Composites Part B 243 (2022) 110165

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

An intelligent Mg anode for protection of the concrete-covered steel tubing

in carbon capture and storage
Peng-Peng Wu a, c, Guang-Ling Song b, c, d, e, *, Yi-Xing Zhu c, Ya-Jun Deng c, Da-Jiang Zheng c
a
College of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan, 030024, Shanxi, China
b
Department of Ocean Science and Engineering, Southern University of Science and Technology, 10088 Xueyuan Rd., Shenzhen, 518055, China
c
Center for Marine Materials Corrosion and Protection, Xiamen University, 422 S. Siming Rd, Xiamen, Fujian, 361005, China
d
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, 422 S. Siming Rd, Xiamen, Fujian, 361005, China
e
School of Engineering, The University of Queensland, St.Lucia, Qld, 4068, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: It is a big concern in the oil/gas industry that the carbonation-induced corrosion of the concrete-covered steel
Mg casing or tubing in underground Carbon Capture and Storage (CCS) may lead to gas leaking and even an
Anode environment pollution disaster. To reduce such a safety risk, the carbonation degree of concrete in the CCS
CCS
project must be detected or monitored, and the corrosion of steel casing/tubing should be inhibited in time. In
Carbonation
this paper, Mg was investigated in comparison with Al and Zn in simulated concrete pore solutions (SCPSs) as an
Intelligenization
intelligent anode that may be used to detect the carbonation degree of concrete and protect the steel in the
carbonated concrete. The results showed that Mg could be more sensitively activated and its anodic current
efficiency could be improved by carbonation, acting as such a smart anode in carbonated SCPSs. In a practical
CCS project, the intelligent detection of the carbonated concrete corrosivity and the protection of the steel casing
in the concrete may both be realized by using such a smart Mg anode. While the Zn and Al could not act as a
smart sacrificial anode since they were not sensitive to the carbonation and they could not provide sufficient
cathodic protection for the steel in the carbonated SCPSs, either.

1. Introduction
The chloride-induced corrosion of reinforcing steel was the main
cause of the failure of structures in marine environments and highways
using deicing salt [1–3]. By breaking the passive film of the steel in
highly alkaline pore solution, chlorides in the pore solution can trigger
severe corrosion of the reinforcing steel and the corrosion products will
lead to cracking, delamination and even spallation of the cover concrete
[3,4]. In return, once the cover concrete is damaged, it will inevitably
facilitate the ingress of chlorides and corrosion of the reinforcing steel. It
is important to monitor the chloride-contamination in concrete and
prevent the corrosion of reinforcing steel [1,2].
The cathodic protection using sacrificial anode has been widely used
in reinforced concrete structures [5,6]. Recent studies implied that the
Mg and its alloys could act as a smart sacrificial anode to detect the
chloride ingress and automatically provide an adequate cathodic pro­
tection current density to protect the reinforcing steel in concrete [7,8].
The intelligence of the Mg anode exists the following behavior: In intact
or fresh concrete which is not corrosive at all, the reinforcing steel is
passive and does not need cathodic protection. In this case, the Mg
anode is also in its passive state and only gives out a very limited current
density for the steel. Thus, the sacrificial anode Mg is almost not dis­
solved. Once the concrete is contaminated by chlorides, the passivity of
the reinforcing steel will be broken down, and corrosion will be initi­
ated. In the same time, the Mg is also activated by the chlorides, and will
give out a significantly current to cathodically protect the steel from
corrosion. In other words, the Mg anode can only offer protection for the
steel when the steel is threatened by corrosion attack and avoid
over-protection of the steel when there is no corrosion risk according to
the degree of chloride contamination in concrete. Such intelligence of
the Mg sacrificial anode to detect the chloride contamination and pro­
tect the reinforcing steel could not be realized by the traditional sacri­
ficial anode Al and Zn, since they are dissolved quickly in the highly
alkaline pore solution of concrete [8]. Based on the basic intelligent

* Corresponding author. Department of Ocean Science and Engineering, Southern University of Science and Technology, 10088 Xueyuan Rd., Shenzhen, 518055,
China.
E-mail addresses: songgl@sustech.edu.cn, guangling.Song@hotmail.com (G.-L. Song).

