of surface
sulphides.28,29 It should be noted that the aim of
the passivation treatment is to remove only the
surface sulphides (and embedded iron) without
attacking the stainless steel itself. The surface
holes left after the removal of the sulphides may
be rinsed with sodium hydroxide to neutralize any
entrapped acid.29 If the acid in these surface holes
is not neutralized, it could cause further pitting on
subsequent exposure to aqueous environments or
even to humidity.
It is useful to regard pit propagation as the
continuation of attack into the stainless steel after
the manganese sulphide is removed. Accordingly,
the steps by which attack is diverted from the
sulphide to the stainless steel surface forms the
key to understanding pit propagation. Several
mechanisms have been proposed, differing mainly
in the degree of emphasis placed on some aspects
of the process.
The most recent - and probably most com-
prehensive - pitting mechanism suggesting how a
manganese sulphide inclusion can initiate a propa-
gating pit in a stainless steel in a chloride solution
is shown in Fig. 14.30 Consider a near-surface
sulphide inclusion covered by a film which is de-
fective in comparison with the film covering the
adjacent stainless steel matrix (Fig. 14a). The
first stage of the attack is the formation of a salt
(chloride) layer over the defective area; this is
accomplished by the transport of metallic ions
through the defective film and their reaction with
the chloride (Fig. 14b,c). The second stage in-
volves the hydrolysis of the chloride, leading to
International Metals Reviews, 1983, Vol. 28, No.5
of stainless steels
FILM
'"
~ ~
(b)
(d)
SALT LAYER
sulphide inclusion in stainless steel; after Ref. 30
acidification (Fig. 14d). The acid formed dissolves
the defective film, and begins to attack the manga-
nese sulphide inclusion and the stainless steel
surrounding the inclusion (Fig. 14e). The pit will
propagate when the acidity has reached a level at
which repassivation of the stainless steel surface
cannot occur. The presence of any hydrogen sul-
phide, formed by the dissolution of the manganese
sulphide inclusion, will also hinder the repassiva-
tion process (see the previous section). The
propagation stage is thought to involve the forma-
tion of a barrier salt layer at the bottom of the pit
(Fig. 14j). Salt layers are reported to form at the
bottom of pits in stainless steel,31 and are be-
lieved to control the kinetics of corrosion via the
dissolution of the salt film.32-35
As noted above, the mechanism represented
in Fig. 14 describes the initiation of pitting at a
near-surface manganese sulphide inclusion
covered by a film. Different initial steps have .
been proposed for a manganese sulphide inclusion
PASSIVE FILM CATHODE PASSIVE FILM
OXIDE MnS OXIDE MnS
15 Initiation of pitting at duplex manganese
sulphide-4lxide inclusion; after Ref. 6
 Sedriks: Sulphide inclusions and corrosion of stainless steels 303

NOBLE insoluble oxide and the stainless steel matrix,

causing the metal to undergo crevice corrosion to
• •• LOW SULPHUR CONTENT
0.6 APPROX. 0.007%
initiate the pit-propagation process.
06 HIGH SULPHURCONTENT
APPROX.0.03%
0.5 LOW-MANGANESE, TITANIUM-CONTAINING AND
CERIUM-CONTAINING STAINLESS STEELS
LJ
u As noted above, a low-manganese stainless steel,
~ 0.4 UHB 904L
(20Cr-25Ni- in which the resistance to pitting is improved by
> 4.5 Mo- 1.5Cu) the presence of higher chromium contents in the
.i sulphides, is now produced commercially in
~•.... 0.3
Europe.6 The steel is basically a low-manganese
z
w Type 316 (Fe-17Cr-12Ni-2. 7Mo--4).3 (max.)Mn)
•....
0 and is available as a low -carbon grade with

I
a.. 0.2 UHB 24
(AISI316) 0.030 oC (max.) or as a conventional grade with
0
/
C>
z O.05 C (max.). The reason for selecting a Type
%

