Corrosion of API-X100 Steel Heat Affected Zones (HAZs) in CO 2-

Saturated Solutions – EIS Investigations

Faysal Fayez Eliyan and Akram Alfantazi

Corrosion group, Department of Materials Engineering, The University of British
Columbia, Vancouver, BC, Canada, V6T 1Z4.

Summary
This paper evaluates and models the corrosion products growth on the HAZs of API-
X100 steel in CO2 solutions. It first outlines the aqueous dissociation of CO2 to generate
H2CO3, H+ , the adsorption and dissolution processes on the ferrite grains, the cathodic
reactions, the cathodic role(s) of Fe 3C, and the precipitation and growth of the corrosion
products. With the use of EIS, over after 5,000, 10,000 and 15,000 s, the charge
transfer resistance, double-layer capacitance, and the resistance of the porosity of the
growing corrosion products, were measured to be fitted with equivalent circuits and to
model the corrosion interactions with proper interfaces. The HAZs cooled down from
950oC at 10oC/s showed a continuous decay in the corrosion resistance which was
lower than that of the base steel. The 30 and 60 oC/s showed intrinsically high charge-
transfer resistance and evidence for thin corrosion products.

1 Experimental Procedures
The tests were carried out in a one-litre, three-electrode, multi-port jacketed cell. The
potentials were measured against the Saturated Calomel Electrode (SCE), of +0.240 V
vs. SHE, and the counter electrode was a graphite rod. The solutions were heated by a

Figure 1: Gleeble© thermal simulation cycles and the microstructures of a) the as-received and the
HAZs simulated by controlled-cooling at b)10, c)30 and d)60oC/s from a 950oC peak temperature.

95oC circulated water stream. A Versastat 4 potentiostat, equipped with computer

software was used to execute the experiments. A Nikon EPIPHOT 300 optical
microscope was used to produce the optical micrographs of the as-received and the
HAZ microstructures. Prior to the microstructural analysis, selected samples were wet-
ground up to 1200 grit finish and polished with 6 and 1 μm diamond suspensions. They,
then, were immersed in a Nital etchant (2 mL of 70% nitric acid and 98 mL of
anhydrous, denatured ethyl alcohol) and treated with alcohol swapping and dried in an
air stream. A Gleeble© 3500 thermal simulation machine was used to simulate three
HAZs by heating the samples to a peak 950 oC at 100oC/s, and then by cooling at 10, 30
and 60oC/s as shown in Figure 1. The microstructure of the as-received consists of
ferrite, pearlite and bainite and that of the 10 oC/s HAZ consists of large equiaxed ferrite
and some dispersed pearlite. The microstructure of the 30 oC rate of 10 points per /s
HAZ is acicular-ferritic, and the microstructure of the 60 oC/s consists mainly of
martensite-retained austenite (M/A).The test solutions were kept at 90 oC, and the pH,
which was unbuffered, was between 4.2 and 4.8. EIS tests were carried out over after
5000, 10,000 and 15,000 s of free immersion, with a range of frequency from 10,000 to
0.01 Hz and a sampling decade.

