CorrosionScience,Vol. 39, No. 1, pp.

15%173,1997
Copyright 0 1996Elsevier Science Ltd

Pergamon

Printed in Great Britain. All rights reserved

001&938X/97 %17.00+0.00

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

associated with the formation of soluble compounds,

probably FeHCOz and Fe(HCO&.
More recently, Blengino et ~1.~have reported results from studies involving the application
of electrochemical
impedance
spectroscopy,
infrared spectroscopy
and energy dispersive
spectroscopy of the films developed on iron exposed to a carbonate-bicarbonate
solution in
the active-passive
potential range at various temperatures.
It is concluded that the corrosion
products have a bilayer structure, in conformity with the suggestions of Riley and Sykes,
with FeCOs, complex ferrous-ferric
oxides (y-Fe20s/Fes04
containing Na+) and ferrous or
ferric hydroxycarbonates,
Fe,(OH),(COs),,
the latter increasing with increasing potential
and temperature.
Blengino et al. suggest that the fact that they found only very small
amounts of Fe304, in contrast to the findings of other workers, can be attributed to timerelated phenomena,
since their work involved relatively short exposure times compared with
those involved in crack growth experiments.
The authors conclude that the electrochemical
phenomena
involved in the SCC of iron and mild steels in bicarbonate
environments
appear
to be very complex, a statement with which it is difficult to disagree in the light of the
conclusions
from the various studies mentioned above.
Blengino et al9 state that the intrinsic chemical nature of the corrosion products do not
play an essential role in the SCC mechanism, which is understandable
if by mechanism they
mean the dissolution
process at the crack tip and the chemical nature of the corrosion
product films excludes other properties.
Thus, intergranular
SCC of ferritic steels in
carbonate-bicarbonate
solutions is markedly dependent on potential, the lower potential
boundary approximating
to the potential [about -0.7 V (SCE)] of maximum current in the
large oxidation
peak observed in potentiodynamic
polarization
curves.6 Since most
authors agree that iron dissolves in some form of Fe(I1) in that oxidation peak, the lower
potential for SCC appears likely to be associated with the start of the passivation
process
that culminates in the cessation of SCC at the upper potential of the cracking domain, the
limits of which are reasonably defined by potentiodynamic
polarization
curves at relatively
fast and slow sweep rates. Most authors appear to agree that, at potentials above the
cracking domain, y-FezOs is formed, although Blengino et aL9 consider Fe,(OH),(CO&
the
filming substance
at such potentials.
However, their acceptance that the short exposure
times in their experiments
accounts for the very low amounts of Fe304 detected raises
questions as to the long-term stability of ferric hydroxycarbonate
and the possibility of its
conversion to y-FezOs. Nevertheless,
the various programmes
of work mentioned above do
not provide an explanation
of the boundaries
of the SCC domain. That may be due to lack
of information,
except for a few solution
compositions
and temperatures,
on the
experimentally
determined
boundaries
for SCC of C-Mn steel in carbonate-bicarbonate
solutions of different compositions,
and that was an objective of the present work.
EXPERIMENTAL

METHODS

The work involved a low-C steel containing

(wt%) C =0.05, Mn =0.33, Si = 0.01,
S = 0.035 and P = 0.032, the low C content assisting in crack growth at ambient temperature
where most of the measurements
were to be made. The steel was hot forged and rolled from
5 cm x 5 cm x 30 cm billets to a 1.25 cm rod, the latter subsequently
being cold drawn to
5 mm diameter with appropriate
interstage annealing.
The slow strain rate test (SSRT)
specimens, 18 cm long, were machined to produce a gauge length 12.7 mm long and 2.5 mm
in diameter, polished with emery paper to 3/O grade finish and vacuum annealed at 960C
for 1 h. The test specimens were contained
in glass cells closed at each end with rubber