https://doi.org/10.1016/j.compositesb.2022.110165
Received 11 April 2022; Received in revised form 18 June 2022; Accepted 22 July 2022
Available online 31 July 2022
1359-8368/© 2022 Elsevier Ltd. All rights reserved.
P.-P. Wu et al.
Fig. 1. Schematic illustration of the underground CO2 storage, the carbonation
of the cover concrete, and the smart Mg anode for intelligent corrosivity
detection and corrosion protection for the pipe in the concrete.
concept, an optimized Mg–Al alloy has recently been developed [9].
Along the line of the Mg special electrochemistry, the traditional sacri­
ficial Zn anode could even be intelligentized by Mg alloying [10].
Apart from the chloride contamination, concrete carbonation actu­
ally more widely exists in many structures, which can also cause severe
corrosion damage to reinforcing steel due to the porosity of the concrete
[11–13]. In fact, concrete carbonation is responsible for the failure of
reinforced concrete in most of the environments other than marine
conditions [14,15]. Carbonation can lower the pH value of the concrete
pore solution [16–19]. Although in the early stage the formed calcium
carbonate may to some extent seal concrete pores or reduce concrete
porosity [20,21], long-term carbonation will generate large numbers of
macro-pores and cracks in the concrete after the deposited calcium
carbonate has built up high enough expansive pressure in the concrete
pores. Thus, concrete carbonation process can be accelerated in return
because of many new and large cracks generated [19,22]. The cracks can
further evidently speed up the carbonation development toward the
steel/concrete interface [23]. After carbonation reaches the interface,
the passive film on the steel will be dissolved, and the steel be activated
and corroded rapidly. In some industrial-polluted area with a high CO2
concentration, the carbonation induced corrosion of the reinforcing
steel can be very fast [19].
One of the most severe carbonation-induced corrosion can be in
Carbon Capture and Storage (CCS) projects, because the carbon steel
pipelines used in the projects are not corrosion resistant [24]. During
CCS, the CO2 from a variety of sources, like power and cement pro­
duction plants, is captured, compressed and injected into a subsurface
geologic “reservoir” for storage or future utilization (Fig. 1) [25,26].
However, in spite of the high efficiency in emission reduction or clean
industrial production, there is a big concern that leakage of CO2 may
occur from the “reservoir”. Just like the concrete-covered reinforcing
steel, the pipelines in the CCS are normally covered by concrete or
cement [27] (see Fig. 1). The internal corrosion of the pipelines in CCS is
much less severe than that in oil/gas exploitation, because the latter is a
result of the tubing/casing steel chemically reacting with the mixed
aggressive medium (containing corrosive water or acids) from the un­
derground gas/oil [24], while the former is caused by the “dry” CO2
captured from industrial production plants [28]. Therefore, the internal
corrosion of the pipelines in CCS is not listed as an important topic in this
2
Composites Part B 243 (2022) 110165
paper. The external surface of such steel tubing or casing exposed in the
high alkalinity concrete (or concrete pore solution) is usually very well
passivated and not corroded [29]. However, the concrete and soil rock
matrix are full of cracks and pores [30]. The high-pressure CO2 stored in
the underground “reservoir” could diffuse through the cracks or pores,
reaching the cover concrete, and carbonation of the concrete will occur.
The steel could be corroded in the carbonated concrete. Although the
concrete carbonation in normal environments above ground is relatively
slow, the detrimental effect of the concrete carbonation on the corrosion
damage is extraordinarily severe to the steel tubing or casing in CCS [1,
3], because the CO2 can be several orders of magnitude more concen­
trated in this case than in normal air above ground. In fact, the con­
centration or pressure of the CO2 injected into a deep underground
“reservoir” for storage is so high that the CO2 may be in a supercritical
state [24,31,32]. This means that the carbonation rate and the carbon­
ation degree of the cover concrete in CCS may be far beyond the normal
level in air [24,33]. Such an extreme concentration and extraordinary
state of CO2 in the geo-condition may rapidly acidify the concrete pore
solution [24,34]. Hence, the steel pipe covered by the carbonated con­
crete may be quickly and severely corroded (see Fig. 1), resulting in
unexpected groundwater contamination and an environmental issue
[24,35]. For example, the wellbore failure at a facility in Kansas released
about 3000 tons of CO2 leakage [36]. It is important to monitor and
prevent this type of underground corrosion damage.
Since Mg can intelligently monitor and prevent the corrosion of steel
in the chloride contaminated concrete [7–9], it may also be used as a
smart detector to detect concrete carbonation and as an intelligent
anode to cathodically protect steel in carbonated concrete. In theory, Mg
is passive when pH > 12, but it can be anodically dissolved at pH <
11.50 [37], slightly earlier (or higher) than the corrosion of steel that
normally occurs at pH < 9 [14,38,39]. Thereby, if concrete is carbonated
and the reinforcing steel or tubing is de-passivated, the Mg will be
activated before the steel corrosion, and the actively dissolving Mg will
give out a current density to protect the steel. As the current density
from the Mg anode depends on the carbonation degree, it can intelli­
gently vary with the corrosivity of the carbonated concrete, and auto­
matically transition from passive to active state due to concrete
carbonation. Hence, it can smartly provide a current to protect the steel
according to the carbonation degree. In other words, the Mg behaves
similarly to its intelligent detection and protection for corroding steel in
chloride-contaminated concrete [7–9]. If the smart Mg anode is
reasonably distributed, the intelligent detection and protection system
may even be able to identify the most corrosive location and effectively
protect the steel from corrosion attack in the riskiest area (see Fig. 1). It
should be noted that the widely used traditional Al anode is passive in
lower pH solutions and becomes active at pH > 8.5 [37]. It will be
rapidly dissolved in concrete before carbonation. Thus, it cannot be