2 Results and Discussion

With the use of EIS, the nature of change of the interfacial interactions, on which the
morphology and thickness of the corrosion products with time depend, was determined
for each of the microstructures. It initially relates to the degree of surface dominance of
the anodic versus the cathodic reactions, and to the interfacial concentrations of the
- -
adsorbent water molecules and the carbon carrying H 2CO3, , species.
These two factors, which control the rates and
mechanisms of dissolution, concentrations of
species that result, hydrogen generation and
filming are crucially affected by a microstructure
type. It intrinsically contains the active ferrite
phase, whose type, proportion and distribution
control the anodic phenomena, and it also
contains the stable cementite (Fe 3C) phase,
which is of the cathodic significance. And there
are the “foreign” phases, the corrosion products,
forming at interdependent kinetics – with the
kinetics of the surface – which they, depending Figure 2: Schematic representation of
on their thickness, composition and morphology, the main CO2 corrosion interactions.
control, at different degrees, the rates of the reactions and transport. Figure 2 presents
a schematic for the ferritic-pearlitic microstructure, of the as-received material, exposed
to a CO2 corrosion condition, along with the main interfacial interactions. CO 2 to result in
- -
H2CO3 and H+ to diffuse from the bulk solution to the interface. and result
from H2CO3 dissociation, but in our case of pH of nearly 4.5, their amounts are
insignificant to affect markedly the course of the reactions. Schmitt reported that H 2CO3
dissociates at the close vicinity of the surface to result in H+ ions that are to be reduced
at the surface, or that H2CO3 to be directly reduced to result in adsorbed H atoms, in a
rate-determining step, as reported by de Waard and Milliams [1]:
-
e- ads (5)
 -
(resulting from the reduction, not the dissociation of H2CO3) was reported in
-
many relevant mechanistic studies to be reduced to . Ogundele and White
-
proposed that reduction results in adsorbed H atoms, in a rate-determining step,
and it can combine with them to generate H2 molecules as [2]:
- -
e- ads (6)
- -
ads e -
(7)
In the schematic, the cathodic reduction is figuratively represented, with a curved arrow,
-
as H2CO3 and H+ being reduced to result, through many steps, in H2 and on the
pearlite grains.
In regard to the multi-step dissolution of ferrite, it proceeds, as indicated in the diagram,
upon the adsorption of H2 O as [3]:
e e ads e- (8)
e ads e e -
(9)
e e (10)
In Figure 3, the Nyquist profiles,
selectively, for the as-received, 10 and
60oC/s HAZs in 10 and 50 g/L NaCl
solutions, are shown. The governing
interactions, overall, seemed to be the
same, but the rates of the corrosion
products growth, primarily depending on
the microstructure, were evidently
different. They were, therefore, of
different admittance (Ycp ) and resistance
(Rcp) values, and they were different in
affecting the double layer charge transfer
resistance (Rch) and capacitance (Qdl ).
The Nyquist profiles consisted of Figure 3: Selected Nyquist profiles.
overlapped capacitive arcs of the type that reflects the simultaneously occurring
adsorption and filming processes, during the first stages of corrosion in CO 2 -saturated
solutions [4,5]. An EIS test, to be noted, does not determine the degree of surface
dominance of the anodic species (to drive dissolution) versus the cathodic species (to
drive hydrogen evolution). They both, in the beginning, drive multi-step, charge-transfer
reactions whose significance mixedly appears in the second, low-frequency portion of a
Nyquist plot. With time, however, the growth of the corrosion products can resolve for
that, given it strongly depends on the microstructure, to reveal some mechanistic
details.
For the as-received sample, in 10 g/L solution, the capacitive arcs increased in size,
with time, to indicate an increasing resistance against the charge transfer (lower
corrosion rates) under thickening corrosion products. With time, the surface area
available for anodic adsorption decreases, as a result of ferrite dissolution, as
represented in Figure 4a, which becomes increasingly faster and less reaction
controlling.
 Figure 4: Schematic representations for the main interfacial changes a ferritic-pearlitic steel
microstructure undergoes during the free immersion in a CO 2-sat urat ed solution.
The cathodic reduction, which becomes the slower process, sustains onto the pearlite
grains. The relatively high proportion of pearlite makes the overall reactions increasingly
under the cathodic control, and provides better chances for effective precipitation to
develop by the “anchoring” effect [6] and by the better stagnation [7] for the ionic Fe2+
-
and species, within the pores of pearlite (or Fe 3C) network, to react and precipitate
[86], as represented in Figure 4b, as:
-
e e (11)
Ogundele et al. and Linter et al. reported that Fe(OH)2 could
-
first form, but it reacts with CO2 and H2CO3 , or (more
likely if the pH in our case is at least 6.8) to result, in series of
reactions, in FeCO3 [7,8]. The corrosion products continue
growing by the coupled anodic and cathodic reactions
sustaining onto and through them as represented in Figure 4c,
and by chemical transformations that result in new products,
such as Fe2O3 and Fe3O4 . The equivalent {R(Q(R(QR)))}
circuit, which was used commonly, previously in many CO 2
corrosion studies, was considered to fit the EIS data and
represent the transformations from the early stages of
dissolution till complete filming, as represented in Figure 5.
The constant phase element (CPE) is denoted in the beginning
as Qp to represent the heterogeneous capacitance across the
pearlite network, and denoted as Qcp to represent the
capacitance across the corrosion products. The circuit Figure 5: The
achieved a precise fitting with the EIS data. The charge transfer, equivalent circuit
for the as-received sample, over time, increased from nearly 200 proposed for the as-
to 600 Ω.cm , and the double layer was pseudo-capacitive, as nch received during a)
2
dissolution and b)
was less than 0.7, especially in the beginning, indicating that the growth of the corrosion
precipitation began well before 5000 s of immersion. The products.
admittance of the corrosion products decreased and so did the porosity resistance (R p)
indicating that the channels of transport were increasingly occupied by precipitating
products. The 10oC/s HAZ did not a show a sensible increase in the charge transfer,
which was lower than that of the as-received, and its double layer was notably more
capacitive. That corresponds to a standing s urface activity, and to not as effective
corrosion products formed. That was probably, mainly, due to that the vigorous
dissolution of ferrite, the main constituent of the 10 oC/s HAZ, was not matched by the
physical and electrochemical effects a greater pearlite proportion would induce to
facilitate for a more effective, thicker precipitation. The proportion of pearlite in the
10oC/s HAZ is significantly low, to lead, as represented in Figure 6, to a predominant
anodic process, during which much of Fe 2+ diffused to the bulk solution, and to lead to
considerably thinner/more porous corrosion products to form, which seemed capacitive
and of high porosity resistance that did not change over time.