SC of C-Mn steel in CO,-HCO;-CO:-

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

The effect of pH on the potential range for cracking

The effects of different pH values, by additions of Na2COs or CO2 to 1 M NaHCOs,
upon the average crack velocity from tests conducted at various potentials are shown in Fig.
1. Apart from the obvious shift in the potential range for cracking, the intergranular form of
the latter was only observed towards the higher values of that range for any solution, with
the observation of transgranular cracks or fissures at lower potentials. At higher pH values,
obtained by adding various amounts of NaHCOs to 1 M Na2C03, only intergranular
cracking was observed, the potential range for such and the average crack velocities varying
with the solution pH, as is apparent from Fig. 2. The transition from intergranular to
transgranular cracking as the potential was lowered was also displayed with more dilute
NaHCOs solutions than that shown in Fig. 1, but with CO2 added, and also by NH4HC0s/
NH4NHC02 solutions at concentrations of 100 or 210 g/l, although not at 10 g/l, as
apparent from Figs 3 and 4. (Since the exact molecular weight of the mixed NH4HC03/
NH4NH2C02 is not known, its concentration is expressed in g/l.)
Transgranular cracks or fissures were only observed in the necks of SSRT specimens and
were readily distinguishable from their intergranular counterparts, as apparent from Figs 5
and 6. The latter shows one of the deepest transgranular cracks observed and was produced
in 0.1 M NaHCOs where only transgranular cracks were obtained over the potential range
from 0.275 to 0.425 V (SCE), whereas at the higher concentrations of 0.25 and 0.5 M
NaHCOs the transition from intergranular to transgranular cracking was observed as the

R. N. Parkins and S. Zhou

162

Intergranular

10

IM NaHCO, Sat. with CO* pH 7.7

lMNaHC03
pH8.6
o + 1M NaHCO3 + 0.17M Na2C03 pH 9.0
A A IM NaHC03 + 0.75M NafZ03 pH 9.6

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

the influence of severe plastic deformation

during the final stages of the test, in conformity
with their depths usually being less than one grain diameter. Moreover,
transgranular
fissures were usually associated with potentials in the active range, i.e. below those at which
an active-passive
transition
occurs and associated with intergranular
cracking yet above
those at which hydrogen
discharge
is possible
for the pH values involved.
Such
considerations
resulted in cyclic loading tests being conducted
in selected solutions
at
potentials where the intergranular
or transgranular
forms occurred in SSRT, such loading
sustaining
the micro-plastic
deformation
that is necessary for continued
crack growth
without the relatively gross deformation
associated with SSRT. The cyclic loading tests were
conducted in 1 M NaHC03 + 0.17 M Na2C03 at potentials of -0.525 and - 0.650 V, in
0.1 M NaHC03
at -0.350 V and in 0.1 M NaHCOs saturated with CO2 at - 0.350 V,
involved maximum loads of 100, 110 and/or 132% of the yield stress and with a fluctuating
component
of load corresponding
to 20% of the maximum value. All cyclic loading tests
were conducted
at ambient temperature
for various times from 48 to 864 h and involved
frequencies of 7 x lop4 or 0.08 Hz.
The cyclic loading tests in 1 M NaHCOs + 0.17 M Na2C03 (pH 9.0) at - 0.525 V (SSC)
produced intergranular
cracks in conformity
with the SSRT results (Fig. 1). The average
crack velocity showed some small dependence upon loading conditions, tending to increase
with maximum stress and frequency, but those effects were small by comparison
with the

SSC of C-Mn

steel in CO,-HCO;-CO:-

solutions.

163

0 0.75M NaHCO3 + 1M NazC03 pH 10.0

0.5M NaHCO, + 1M Na2C@ pH 10.2
0 0.35M NaHCO, + 1M Na2CO3 pH 10.4
A 0.25M NaHC03 + 1M Na2CO3 pH 10.6
. O.lM NaHC03 + 1M Na2C03 pH 11.0
l

0
0.0moo.o..
l

I.5

Fig. 2.

The effect of potential

solutions

AAAmmoAAAmmm
I
-0.6

I
-0.7

Potential

I
-0.8

V (see)

on the average crack velocity for low-carbon

of different pH value at ambient temperature.

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

Sat. with COl, pH 6.7

Sat. with CO*, pH 7.2

0000

-0.2

-0.3

-0.4

Potential
Fig. 3.

The effect of potential on the average

NaHC03 solutions saturated

0
I
-0.5

0
i
-0.6

V (see)

crack velocity for low-carbon steel in 0.1 and 0.3 M

with CO2 at ambient temperature.

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.

The effects of temperature

Some data are available14 showing that increasing
temperature
causes increases in
average crack velocities and changes in the potential range for intergranular
cracking of a
C-Mn steel in 1 M NaHCOs + 0.5 M Na2C03 solution. SSRT were conducted in the present
work at various temperatures
in different solutions,
Fig. 10 showing the average crack
velocities in 1 M NaHCOs + 0.75 M Na2C03 solution. Clearly the crack velocity at the most
potent potential increases with increasing temperature
and the potential for cracking shifts
in a negative direction. Transgranular
fissures were observed with the lower potentials in
that solution but when it was replaced by 1 M NaHC03 saturated with CO2 transgranular
cracking was only observed at ambient temperature,
as depicted in Fig. 11. Otherwise, Fig.
11 shows similar effects for increasing
temperature
to those in Fig. 10. Tests were also

SSC of C-Mn steel in CO*-HCO;-CO$-

j-6-

Intergranular

solutions. I

165

Transgranular

1/*-o.