activated by carbonation to effectively protect steel after the cover
concrete is carbonated. Similarly, the traditional Zn anode tends to be
passivated at pH < 9.5 [37], and cannot provide sufficient cathodic
protection for the activated steel in carbonated concrete, either. In
theory, Mg should be an ideal intelligent anode for detection of concrete
carbonation and protection of activated steel in carbonated concrete.
Unfortunately, this postulated intelligence of the Mg anode for steel in
carbonated concrete has not been experimentally verified so far.
In this paper, to verify the intelligence of Mg anode acting as a smart
corrosivity-detector and corrosion-preventor for steel in carbonated
concrete, the corrosion behavior of Mg was compared with that of Al and
Zn anodes in SCPSs. Since the carbonation can reduce the alkalinity of
the concrete pore solution, causing corrosion cause of steel in the
carbonated concrete, the SCPSs with different pH values (12.63, 11.50,
10.50, 9.50 and 8.50) were used to simulate the concrete carbonation
process. Polarization curves were measured firstly to reveal the effect of
the carbonation on the corrosion of these metals in the SCPSs. Galvanic
corrosion tests were further performed to reveal the anodic dissolution
of Mg anodes in the SCPSs when they were coupled with the steel.
P.-P. Wu et al.
Fig. 2. Schematic diagrams for (a) potentiodynamic polarization tests and EIS
measurements after immersion and (b) galvanic corrosion tests and corre­
sponding EIS measurements at Egs.
Corrosion behavior during the self-corrosion and galvanic corrosion of
the steel and Mg anodes were then also analyzed according to their
corrosion morphologies and electrochemical impedance spectra.
2. Experimental
2.1. Materials and solutions
Carbon steel #45 (C: 0.42–0.50 wt %, Si: 0.17–0.37 wt %, Mn:
0.50–0.80 wt %, Cr, Ni and Cu: < 0.25 wt %, others: < 0.035 wt %) was
used as the cathode. Pure Al (>99.999 wt %), pure Zn (>99.99 wt %)
and pure Mg (>99.9 wt %) were used as the sacrificial anodes. Before
corrosion tests, these metals were grounded with SiC paper up to 2000
grits, rinsed with deionized water and dried in warm air. The exposed
area of all the steel and sacrificial anodes was 1 cm2. A saturated Ca
(OH)2 solution (pH = 12.63 at room temperature) was used as the basic
simulated concrete pore solution (SCPS). To simply simulate the
carbonation process of concrete, the SCPS was mixed with NaHCO3
powder to adjust the solution pH value to 11.50, 10.50, 9.50 and 8.50.
Since the corrosion of the sacrificial anodes might be affected by the Ca
(OH)2 concentration, the Ca2+ concentration was also measured by an
Inductively Coupled Plasma Optical Emission Spectrometer (ICAP 7000
SERIES, ThermoFisher Scientific). It was found that the Ca2+ concen­
tration rapidly decreased from 0.02 mol/L in the saturated Ca(OH)2 to
0.000009 mol/L and 0.000006 mol/L in the pH 11.50 and 10.50 SCPSs.
Such a low Ca2+ concentration had almost no impact on the corrosion of
these steel and sacrificial anodes.
2.2. Corrosion tests
All the electrochemical tests were performed using a potentiostat
(Gamry Interface 1010E). At least 3 parallel measurements were
Fig. 3. The polarization curves of the steel in the different pH SCPSs.
3
Composites Part B 243 (2022) 110165
performed for each test. Potentiodynamic polarization was performed
by using a standard three-electrode system with an Ag/AgCl/Sat. KCl
electrode as the reference electrode, a Pt foil (15 mm × 15 mm × 0.2
mm) as the counter electrode. The steel and sacrificial anodes were used
as the working electrode. The schematic diagram for the polarization
was depicted in Fig. 2(a). All the polarization curves were obtained from
a cathodic potential to anodic at a scan rate of 0.5 mV/s. Before polar­
ization, the samples were immersed in the SCPSs for 10 min to obtain a
relatively steady open circuit potential (OCP). It should be stressed that
under these polarization conditions, all the metal samples were not
really stable, but in a relatively steady state in 10 min immersion after
their OCPs varied slowly. Fortunately, the polarization curves of the
metals had become relatively insensitive to these parameters when the
scan rate was so low. In this case, the corrosion performance was mainly
determined by the composition of SCPSs [40].
Galvanic corrosion tests were performed to obtain the galvanic
corrosion potential (Eg) and galvanic corrosion current density (ig) be­
tween the steel and the sacrificial anodes. The experimental Eg and ig can
be obtained by measuring the potential and current density between the
coupled steel and Mg, Al or Zn. The schematic diagram of the galvanic
corrosion tests was depicted in Fig. 2(b). Distance of the steel and the
sacrificial anodes was about 3 cm.
Electrochemical impedance spectroscopy (EIS) was used to analyze
the corrosion behavior of the sacrificial anodes at Egs and after immer­
sion by using the standard three-electrode system. The schematic dia­
gram for the EIS measurement during the immersion and at Egs is shown
in Fig. 2(a) and (b), respectively. The counter electrode in Fig. 2(b) was
only used in the EIS measurement at Egs, while during the galvanic
corrosion test it was disconnected. All the EIS measurements were per­
formed over a frequency range from 105 to 10− 1 Hz with a 5 mV
amplitude. The points below 10− 1 Hz were relatively scattered and not
included in this paper. The EIS results were further fitted in the
Zsimpwin software.
For the Mg, the negative difference effect (NDE) that can lower its
anodic current efficiency may be induced by anodic polarization (or
simply by galvanically coupling with steel) in a lower pH SCPS [41–43].
To simply reveal the NDE of the Mg during the galvanic corrosion test,
the corrosion rate (Cw ) of the Mg after 48 h galvanic corrosion tests were
measured by the weight loss measurement according to the following
equation:
Δm
(1)
Cw =
At
where the Cw is the corrosion rate in mg/day/cm2, the Δm is the weight
loss after tests in g, A is the area of the Mg and t is the corrosion duration
in day. To reveal the anodic polarization on the corrosion of the Mg, the
Cw after immersion for 48 h was also calculated. Corrosion products
were ultrasonically cleaned at room temperature in a dilute chromic
acid (40 g/L CrO3 + 2 g/L AgNO3) when measured the weight loss.
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Fig. 4. Polarization curves of the steel and the Al (a, b), Zn (c, d) and Mg (e, f).

