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RN Parkins-The Stress Corrosion Cracking of C-MN Steek Ub CO2-HCO3-CO3 Solutions I, Stress Corrosion Data
RN Parkins-The Stress Corrosion Cracking of C-MN Steek Ub CO2-HCO3-CO3 Solutions I, Stress Corrosion Data
RN Parkins-The Stress Corrosion Cracking of C-MN Steek Ub CO2-HCO3-CO3 Solutions I, Stress Corrosion Data
15%173,1997
Copyright 0 1996Elsevier Science Ltd
Pergamon
PII: SOON-938X(96)00116-3
THE STRESS
CO,HCO,-CO;-
CORROSION
CRACKING
OF C-Mn STEEL IN
SOLUTIONS.
I: STRESS CORROSION
DATA
R. N. PARKINS
and S. ZHOU*
University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, U.K.
Abstract-The
potentials at which intergranular stress corrosion cracking occurs in a mild steel exposed to
solutions of various pH values, obtained by varying the concentrations of CO*, HCO; and CO:- have been
determined, as have those potentials at which quasi-cleavage occurs in similar but lower pH solutions. The potential
range for intergranular cracking is about 100 mV wide at ambient temperature and extends from pH 6.7 to 11.O,the
middle of the potential range falling from about - 0.25 to about - 0.7 V (SCE) as the pH is increased. Intergranular
crack growth rates are reduced by increase in pH and increase with HCO; concentration of the solution, some data
also being collected on the effects of different temperatures. With the lower pH solutions, the different morphology
of quasi-cleavage is reflected in a different potential regime for cracking, both suggesting the involvement of a
different cracking mechanism. Copyright 0 1996 Elsevier Science Ltd
Keywords: A. mild steel, B. polarization, C. hydrogen embrittlement, C. passive films, C. Pourbaix diagram, C.
stress corrosion.
INTRODUCTION
The stress corrosion cracking (SCC) of ferritic steels exposed to carbon dioxide-related
species is now recognised as occurring in various engineering structures ranging from highpressure gas transmission pipelines, through chemical reactors2 to cleaning trains for coal
gas.3 Since the first demonstration of such cracking in laboratory experiments, the
reactions involved in the dissolution of iron and the associated filming reactions have
received considerable attention. Armstrong and Coates4 used rotating disc and ring-disc
experiments to support the suggestions that Fe dissolves under diffusion control as Fe(II),
probably as FeOH +, with subsequent passivation by a Fe(II1) oxide. Davies and Burstein5
proposed, for potentials where SCC occurs, that the stable soluble complex anion
Fe(CO&
is the end product of the dissolution reaction with the deposition of Fe304
films, based upon rotating disc electrode measurements and Auger electron spectroscopy.
Valentini et aL6 made rotating disc electrode measurements on Fe exposed to various
concentrations of potassium carbonate-bicarbonate
solutions over a range of temperatures
and employed energy dispersive X-ray analysis on the films produced. They concluded that
a prepassive layer of hydrous Fe(OH)2 forms at potentials wherein SCC occurs with
electrodissolution of iron through that layer until the thickness of the prepassive layer and
the concentration of Fe2+ cause the formation of FeC03 or, as suggested in a subsequent
publication from the same laboratory, Fe(HCO&. A further publication from the same
source indicates that the anodic dissolution of iron in carbonate-bicarbonate
solutions is
Manuscript received 17 June 1996.
*Present address: National Physical Laboratory, Teddington, Middlesex,
159
TWl 1 OLW.
160
R. N. Parkins
and S. Zhou
METHODS
solutions. I
161
stoppers through which the specimen ends protruded for gripping in the SSRT machines.
The cells contained a Pt counter electrode and a bridge to an external saturated calomel
electrode (SCE), to which all potentials refer. Most tests were conducted at ambient
temperature (23 + 1C) but for tests at elevated temperatures the cell had an electrical
resistance winding over the outside, with a thermocouple contained in a pocket in the cell for
temperature control and a reflux condenser protruding from the top of the cell. The
monotonic strain rate applied was 2 x 10m6 s-l but some tests were conducted under cyclic
loading conditions in the same machines in which the direction of motion of the crosshead
was reversed by the action of magnetic clutches activated by signals from a load cell when
the pre-set values of the minimum and maximum loads were achieved. The average crack
velocity is used as a measure of cracking propensity, it being determined from a diametral
metallographic section through the largest crack in each specimen, the depth of which was
measured and divided by the test time.
Solutions were prepared from Analar grade chemicals and distilled de-ionized water. A
wide range of pH values was obtained by varying the amounts of NaHCOs and Na*COs in
the solutions and by adding CO* to NaHCOs for values below 7.6. A few tests were
conducted in NH4HC0s/NH4NH2C02
solutions and others in a simulated dilute ground
water containing (g/l) 0.112 KCl, 0.484 NaHCOs, 0.181 CaC12.2H20 and 0.131
MgS04.7H20,
saturated with CO2. The latter environment
is associated with
transgranular SCC of pipelines.12 The pH values for these various solutions were
measured before and after each stress corrosion test. The pH changed little during SSRT
in NaHC03/Na2C0s
solutions or in NaHC03 saturated with CO*, but in NaHC03
solutions, despite small differences in the initial pH depending on concentration, the pH
after SSRT was usually slightly higher and in the vicinity of 8.6.