1-7-

A A 10 g/l NH.,HC03 / NH4NH2C02 pH 8.2

q . 100 g/l NH4HC03 i NH4NH2C02 pH 8.3
o .210 g/l NH4HC03 / NH4NH2C02 pH 8.4

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.

conducted in 1 M NaHCOs and in 0.125 M NaHC03 + 0.062 M Na2C03 solutions. The

former could only be used at 23 and 40C because the pH increased markedly with increase
in temperature, the tests at 23C showing the usual transition from intergranular to
transgranular as the potential was made more negative, while at 40C only intergranular
cracking was observed. In the 0.125 M NaHC03 + 0.062 M Na2C0s solution intergranular
cracking was observed at 23 and 40C with no cracking at 60 or 80C. With both of these
solutions the crack velocity was higher for the higher test temperature and the intergranular
cracking potential range moved to lower potentials at the higher temperature. Despite data
for only two temperatures for two of these solutions, activation energies were calculated and
for the 1 M NaHCOs solutions with or without CO* saturation were 20.2 and 20.0 kJ/mol,
respectively, while for the 0.125 M NaHCOs +0.062 M Na&Os solution the value was
42.3 kJ/mol, and for the 1 M NaHCOs + 0.75 M Na2C03 solution it was 34.8 kJ/mol. The
values for the mixed carbonate-bicarbonate
solutions approximate to that (41.8 kJ/mol)
determined for a 1 M NaHCOs + 0.5 M Na2C03 solution using crack growth from a fatigue
precrack as the means of measuring cracking propensity.4
DISCUSSION
A summary of the results from the slow strain rate tests at ambient temperature is given
in Fig. 12, in terms of the mode of failure in some solutions at various pH and potential
values. Ignoring the transgranular fissuring mode of failure, which is shown above to be a

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

steel after SSRT in 0.1 M NaHC03

(SCE) and 22C.

+ 0.75 M Na .2co3

solution

at - 0 .35 v

SSC of C-Mn steel in CO,HCO;-CO~-

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

o O.lM NaHCOs Sat. with CO2 pH 6.7

A O.lM NaHCOs Sat. with CO2 pH 5.6
q Simulated
ground water
Sat. with CO* pH 5.3

Potential
Fig.

9.

V (see)

The effect of potential on RA% from SSRT for low-carbon

saturated with CO2 at ambient temperature.

.
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)

The effect of potential

on the average crack velocity for low-carbon
NaHCOs + 0.75 M Na$Os
solution at different temperatures.

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)

The effect of potential on the average crack velocity for low-carbon

solution saturated with CO2 at different temperatures.

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.

12. Showing the modes of fracture resulting from the application

of different potentials
SSRT on low-carbon
steel in solutions of various pH values at ambient temperature.

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

and the total concentration

of carbonate
and bicarbonate
added to the solution together
with the measured pH values. Figure 13 shows that the HCOF concentration
had some
influence upon the lower bound potentials,
as it did for the upper bound values, with the
lowest pH solutions showing a decreasing potential with increasing HCO; concentration
and the higher pH solutions showing the opposite trend. Armstrong and Coates4 studying
CO;--HCO;
soiutions
in the pH range
8.0-10.7,
concluded
that the potential

HCOs + CO> (6.7/7.7)

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)

Fig. 13. The effect of bicarbonate

concentration
in various solutions on the lower bound of the
potential range for intergranular
SCC at ambient temperature,
(The numbers in brackets give the pH
ranges for the different solutions.)

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)

Fig. 14. The effect of temperature

on the upper (U) and lower (L) boundaries of the intergranular
SCC domain for solutions
of pH 7.7 (1 M NaHC03
saturated
with CO*) and pH 9.6 (1 M
NaHCO, + 0.75 M Na2C03).

R. N. Parkins

172

-7

and S. Zhou

.
10

I
II

PH

Fig. 15.

Maximum

crack velocities from SSRT in various HCO;/CO:values.

Fig. 16.

The effect of HCO;

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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