Fig. 5. (a) (icorr, Ecorr) and (b) (igi, Egi) of the sacrificial anodes on the polarization curves obtained in the SCPSs with varies pH value.

2.3. Surface and micro analyses and EDS was 15 kV.

After 144 h immersion and galvanic corrosion tests, the steel and
sacrificial anodes were rinsed with deionized water and dried in warm
air. Their surface morphologies were immediately observed under an
optical microscope (OM, DVM 6, Leica) and a scanning electron mi­
croscope (SEM, Phenom XL, thermo scientific) equipped with the energy
disperse spectroscopy (EDS). The SEM morphologies were obtained in
back scattered electron mode and the accelerating voltage of the SEM
3. Results and discussions
3.1. Polarization curves
Figs. 3–4 show the polarization curves of the steel, Al, Zn and Mg in
the SCPSs with different pH values. The electrochemical parameters of
corrosion potentials (Ecorrs), corrosion current densities (icorrs) and the

4
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Table 1 For the anodic dissolution at the lower potentials than pA, dissolu­
The electrochemical parameters of the steel, Al, Zn and Mg extracted from the tion of the Fe mainly occurred by the reaction (2) which dominates the
polarization curves. corrosion process [45]. Over the potential of pA, the FeCO3 formed
Materials pH Ecorr (mV) icorr (μA/ Egi (mV) igi (μA/cm2) according to the reaction (3) as well as the reaction (2) and (4). Hence,
cm2) the steel surface was covered by the Fe(OH)2 and FeCO3 . If the steel
Steel 12.63 − 444.8 ± 2.4 ± 1.4 surface was not covered completely by the FeCO3 , the current continued
25.9 to increase until the max anodic current reached at pB. The formed
11.50 − 487.3 ± 1.9 ± 0.2
FeCO3 also dissolved as Fe(CO3 )2−
2 according to reaction (5) in these
10.8
10.50 − 778.5 ± 7.5 ± 2.4 potential regions where the potential was higher than that of pA. Such
12.8 formation of the Fe(CO3 )2− 2 was more likely occurred in the higher pH
9.50 − 763.9 ± 12.7 ± 1.8 SCPS whose pH was near to 10 [46]. Meanwhile, the passivation of the
10.3
steel occurred by converting the Fe(OH)2 and FeCO3 to the Fe3 O4 and
8.50 − 771.4 ± 95.0 ± 6.7
1.3 Fe2 O3 which had a contribution to the decreased anodic current den­
Al 12.63 − 1870.0 ± 228.8 ± − 1210.0 ± 1140.0 ± sities when the steel was polarized at a potential higher than pB [44,45,
6.3 13.7 3.6 38.6 47–49], as Fig. 3(b) and (c) presented. Hence, the increased current of
11.50 − 1732.7 ± 167.4 ± − 1081.0 ± 243.8 ± 15.2
the steel after the passivation current density plateaus (whose potentials
11.0 9.4 3.6
10.50 − 1678.1 ± 105.9 ± − 1076.0 ± 226.9 ± 7.3 were higher than 0.8V) in the SCPS with pH 10.50, 9.50 and 8.50 was
2.6 3.6 4.0 not caused by the dissolution of steel, but resulted from oxygen evolu­
9.50 − 1371.7 ± 7.1 ± 2.6 − 820.1 ± 33.0 ± 0.7 tion which can normally occur at a higher potential in a lower pH value
32.5 1.4 solution [37].
8.50 − 1028.9 ± 3.9 ± 1.7 − 776.2 ± 9.6 ± 1.5
15.3 1.1
The above analysis of the anodic dissolution of the steel provided an
Zn 12.63 − 1378.7 ± 21.6 ± 0.4 − 593.9 ± 9.8 ± 1.0 important basic for understanding the corrosion of the steel in the SCPSs
6.8 17.7 with different carbonation degrees. The polarization curves of steel in
11.50 − 1024.2 ± 2.5 ± 0.2 − 652.8 ± 9.9 ± 0.3 the pH 12.63 and 11.50 indicated that the steel in these two SCPSs was
6.1 50.4
passive and corrosion of the steel could not occur. Their Ecorr and icorr of
10.50 − 1087.0 ± 1.1 ± 0.1 − 781.3 ± 2 ± 0.2
3.4 0.4 steel in Table 1 showed similar Ecorr and icorr in these two SCPSs. With
9.50 − 1176.7 ± 27.5 ± 6.4 − 980.2 ± 262.2 ± 35.6 the SCPS being further carbonated, the Ecorr of steel became more
1.1 7.5 negative and the icorr higher. It should also be noted that the icorr of the
8.50 − 1172.9 ± 21.4 ± 1.6 − 772.7 ± 4.4 ± 1.5 steel in some carbonated SCPS was roughly estimated and might be
1.7 1.0
exaggerated due to the complicated cathodic reaction of the steel. In
Mg 12.63 − 1519.3 ± 4.7 ± 0.5 − 477.4 ± 4.5 ± 0.3
39.1 4.3 addition to the theoretical errors caused by water saturation and steel
11.50 − 1662.8 ± 20.3 ± 1.8 − 960.0 ± 30.1 ± 0.1 passivity in some cases [50], the higher IR drop might also cause a
6.5 0.3 slightly higher estimated icorr value, especially for that in the pH 8.50
10.50 − 1825.2 ± 43.9 ± 6.7 − 1076.7 ± 226.8 ± 26.3
SCPS whose cathodic polarization curves showed higher cathodic cur­
18.7 9.4
9.50 − 1955.1 ± 1383.6 ± − 1374.7 ± 4864.3 ± rent densities near the Ecorr. However, the higher icorrs in these
10.1 116.6 15.5 263.1 carbonated SCPSs at least indicated that the steel might suffer more
8.50 − 2034.0 ± 3597.8 ± − 1221.3 ± 10620.0 ± severe corrosion if its galvanic corrosion potentials after coupling with a
6.1 287.5 18.5 1006.4 sacrificial anode were in these anodic dissolution regions.
Fig. 4 shows the polarization curves of the Al, Zn and Mg in the SCPSs
intersection points (i.e., Egis and igis, theorical galvanic corrosion po­ with different pH values. With the pH of the SCPS decreased, the Al
tential and current density, or the intersection between the cathodic (Fig. 4(a)(b) and Fig. 5) showed the increased Ecorrs/Egis and decreased
polarization curve of the steel with the anodic polarization curve of the icorrs/igis on the polarization curves, indicating the passivity of Al
Mg, Al or Zn) of the anodic polarization branches of sacrificial anodes increased. The Zn (Fig. 4(c)(d) and Fig. 5) showed a complicated change
and the cathodic polarization branches of the steel extracted from the of the icorr with pH of the SCPS until the pH decreased to 10.50. Similar
polarization curves were depicted in Fig. 5 and Table 1. These electro­ change could be found in the igi but the igi in the pH 8.50 SCPS was lower
chemical parameters were used to analyze the corrosion of these metals than that in the pH 9.50 SCPS (Fig. 5(b)). The complicity in these current
theoretically [7,10]. The hydrogen evolution of the cathodic branch density changes could be caused by the deposition of carbonates. The Egi
obtained in the pH 12.63 and 11.50 SCPS in Fig. 3(a) was about at evolution as a function of the pH was reverse compared with the igi. The
− 1.05 V and − 0.9 V. The dramatic anodic current increased in the po­ Mg (Fig. 4(e)(f) and Fig. 5) showed the increased icorrs/igis and decreased
larization curves in Fig. 3(a) were not caused by the surface film Ecorrs/Egis with the pH of SCPS decreased, indicating that corrosion of
breakdown, but resulted from the oxygen evolution since no corrosion the Mg could be activated by the SCPS carbonation.
damage was found on the steel after polarization tests in these SCPSs. Figs. 4 and 5 showed that steel and Mg could be activated while Al
With the pH decreased to 10.50, 9.50 and 8.50, two anodic current and Zn transformed from activation to passivation by the SCPS
peaks could be found, as the pA and pB indicated in Fig. 3(b)(c). Such carbonation. Such transformation was important to the intelligence of
anodic current peaks were caused by the dissolution-precipitation the sacrificial anodes, which will be discussed later. The steel was pas­
mechanism of the Fe in these SCPSs due to the presence of bicarbon­ sive in the pH 12.63 and 11.50 SCPS (Figs. 3(a) and 5(a)), and thus it did
ate according to the following reaction [44,45]: not need cathodic protection. However, the Al and Zn showed the higher
icorrs in these SCPSs (Fig. 4(a)(c) and 5(a)) and their lifespan could be
Fe + 2H2 O→Fe(OH)2 + 2H+ + 2e− (2) shortened. With the SCPS further carbonated, corrosion of the steel was
activated (Fig. 3(b)(c) and 5(a)) and the sacrificial anodes should pro­
Fe + HCO−3 →FeCO3 + H+ + 2e− (3) vide the sufficient cathodic protection for the steel. However, the Al and
Zn transformed into the passivation and they showed increased Ecorrs
Fe(OH)2 + HCO−3 →FeCO3 + H2 O + OH− (4) and decreased igis (Fig. 4(a)–(d) and Fig. 5(a)). Thus, they cannot pro­
vide the sufficient cathodic protection for the steel in these SCPSs (Fig. 5
FeCO3 + HCO−3 ⇌Fe(CO3 )2−2 + H+ (5) (b)). For the Mg, it showed the decreased Ecorrs (Fig. 4(e)(f) and Fig. 5