EXPERIMENTAL
RESULTS
162
Intergranular
10
10.
AAA
AA
00
00
00
00
00
00
I
-0.3
-0.4
-0.5
Potential
-0.6
-0.7
V (see)
Fig. 1. The effect of potential on the average crack velocity for low-carbon steel in 1 M NaHC03
solutions of different pH value at ambient temperature.
potential
was lowered.
The containment
of cracks in the necks of SSRT specimens
may
reflect the severity of that test, with transgranular
penetrations
induced by corrosion under
SSC of C-Mn
steel in CO,-HCO;-CO:-
solutions.
163
0
0.0moo.o..
l
I.5
Fig. 2.
AAAmmoAAAmmm
I
-0.6
I
-0.7
Potential
I
-0.8
V (see)
steel in 1 M Na2COx
dependence on test time, as apparent from Fig. 7. The latter shows a broken line indicating
the slope that would result if cracks initiated in the early stages ceased to propagate, but the
experimental results show a time dependency indicating continuing crack growth within the
duration of these tests. On the other hand, the number of cracks increased with test time,
indicating the continuing nucleation of cracks, as is often observed13 with cyclic loading
tests that promote intergranular cracking. In the cyclic loading tests in the same solution but
at the potential of -0.650 V, where SSRT gave transgranular fissures, no cracks were
produced even in tests with the maximum stress at 132% of the yield stress and conducted
for 864 h. Similarly in the cyclic loading tests involving 0.1 M NaHC03, with or without
COz saturation, at - 0.350 V, no cracks were produced in 384 h tests at the maximum stress
of 132% of the yield stress, despite the transgranular cracks (Fig. 6) produced in SSRT.
These results, showing that the intergranular cracking observed in SSRT is readily
reproduced under cyclic loading conditions, but not the transgranular fissures observed in
certain solutions at particular potentials, indicate that the severity of the SSRT is involved in
producing the transgranular form.
It is mentioned above that the transgranular cracks observed with the higher pH
solutions could not be due to the ingress of hydrogen into the steel, because the potentials
involved were appreciably above the equilibrium value for discharge of hydrogen. However,
a different type of transgranular cracking was produced in the SSRT conducted in simulated
ground water or dilute NaHC03 solutions saturated with COz. Figure 8 shows part of a
fracture surface from one specimen and displays what is often referred to as quasi-cleavage
and frequently attributed to the ingress of hydrogen into the steel. Such cracks were not
164
R. N. Parkins
and S. Zhou
Intergranular
I
P-q
\ \
,Transgranular
\I
0,
\
0
-=.
\
b
I
/
\
I
1
1
,
,
,
I
i
-f
o
q
l 0. IM NaHC03
. 0.3M NaHCO3
0000
-0.2
-0.3
-0.4
Potential
Fig. 3.
0
I
-0.5
0
i
-0.6
V (see)
confined to the necked region of SSRT specimens and secondary internal cracks, i.e. not
connected
to the surface of the specimen and therefore not due to dissolution,
were
observed, with marked decreases in the ductility to fracture as the test potential was lowered.
The latter effect is apparent from Fig. 9 where the beginnings of the marked fall in RA%
approximate
to the equilibrium
potentials
for hydrogen discharge ( = -0.56 to -0.64 V,
depending
on pH). Similar effects have been reported* for a different steel in other
simulated ground waters to which CO2 at different partial pressures was added and are
considered to relate to the transgranular
cracking of high-pressure
pipelines in service.
j-6-
Intergranular
solutions. I
165
Transgranular
1/*-o.
1-7-
1
0
-0.3
Fig. 4.
A
0
0
I
-0.4
A
0
0
I
-0.5
I
-0.6
I
-0.7
Potential V (see)
The effect of potential on the average crack velocity for low-carbon steel in NH4HC03/
NI%,NH#Z02 solutions at ambient temperature.
R. N. Parkins
Fig. 5.
Fig. 6.
Inte xgranular
Transgranular
cracking
and S. Zhou
in low-carbon
steel after SSRT in 1M NaHCOll
solution at -0.65 V (SCE) and 80C.
crack in low-carbon
+ 0.75 M Na .2co3
solution
at - 0 .35 v
100
solutions. I
161
1
1000
Time (hr)
Fig. 7. The effect of test time on average SCC velocity in cyclic loading tests involving different
maximum stresses, in low-carbon steel exposed to 1 M NaHCOs+0.17 M NarCOs solution at
-0.525 V (SCE) and 22C; frequency 0.08 Hz, unless indicated otherwise. The broken line shows the
slope (- 1) that the regression line would take if cracks initiated in the early stages of a test soon
ceased to propagate, i.e. a constant crack depth was divided by increasing time.
Fig. 8.
Part of the fracture surface of a low-carbon steel specimen after SSRT in 0.01 M NaHCOs
solution saturated with CO1 at -0.9 V (SCE) and 22C, showing quasi-cleavage.