i=
•....
n: 0.1
o also found in Type 304 and 904L stainless steels,
o 0.4 0.8 1.2 1.6 2.0
ACTIVE
MANGANESE CONTENT,
16 Effect of manganese content on pitting poten-
tial of various stainless steels in oxygenated
5% NaCI solution; after Ref. 36
intersected by the surface and so not covered by
any film; pits are suggested to initiate by crevice
corrosion at the sulphide/metal interface. As
shown in Fig. 13, attack is generally greatest right
at the anode/cathode junction. The low electronic
conductivity of the sulphide would tend further to
localize the attack at the junction, helping a
crevice to develop.21 The adsorption of chloride
ions onto the sulphide would accelerate the anodic
dissolution of the sulphide, 18 while the H2S pro-
duced by the dissolving sulphide would hinder the
passivation of the metal.
The formation of a crevice in the pit-initiation
316 base is evident from Fig. 16,36 where it is
UHB 3MM
seen that the effect on the pitting potential of
(AISI304)
lowering the manganese content to O.2% is greatest
for the Type 316 composition. While this effect is
5.0 5.4 it is of somewhat lower magnitude for these two
wt-olo
compositions. The same pattern is seen in a para-
meter that is related to crevice -corrosion re-
sistance, the 'critical crevice solution' ,37 in that
lowering the manganese content in Type 316 has a
greater effect than in Type 304 (see Table 4).
However, even in molybdenum -free grades such
as Type 304, there is a significant decrease in
attack on sulphides by dilute acids as the manga-
nese content of the alloy is reduced, as shown in
Fig. 17.14 (The compositions of the alloys defined
by the Mn/S ratios shown in Fig. 17 are given in
Table 2).
Other stainless steels which exhibit high
pitting resistance and also have very low manga-
nese contents are the new high -chromium, low-
interstitial ferritic grades 29-4 and 29-4-2
produced by vacuum induction melting, and the
titanium -stabilized grade 29 -4C produced by AOD.
The 29-4 and 29-4-2 grades contain about O.03'/'oMn
and O. 01 S, whereas the 29-4C grade contains
%

process can also be aided by duplex inclusions, as about O. 2 Mn and O.002°/oS, as well as about
%

shown In Fig. 15.6 The geometry of the duplex in- 0.5°/oTi. While stainless steels containing 29°/oCr
clusion causes a crevice to be formed between the and 4°/oMo would be expected to have high pitting

Table 4 Effect of manganese content of Type 304

and 316 stainless steels on critical ~
crevice solutions k 'V- :0.5%HCI
30

.- - ---
C\l
IE --e-- : 1.0%H2S04
(jI
....
Composition Critical w /
/

variants, crevice ~ 20 /

wt-"lo solution* 0:::

!
Steel

304
Mn

0.18
S

0.017
pH

2.05
CI- (M)

1.5
Z
o
en
o
~
o
10
I
I
I
•
I

u
304 1. 11 0.015 2.10 1.5 I

o ---- ....•
316 0.25 0.014 1. 70 3.5 0.1 0.2 0.5 I 2 5 10 20
316 1.46 0.019 2.05 2.5 Mn/S RATIO IN METAL

17 Effect of Mn/S ratio of 18. 5Cr-12Ni stainless

* A lower pH and higher chloride content of the steel on corrosion rate in dilute acids; attack
critical crevice solution is indicative of increased was found to be localized at sulphides; after
resistance to crevice corrosion. Ref. 14

International Metals Reviews, 1983, Vol. 28, No.5

304 Sedriks: Sulphide inclusions and corrosion of stainless steels

Table 5 Effect of sulphur content of low- NOBLE

manganese (0.0001 wt-o;o)experi- 600
mental Fe-14Cr-12Ni stainless 316L 316Ti
steel on pitting in 10 wt-O/oFeCl3 P/M
solution at 25°C for 72 h 500
P/M
S, wt-o;o Corrosion rate, * mpyt ill
U
tf) 400 CONV.

0.008 5.6 ~ CONV.