5
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Fig. 6. Egs (a, c, e) and igs (b, d, f) evolution of the Al (a, b), Zn (c, d) and Mg (e, f) coupled with the steel during the galvanic corrosion tests in the SCPSs with
different pH.

Table 2
The Egs and igs of the Al, Zn and Mg coupled with the steel in the SCPSs with various pH values.
Materials pH Time (h)

0.5 48 96 144

Eg (mV) ig (uA/cm2) Eg (mV) ig (μA/cm2) Eg (mV) ig (μA/cm2) Eg (mV) ig (μA/cm2)

Al 12.63 − 1217.2 ± 19.2 1085.9 ± 15.3 − 1103.2 ± 7.3 60.6 ± 2.0 − 1101.4 ± 9.1 38.6 ± 1.5 − 1101.6 ± 8.9 31.5 ± 0.9
11.50 − 1110.0 ± 6.5 239.6 ± 7.8 − 1096.8 ± 6.8 170.9 ± 26.9 − 1075.3 ± 17.1 142.5 ± 35.6 − 1032.4 ± 29.3 87.8 ± 2.4
10.50 − 1039.4 ± 8.5 167.8 ± 10.1 − 1028.4 ± 10.5 96.6 ± 6.7 − 1006.4 ± 11.2 76.7 ± 2.4 − 996.4 ± 22.5 65.3 ± 6.1
9.50 − 851.0 ± 4.7 43.4 ± 4.4 − 809.7 ± 7.2 20.8 ± 1.1 − 464.3 ± 46.7 25.4 ± 1.9 − 548.5 ± 125.3 32.1 ± 15.6
8.50 − 738.6 ± 6.0 2.0 ± 0.1 − 726.7 ± 13.0 0.4 ± 0.1 − 82.9 ± 101.9 0.9 ± 0.7 − 29.3 ± 7.3 0.4 ± 0.3
Zn 12.63 − 554.8 ± 38.1 9.4 ± 1.0 − 422.9 ± 53.6 4.4 ± 1.5 − 396.1 ± 26.9 3.3 ± 1.3 − 388.4 ± 29.3 3.5 ± 2.0
11.50 − 372.2 ± 5.2 0.6 ± 0.1 − 356.2 ± 26.3 0.3 ± 0.1 − 323.4 ± 34.3 0.2 ± 0.1 − 332.2 ± 50.0 0.4 ± 0.3
10.50 − 912.8 ± 8.1 29.9 ± 2.1 − 355.1 ± 22.4 6.8 ± 4.0 − 301.4 ± 24.7 1.9 ± 1.9 − 308.2 ± 42.6 2.8 ± 2.7
9.50 − 961.5 ± 12.0 128.0 ± 20.8 − 726.9 ± 1.7 0.3 ± 0.0 − 644.6 ± 76.5 0.2 ± 0.0 − 151.0 ± 22.0 0.1 ± 0.0
8.50 − 901.9 ± 8.4 333.4 ± 24.5 − 736.8 ± 9.5 2.5 ± 1.2 − 82.8 ± 26.3 2.3 ± 0.4 − 74.1 ± 11.3 1.6 ± 0.6
Mg 12.63 − 466.4 ± 5.9 6.2 ± 0.5 − 263.7 ± 12.5 0.3 ± 0.1 − 249.0 ± 25.2 0.1 ± 0.0 − 236.6 ± 2.7 0.1 ± 0.0
11.50 − 1028.4 ± 15.4 36.8 ± 1 − 425.7 ± 8.7 4.2 ± 0.6 − 480.9 ± 47.1 7.8 ± 2.0 − 549.3 ± 21.7 14.8 ± 2.5
10.50 − 1178.0 ± 14.1 611.2 ± 55.3 − 1166.1 ± 8.1 343.8 ± 11.3 − 1142.9 ± 8.9 237.0 ± 4.3 − 1128.0 ± 7.1 174.7 ± 2.4
9.50 − 1494.5 ± 63.6 4717.5 ± 381.3 − 1348.4 ± 87.5 316.6 ± 119.8 − 976.3 ± 19.0 53.2 ± 8.8 − 986.9 ± 22.2 61.6 ± 7.6
8.50 − 1345.3 ± 58.6 15930.6 ± 899.1 − 915.0 ± 32.1 352.3 ± 88.3 − 1053.2 ± 27.5 1310.3 ± 155.6 − 1101.4 ± 25.7 334.3 ± 54.8