168
R. N. Parkins
40-
and S. Zhou
Potential
Fig.
9.
V (see)
.
Intergranular
-/
steel in various
solutions
8OC
\
./
.
.
I
i
AAA
AAA
0
0000
0
0
0
000
10.
0
0
-0.5
-0.6
-0.7
-0.8
Potential
Fig.
0
0
V (see)
steel in 1 M
SSC of C-Mu
steel in CO,HCO;-CO~-
solutions.
169
60C
.ar
Intergranul
23C ,
Transgranular
/
P
,
:
I
.
\
0
I
A
AAAA
0000
0
Cl
000000
-0.3
I
-0.4
Potential
-0.5
-0.6
-0.7
V (see)
Fig. 11.
steel in 1 M NaHCOs
o-
-0 .2 -
.o
No cracking
Transgranular
fissures
lntergranular
cracking
Quasi-cleavage
00
0
g
-0
.4 - -0
00
>
-0 .6 - 00
-0
.8 -
-1.
O_
5
:d
.. .
..
8
8
8
0
.:
::
0
0
0
11
13
PH
Fig.
in
R. N. Parkins
170
and S. Zhou
consequence
of the severity of the SSRT, the intergranular
mode occurs within a relatively
narrow potential
range, but across a wide range of pH values. The potential
range for
intergranular
cracking moves to higher values the lower the pH, but ceases at pH 6.3/6.7 on
the lower pH side and at 11.0/l 1.2 on the higher side. Note that the quasi-cleavage
promoted
in solutions of the lowest pHs occurred at markedly lower potentials than the transgranular
fissuring promoted
by the same solution, suggesting a different mechanism
of cracking.
Since the pH values of the solutions
to which Fig. 12 refers involved changes in the
concentrations
of NaHC03, Na2C03 or CO*, it appeared possible that the potentials of the
cracking domain would show also some dependence upon those concentrations.
Figure 13
shows the lower SCC bound potentials as a function of HCO, concentration,
the plot for
the upper bound potentials showing identical characteristics,
except that the potentials were
about 100 mV higher than those shown in Fig. 13. The HCO;
concentrations
were
calculated from
log
_w:-I
WCO;l
= pH - 10.34
or
WO;l
log [H2C03]
= pH - 6.38
NH,HC03/NH.+NH2C02
(8.2/8.4)
g _o,6
v,
%
x5
2 -0.7
2
Equal N HCOs/COs
,P-d
*-
/-
(9.619.8)
*
--v
_/-~ /+,*(
IM Na2C03 + HC03
*- R
(10/l I)
B
I
0.5
Bicarbonate
I
1.0
concentration
I
1.5
(mol/l)
SSC of C-Mn
steel in CO*-HCO;-CO:-
solutions.
171
corresponding
to the onset of passivity was pH dependent but independent of
CO:- - -HCO; concentration and Fig. 13 shows that the lines for the different solutions
are more markedly displaced according to their pH ranges than by HCO, concentration.
The boundaries of the intergranular SCC domain are likely to be associated with particular
reactions and are discussed in an accompanying paper.16
The effect of temperature upon the potential range for intergranular cracking is shown in
Fig. 14 for the two solutions to which Figs 10 and 11 refer. The cracking ranges move to
lower potentials with increase in temperature for both solutions, with similar slopes for the
upper and lower cracking boundaries. The boundaries for the 1 M NaHC03+0.75 M
Na2C03 solution observed in the present work agree with those observed in the early work
on this system at various temperatures in a 1 M NaHC03 + 0.5 M Na2C03 solution and
those data are included in Fig. 14. The data for the two solutions, 1 M NaHCO, and
0.125 M NaHC03 + 0.062 M Na2C03, which only promoted intergranular cracking at 23
and 40C conform to the trend for the cracking range to move to lower potentials the higher
the pH.
Just as the indications of Fig. 13 are that HCO; concentration as well as pH has
implications for SCC potentials, this is also true for crack velocities. Thus, Fig. 15 shows a
plot of the maximum crack velocities observed with the various solutions in terms of their
pH values and while there is a trend for the velocity to decrease with increasing pH,
considerable variations are apparent for solutions of similar pH. While Fig. 1 shows no
significant change of maximum velocity with change in the amount of Na2C03 addition to
1 M NaHC03, Fig. 2 shows marked changes in velocity with different amounts of NaHC03
added to 1 M Na2C03. Figure 16 shows a plot of the maximum velocity against the HCO;
concentration,
calculated from equation (l), for equal normality NaHCOs/Na2C03
solutions and for 1 M Na2C03 to which various amounts of NaHC03 were added.
Although there is some scatter, both types of solution show increasing velocity with
Temperature
(C)
R. N. Parkins
172
-7
and S. Zhou
.
10
I
II
PH
Fig. 15.
Maximum
Fig. 16.
Bicarbonate
concentration
concentration
on crack velocities
solutions.
solutions
with different pH
(mol/l)
in SSRT in various
HCO;/CO:-
increasing
HCO;
concentration,
suggesting
that HCO;
is involved in the dissolution
process that results in crack growth, as initially suggested by Davies and Bursteims
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