0.012 13.0
0.024 17.2
0.089 41.0
0.170 157.0
0.009t 170.0
*Attack on sulphide inclusions.
t1 mpy == 25.4 /lm/year.
tCommercial Type 304 containing 1. 76 wt- °1
manganese.
and crevice -corrosion resistance, the fact that any
sulphides present must be chromium sulphides, or
chromium plus titanium sulphides in the case of
29-4C, must contribute to resistance to localized
corrosion.
It should be recognized, however, that the re-
placement of manganese sulphide by chromium
sulphide brought about by lowering the manganese
content of the alloy does not prevent pitting under
severe conditions. This is strikingly evident from
the data given in Table 5,38 for stainless steels
with a very low manganese content exhibiting
pitting attack in a ferric chloride solution. The
compositions of the stainless steels are such that
the sulphides would be chromium sulphides, so the
data in Table 5 represent pitting attack at
chromium sulphides. However, the manganese-
sulphide- containing Type 304, at a comparable
sulphur level, suffers much more pitting than the
stainless steel containing chromium sulphides.
Other workers39 have reported that, in the
absence of sulphides, pitting will initiate at less
active sites such as oxides, provided the conditions
are aggressive enough.
In Table 3, titanium sulphide is also given as
'insoluble in acids', and hence its introduction into
the microstructure as a replacement for manga-
nese sulphide (see Fig. 7) could also be expected
to improve pitting resistance. Traditionally,
titanium additions to stainless steel have been re-
garded as detrimental to pitting resistance. Labo-
ratory pitting tests in ferric chloride and pitting-
potential measurements in O. 1 N sodium chloride
on laboratory-prepared 18Cr-14Ni stainless
steels containing O. 19, O. 22, and O. 31°loTi have
indicated that titanium decreases pitting resis-
tance ,40 and this has been supported by other
laboratory41 and atmospheric42 tests. However,
Table 6 Chemical composition of powder-
metallurgy steels in Fig. 18, wt-o;o
Steel C Mn S Cr Mo
316L 0.007 0.6 0.009 16.5 2.45
316Ti 0.056 O. 3 0.010 16.9 2.33
.J
<{ 300
~z
W
I-
0 200
a..
t9 P/M
z
~ P/M CONY.
I- 100
a:
0 CONV.
a
ACTIVE I 30° I 80° I
18 Pitting potentials of Type 316L and 316Ti
stainless steels produced by powder metallurgy
(P 1M) and conventional (CONY0) techniques;
materials tested in 1 M NaCI at 30° and 80°C;
after Ref. 43
recent studies43 of titanium-stabilized and low-
carbon Type 316 stainless steels have shown that
the titanium -containing varieties exhibit more
noble pitting potentials, indicating greater pitting
resistance (see Fig.18).43 This has been attributed
to the replacement of manganese sulphide by
titanium sulphide ~43 The compositions of these
Type 316Ti and 316L alloys produced by powder
metallurgy are given in Table 6. Since much of
the titanium in Type 316Ti would be expected to be
tied up as a carbide, and since the manganese con-
tent is very low (Le.0.3 ),it %
remains to be
demonstrated that titanium sulphide is present in
this alloy rather than chromiurn sulphide. The
improved pitting resistance could be accounted for
by the presence of chromium sulphide.
It must be concluded, therefore, that there is
as yet no unambiguous evidence to support the
view that replacing manganese sulphide by titanium
sulphide is beneficial to pitting resistance.
Further definitive work is needed in this area, not
only with regard to pitting, but also for crevice
corrosion, particularly since titanium -stabilized
austenitic, ferritic, and duplex grades with added
titanium have been reported to give better results
in crevice-corrosion tests in sea water .44
Mischmetal may be added to 6°loMo stainless
steels such as 6X,and to 4. 5°loMo stainless steels
such as 904L, to slow down (J-precipitation kinetics
at grain boundaries. It remains to be established
whether the sulphides found in alloys such as 6X
and 904L are cerium oxysulphides and, if so,
whether they are resistant to pit initiation. It
Ni Ti should be noted that any such determination should
not be confused by the presence of (J,which in high-
11.8 molybdenum alloys can have a deleterious effect
12.7 0.49 on pitting resistance. An example (for Type 317L
stainless steel) of how (J can lower the pitting

International Metals Reviews, 1983, Vol. 28, No.5

 Sedriks: Sulphide inclusions and corrosion of stainless steels 305

NOBLE500 600
0.20
L ()VISIBLE IN ~
wu 0.16 I MICROSTRUCTURE I
If)
(0)
> 0.12
-i"
<{
i= 0.08
z
W
I-
o
Q.. 0.04
(9
Z
~I- o
0:: ACTIVE
(a) (b)
1000 1200 1400 1600 1800 2000 2200
REHEATING TEMPERATURE J of a longitudinal grinding; b transverse grinding

19 Effect of reheating for 8 h at various tempera- 20 Schematic of effect of directionality of grinding

tures on pitting potential of Type 317L stain- with 80 grit paper on sulphide stringers; note
less steel in 60°C aqueous 10000 ppm chloride that specimens with longitudinal grinding have
solution acidified to pH 2 with H2S04; (a) de- pitting potential 60 mV more noble than those
notes as-received material (courtesy of INCO) with transverse grinding; after Ref. 46