6
P.-P. Wu et al.
Fig. 7. Surface morphology of the steel after galvanic corrosion tests with the
Al, Zn and Mg in the SCPSs with different pH values.
(a)) and increased igis (Fig. 5(b)) with the SCPS carbonation and could
provide the sufficient cathodic protection for the steel.
3.2. Galvanic corrosion tests
To further confirm the intelligence of the Al, Zn and Mg when they
act as the sacrificial anodes, the galvanic corrosion tests were performed
in the different pH SCPSs for 144 h and these results were presented in
Fig. 6 and Table 2. The Egs of the Al coupled with the steel in the SCPSs
increased with the pH decreasing and the Egs in the pH 9.50 and 8.50
were much higher than in other SCPSs. The igs of the Al decreased
gradually with the pH decreasing in the SCPSs with pH range of
12.63–9.50. In the pH 8.50 SCPS, the igs was much lower than that in the
higher pH value SCPSs. The Egs of the Zn increased with the pH
decreasing and prolonging the galvanic corrosion tests in the pH range
7
Composites Part B 243 (2022) 110165
of 12.63–10.50. In the pH 9.50 and 8.50 SCPSs, the Zn showed the more
negative Egs values initially but these Egs was much higher in the final
tests than those in the higher pH SCPSs. All the igs of the Zn decreased to
several or a few tenths of μA/cm2 in all the SCPSs. The Egs of the Mg
coupled with the steel in the SCPSs decreased with the pH decreasing
and these Egs increased generally during the later stage of galvanic
corrosion tests. The Mg showed the increased igs with the pH of SCPSs
decreasing and these igs showed the decreased values during the later
stages of galvanic corrosion tests.
The galvanic corrosion tests of the Al and Mg were in agreement with
the polarization tests. In the pH 12.63 and 11.50 SCPSs where the steel
was passive and did not need cathodic protection, the Al could provide
much higher cathodic current for the steel and this could over-protect
the steel. For the Mg, it showed the lower igs and higher Egs in these
two SCPSs and the steel was just slightly polarized into its cathodic sites
and could not be over-protected. However, in the lower pH SCPSs where
corrosion of the steel could be activated and the steel need cathodic
protection, the Al could not provide the sufficient cathodic protection
for the steel while the Mg showed the increased igs and decreased Egs
and could provide the sufficient cathodic protection for the steel. For the
Zn, it showed the much lower igs in all the SCPSs and it could not provide
the sufficient cathodic current for the steel in the lower SCPSs. This was
not agreement with the polarization test results where the Zn showed
much higher igis in the pH 9.50 SCPS than other SCPSs. This was caused
by the protective surface film formation during the galvanic corrosion
tests and this will be discussed later.
3.3. Corrosion morphologies of the steel
Figs. 7 and 8 present the OM and SEM surface morphologies of the
steel after galvanic corrosion tests with the Al, Zn and Mg in the different
pH SCPSs. To better reveal the corrosion mechanism of the steel and the
protection of these sacrificial anodes during the galvanic corrosion tests,
the (igs, Egs) relative to the polarization curves of steel were also sum­
marized in Fig. 9. It could be found that the steel coupled with the Al in
the pH 9.50 SCPS (Fig. 7(a)) and coupled with the Zn in the pH 10.50
and 9.50 SCPS (Fig. 7(c)) showed the red rust. The corresponding SEM
micrographs in Fig. 8(a)(c) showed the rough surface. The corrosion
products in these cases mainly consisted of Fe(CO3 )2−
2 since the corre­
sponding Egs were in the pA and pB regions, as Fig. 9(c)(d) present. In
such cases, corrosion of the steel mainly occurred by the reactions (2)–
(5) and the Fe(CO3 )2− 2 was the main corrosion products due to the
relative higher pH in these bicarbonate solutions [46], as illustrated
before. However, the EDS results showed the lower C content. This
should be attributed to that the corrosion product were relatively loose
and easily peeled off in the sample preparation process used for SEM
observation. The OM graphs in Fig. 7(b)(d) showed the brown corrosion
product. These corrosion products in Fig. 8(b)(d) showed the atomic
ratio of Fe: C: O = 1: 1: 3 and thus could be confirmed as the FeCO3. Such
similar crystals characteristic of the FeCO3 was also reported before
[24]. Since the Egs of the steel coupled with the Al and Zn in Fig. 9(e)
were also in the anodic dissolution regions, the FeCO3 formation mainly
occurred based on the reactions (2)–(4) in the SCPS whose pH was about
8.50 [44,46].
All the steels after coupled with the Mg were not corroded but was
covered or partially covered by some deposits. The steel after coupled
with the Mg in the pH 10.50 SCPS was covered by the uniform white
deposits in Fig. 7(e) and Fig. 8(e). The selected zone in the dashed boxes
of Fig. 8(e) showed the typical Mg oxides/hydroxides characteristic
which was also reported in the previous studies [7,51,52]. This could
also be confirmed by the EDS results which mainly consisted by the Mg
and O. The MgCO3 might also existed in the deposits and the C might
result from the air or the CO2−
3 in the SCPSs. In the pH 9.50 SCPS in Fig. 7
(f), the deposits on the steel were also found but their distribution was
not uniform and only part of the steel was covered. The SEM image in
P.-P. Wu et al.
Fig. 8. The typical SEM morphologies of the steel coupled with the sacrificial anodes in different pH SCPSs.
Fig. 8(f) showed that these deposits showed the needle-like compounds
which was also the typical characteristic of the Mg oxides/hydroxides
formed on the Mg [52]. These deposits in Fig. 8(f) were too thin, leaving
to the higher Fe content in the EDS results since the electrons during the
EDS tests can easily penetrate the deposits. However, the deposit was not
found on the steel after coupled with the Mg in other SCPS. This might
be caused by the relative lower igs of the Mg in the SCPS with pH higher
than 10.50 and the higher hydrogen evolution rates on the steel in the
pH 8.50 SCPS since it was found that the hydrogen evolution rate was
quite higher in the pH 8.50 SCPS.
Apart from these typical surfaces in Figs. 7(a)-(f) and 8(a)–(f), the
steel surfaces after galvanic corrosion in other conditions were not
corroded and their surface morphologies were similar to that after
coupled with the Mg in the pH 11.50 SCPS (see Figs. 7(g) and 8(g)).
Although the Egs of the Zn and Mg coupled with steel were near the Ecorr
in the pH 12.63 and 11.50 SCPS (Fig. 9(a)(b)), the steel was not corroded
due to its passivation in such alkaline SCPSs. For the other conditions,
8
Composites Part B 243 (2022) 110165
the uncorroded steel was mainly caused by the sufficient cathodic pro­
tection by the sacrificial anodes, especially by the Mg, as Fig. 9
indicated.
The surface morphologies of the steel after galvanic corrosion tests
further confirmed that only the Mg could provide the sufficient cathodic
protection for the steel. It should also be noted that the steel could be
over-protected by the Mg in the pH 9.50 and 8.50 SCPSs during the
initial galvanic corrosion tests due to the hydrogen evolution. However,
such over-protection could be rapidly suppressed since the Egs of the
Mg/steel couples in these two SCPSs increased to a nobler value and no
hydrogen evolution occurrence was found during the later stage of
galvanic corrosion tests.
3.4. Corrosion morphologies of the Al, Zn and Mg
Fig. 10 presents the corrosion morphologies of the Al after immersion
and coupled with the steel in the different pH SCPSs for 144 h. The plate-
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Fig. 9. igs and Egs of the sacrificial anodes coupled with the steel during the galvanic corrosion tests (igs and Egs are also listed in Table 2).