Figure 6: Schematic representations for the main interfacial changes the ferritic microstructure of the
o
10 C/s HA Z undergoes during the free immersion in a CO 2-saturated solution.

To compare, we carried out, in a previous study, a similar EIS analysis for the 10 oC/s
HAZ in bicarbonate solutions at 90 oC [9] to find that its behavior, quite interestingly, was
different from that investigated in this study. In bicarbonate solutions, the 10 oC/s HAZ
was of significantly greater tendency than the base as-received steel to form thick,
compact corrosion products, which were simulated by multi-time constant based
circuitry. That reveals the important role(s) of bicarbonate, in mildly alkaline solutions, in
promoting for more effective precipitation on the ferritic microstructures, unlike with
H2CO3, in lower pH CO2-satureated solutions, which made the 10 oC/s HAZ increasingly
more vulnerable to dissolve rather than to passivate. The charge-transfer resistance of
the 60oC/s HAZ, which was of an EIS response similar to that of the 30 oC/s HAZ, was
higher than that of the 10oC/s HAZ. They decreased with time, which makes the
corrosion layers growth behavior, given that the initial charge-transfer resistance could
be high intrinsically, difficult to determine. The possible roles of martensite and bainite in
these microstructures – of the 30 and 60oC/s HAZs – with the filming process require,
therefore, special future investigations to clearly associate them to the seemingly thin
corrosion products on the 30 and 60 oC/s HAZs. Increasing the chloride concentration,
for the 10oC/s HAZ, generally, mostly made the charge transfer resistance lower and
made the permittivity of the corrosion products higher.

3 References
[1] C. de Waard, D. Milliams, Carbonic acid corrosion of steel, Corrosion 31 (1975)
177-181.
[2] G. Ogundele and W. White, Observations on the influences of dissolved
hydrocarbon gases and variable water chemistries on corrosion of an API-L80
steel, Corrosion 43 (1987) 665-673.
[3] J. Bockris, D. Drazic, The kinetics of deposition and dissolution of iron: Effect of
alloying impurities, Electrochimica Acta 7 (1962) 293-313.
[4] F. Farelas, M. Galicia, B. Brown, S. Nesic, H. Castaneda, Evolution of dissolution
processes at the interface of carbon steel corroding in a CO2 environment
studied by EIS Corrosion Science 52 (2010) 509-517.
[5] Y. Chen, W. Jepson, EIS measurement for corrosion monitoring under
multiphase flow conditions, Electrochim. Acta 44 (1999) 4453-4464.
[6] K. Videm, J. Kvarekvaal, T. Perez, G. Fitzsimons, Surface effects of the
electrochemistry of iron and carbon steel electrodes in aqueous CO 2 solutions,
CORROSION/1996. Paper no. 1, NACE, 1996.
[7] C. Palacios, J. Shadley, Characteristics of corrosion scales on steels in a CO 2 -
saturated NaCl brine, Corrosion 47 (1991)122-127.
[8] B. Linter, G. Burstein, Reactions of pipeline steels in carbon dioxide solutions,
Corrosion Science 41 (1999) 117-139.
[9] F. Eliyan, A. Alfantazi, Corrosion of the Heat-Affected Zones (HAZs) of API-X100
pipeline steel in dilute bicarbonate solutions at 90°C – An electrochemical
evaluation, Corrosion Science. In press.