potential - i.e. make the alloy less resistant to Recent studies of the effect of laser melting
pitting - is shown in Fig. 19. of surface layers of Type 304 stainless steel
suggest that this may also improve the pitting re-
Crevice corrosion also initiates at any manga-
sistance.47 Potentiostatic polarization curves
nese sulphide inclusions that are present, 45 and
taken from the laser-melted surfaces do not show
the depassivating effect of dissolved hydrogen
the increasing current response typical of a stain-
sulphide produced locally by the dissolving inclu-
less steel undergoing pitting. A complex curve
sions (see Fig. 12) is likely to facilitate attack.
suggesting pit nuc leation and rapid repassivation
Lowering the manganese content of Type 304,
was found instead (see Fig. 21),47 and no pits were
316, and 904Lstainless steels, with the resultant
found on the surface at the end of the test. This
increase in the chromium content of the sulphide,
could be attributed to either the removal or the
is reported to improve crevice-corrosion resis-
redistribution of the manganese sulphide in the
tance in a laboratory solution containing
laser-melted surface layers. Further studies
O. l NaCI + O. 1 K3Fe(CN)6. 44 Reportedly, this
% %

aimed at identifying the usefulness of this tech-

improvement was evident only for specimens
whose surfaces were not pickled. No beneficial nique for special applications seem desirable.
effect of the low manganese content was evident
for specimens with pickled surfaces. These ob- DISCUSSION
servations are consistent with the removal, during
the pickling process, of the reactive manganese The recognition that manganese sulphides are
sulphides from the surface. probably the least resistant pit-initiation sites in

NOBLE
SURFACE TREATMENTS +1.5
TYPE 304
Stainless steel semifinished products are often
delivered from the mill in the pickled condition. LASER
Pickling' generally produces a highly' corrosion- +1.0 I MELTED
./~SURFACE
resistant stainless steel surface because of the ,.-"'"
material that has been removed. This can include w
U , /

millscale retained from the hot-rolling operations, (/) \

\
chromium-impoverished surface layers resulting +0.5 \
>
from chromium loss at elevated temperatures, ",'
-i
embedded iron from working and processing
<{
F /
AS-RECEIVED
z
equipment, and manganese 'sulphide inclusions. w o SURFACE
Subsequent cutting and grinding operations, such b
a..
as may be encountered in manufacturing, will re-
generate a less corrosion-resistant surface with
exposed manganese sulphides and possibly newly -0.5
embedded iron particles. Even the directionality 10-1
of grinding can affect the corrosion behaviour of
ACTIVE
the surface if the sulphide is present as stringers CURRENT DENSITY, J.LAcm-2
elongated in the direction of the original hot work-
ing, as shown in Fig. 20.46 A final acid pickling or 21 Effect of laser melting of surface of Type 304
passivation treatment should be given if the stainless steel on its anodic behaviour in
original corrosion resistance is to be restored. O. 1 M NaCI solution; after Ref. 47

International Metals Reviews, 1983, Vol. 28, No.5

 306 Sedriks: Sulphide inclusions and corrosion of stainless steels
NOBLE molybdenum content in conjunction with a high
1200 nitrogen content. Figure 22 (Ref. 49) shows the
• = PLAIN SPECIMEN
A= SPECIMEN WITH CREVICE
effect of nitrogen content on pitting potential.
Using a low molybdenum content together with a
1000 high nitrogen content to improve pitting resistance
necessitates relatively high levels of manganese
••.......
UJ
• 1 (e.g. 4/ to ensure the solid solubility of nitrogen
0)

in the chromium-containing austenite.

U
(/)
800 From a mechanistic viewpoint, it would be of
~ particular interest to examine the role of molyb-
denum, or of molybdenum + nitrogen, in preventing
-J
« 600 pitting attack at manganese sulphide inclusions.
i= The commercial pit -resistant molybdenum stain-
z
.-
w
o
0.. 400
less steels, such as Types 316 and 317, and the
molybdenum + nitrogen stainless steels, such as
the European grade REX 734, contain sufficient
C)
z manganese and sulphur to form manganese sul-

.-a:
i=
200
phide inclusions .

o ACKNOWLEDGMENTS
o 0.1 0.2 0.3 0.4 0.5
ACTIVE Many of the tables and figures are used in this
NITROGEN CONTENT OF STEEL,wt-% review by permission of copyright owners. The
author wishes to acknowledge permissions granted
22 Effect of nitrogen content on pitting potential by Nippon Sutenresu Giho, the American Society
of·22Cr-20Ni-4Mn-2. 8Ma-0. 03C-0. 01S for Metals, The Electrochemical Society, the
stainless steel in aerated aqueous solution National Association of Corrosion Engineers,
containing 0.6 M NaCI and 0.1 M NaHC03; Metaux-Corrosion lndustrie, M~moires Scien-
after Ref. 49 tifiques Revue Metallurgie, Werkstoffe und Korro-
sion, and Nyby Uddeholm AB.

today's commercial stainless steels has served to

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© 1983 The Metals Society and the American Society fQr Metals

International Metals Reviews, 1983, Vol. 28, NO.5