Fig. 10. Corrosion morphologies of the Al after immersion (a, c, e) and galvanic corrosion (b, d, f) for 144 h in the SCPS with pH of (a)(b) 12.63, (c)(d) 10.50 and (e)
(f) 9.50.

9
P.-P. Wu et al.
Fig. 11. Corrosion morphologies of the Zn after immersion (a, c, e) and galvanic corrosion (b, d, f) for 144 h in the SCPS with pH of (a)(b) 12.63, (c)(d) 10.50 and (e)
(f) 9.50.
like corrosion products of Al in the saturated Ca(OH)2 were the calcium
metaaluminate and calcium aluminum hydroxide hydrate (CaAl2O4 and
Ca2Al(OH)7⋅3H2O) [7,53] and the corrosion product after immersion
were slightly denser than that after galvanic corrosion tests, as Fig. 10(a)
(b) presented. The corrosion products in the pH 10.50 SCPS (Fig. 10(c)
(d)) was thinner and showed lots of cracks. Such corrosion products
were different with that formed in the saturated Ca(OH)2 and this was
caused by the very limited Ca2+ content in this SCPS. The corrosion of Al
mainly occurred in such alkaline SCPS by consuming the hydroxide ion
and forming the soluble meta-aluminate [37]. It should also be noted
that the surface film formed in the pH 10.50 SCPS could be easily peeled
off after rinsed with the de-ionized water. Such surface film could pro­
vide very limited protection for the Al and the Al could still be corroded
rapidly. Hence, the Al showed the higher igs than that in the saturated Ca
(OH)2 during the latter galvanic corrosion tests, as Fig. 6(b) presented.
The Al after immersion in the pH 9.50 SCPS in Fig. 10(e)(f) showed the
similar corroded surface with that in the pH 10.50 but the surface was
much denser. This should be caused by the much lower icorr. However,
the Al after coupled with the steel in pH 9.50 SCPS showed the wider
cracks, indicating corrosion of the Al could be accelerated due to the
anodic polarization. The surface morphologies of Al in Fig. 10 were in
agreement with the electrochemical tests that the Al was dissolved
quickly in the high pH SCPSs but the dissolution rates decreased as the
pH decreased.
Fig. 11 shows the corrosion morphologies of the Zn after immersion
and coupled with the steel in the different pH SCPSs for 144 h. The
corrosion morphologies in the saturated Ca(OH)2 showed plate like Ca
10
Composites Part B 243 (2022) 110165
(Zn(OH)3)2⋅2H2O which was also reported in the previous studies [10].
These corrosion products were believed to protect the Zn substrate from
further dissolution and thus the igs decreased during the galvanic
corrosion tests, as Fig. 6(d) presented. In the carbonated SCPS with pH of
10.50, the Zn showed the uncorroded surface after immersion in Fig. 11
(c) and some corrosion products could be found after galvanic corrosion
tests in Fig. 11(d). However, the corroded area did not propagate along
the substrate. The uncorroded surfaces were also found in Fig. 11(e)(f)
where the Zn surfaces were covered by the compact film. The corrosion
product in these surface was comprised by the protective zinc hydrox­
ides and carbonate [37]. With the pH decreased, the relative content of
the zinc carbonate increased with the increasing of the bicarbonate
which broaden the passivation domain of the zinc [37], leading to
decreased igs in a wide pH range from 11.50 to 8.50 in carbonated SCPSs
during the galvanic corrosion tests.
Fig. 12 shows the corrosion morphologies of the Mg after immersion
and coupled with the steel in the different pH SCPSs for 144 h. The
corrosion products formed on the Mg in the saturated Ca(OH)2 showed
the compact Mg oxides/hydroxides which was also revealed by the
previous work [10], as shown in Fig. 12(a)(b). The surface film formed
in the pH 11.50 SCPS also showed the net-like Mg oxides/hydroxides
and these corrosion products were same to the deposits on the steel in
Fig. 8(e). The morphologies shown in Fig. 12(a)–(d) indicated that the
surface film formed in the carbonated SCPS could be more porous and
thus the igs of the Mg/steel couples showed the slightly higher values
than that in the uncarbonated SCPS, as Fig. 6(f) presented. With the pH
further decreased to 10.50, the corroded surface in Fig. 12(e)(f) showed
P.-P. Wu et al.
Fig. 12. Corrosion morphologies of the Mg after immersion (a, c, e, g) and galvanic corrosion (b, d, f, h) for 144 h in the SCPS with pH of (a)(b) 12.63, (c)(d) 11.50,
(e)(f) 10.50 and (g)(h) 9.50.
lots of cracks and the surface film was comprised by the magnesium
hydroxides and magnesium carbonate [54,55]. The Mg surface after
corrosion in pH 9.50 SCPS also showed the cracks and some tiny pores
could be found on the surface film whose composition was mainly the
magnesium carbonate [56]. Such surface film in Fig. 12(f)(h) apparently
cannot prevent the Mg substrate from dissolution and the Mg could
provide the sufficient cathodic protection for the steel, as Fig. 6(f)
showed.
3.5. EIS results
The EIS was used to further confirm the corrosion mechanism of the
Al, Zn and Mg during the immersion and galvanic corrosion tests. To
analyze the EIS results, an original equivalent electric circuit (EEC)
shown in Fig. 13(a) was used to fit these spectrums. This EEC was also
widely used in the previous EIS fitting [7,10,52]. In the EEC shown in
11
Composites Part B 243 (2022) 110165
Fig. 13(a), the Rs was the solution resistance, the Cf and Rf were the
surface film capacitance and the corresponding film resistance, the Cdl
and Rt represented the double layer capacitance and the charge transfer
resistance at the interface of the film and the substrate where no other
electrochemical steps were involved, the Ca and Ra described the pseudo
capacitance and resistance at the film/metals interface due to the mul­
tiple electron transfers which could limit the electrochemical reaction,
the RL and L were the inductance and the corresponding resistance
which describe the local dissolution of the surface film [41,57]. The
Nyquist plots fitted by the inset EEC in Fig. 13(a) were characteristic of
the capacitive loops followed by one inductive loop and another
capacitive loop, as Fig. 13(a) presented. In some cases, the Rt was too
small and can be neglected. In such cases, the Cdl then could be included
into the Ca and the corresponding original EEC could be simplified into
the inset EEC shown in Fig. 13(b). If the local dissolution of the surface
film does not occur, the RL and L could be removed and the
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Fig. 13. The typical Nyquist plots and the corresponding EEC used to fit these EIS results.

Fig. 14. Evolution of Nyquist plots for Al during immersion in the SCPSs with different pHs (a) 12.63, (b) 11.50, (c) 10.50 and (d) 9.50.

corresponding EEC was shown like that in Fig. 13(c). The Nyquist plots 1
fitted by this EEC mainly showed one complete capacitance loop (Fig. 13 Cf =
(Yf × Rf )n1
(6)
(c) and two capacitances (Fig. 13(d)). The time constant of the two ca­ Rf
pacitances of the Nyquist plots in Fig. 13(c) were too close to be
distinguished well. If the surface film was protective enough, the where the Yf and n1 are the admittance of the CPEf in Ω− 1 ⋅ cm− 2 ⋅ sn1 and
Nyquist plots were characteristic by one incomplete capacitive loop its power index number. For the Cdl and Ca, they were calculated by the
[58]. In such cases, the Ca and Ra could also be removed, as Fig. 13(e) Burg’s equation [60]:
presented. 1 1 n2 − 1
(7)
1

Due to the imperfect surface of the electrodes, the capacitances were C = Y n2 ( + ) n2

Rf R
replaced by the constant phase angles (CPE) in the EIS fitting. The Cf
were further calculated by the following equation [59]: where the Y is the admittance of the CPEdl or CPEa in Ω− 1 ⋅ cm− 2 ⋅ sn2 and

12
P.-P. Wu et al.
Fig. 15. Evolution of Nyquist plots for Al at Egs in the SCPSs with different pHs (a)(b) 12.63, (c) 11.50, (d) 10.50 and (e) 9.50.
n2 is the powder index number, R is the Rt or Ra. Since the corrosion
resistance of the sacrificial anodes could be estimated by the Rf and Ra,
only the Rf and Ra were discussed later.
Figs. 14 and 15 present the Nyquist plots and the fitted curves of the
Al during the immersion and galvanic corrosion tests. The fitting results
were listed in Table 3. The Al showed the similar Rf and Ra in the SCPSs
with a pH range from 12.63 to 10.50 and this was attributed to their non-
protective surface film which showed the cracks and crevices in Fig. 10
(a)–(d). With the pH decreased to 9.50, the Rf and Ra increased, indi­
cating the surface film became more protective and the Al transformed
from actively corrosion to stable passivation. This was also confirmed by
the relatively intense corrosion morphology in Fig. 10(e)–(f).
Figs. 16 and 17 present the Nyquist plots and the fitted curves of the
Zn during the immersion and galvanic corrosion tests in the SCPSs with
different pHs. The fitting results are listed in Table 4. Although the Zn
showed much smaller capacitive loops initially in the high frequency
region in some cases, the radius of these capacitive loops expanded
rapidly, leading to increased Rf (see Figs. 16 and 17 and Table 4). The
increased Rf was attributed to the protective surface film, such as the
Ca(Zn(OH)3 )2 ⋅2H2 O, zinc hydroxide and carbonate whose protective­
ness cannot be altered by the anodic polarization, as Fig. 11(a)–(f)
showed. Such surface film could suppress the dissolution of the Zn
during the galvanic corrosion tests, leaving to the increased Rf and Ra
values and the decreased igs, as Figs. 17 and 6(d) presented.
Figs. 18 and 19 present the Nyquist plots and the fitted curves of the
13
Composites Part B 243 (2022) 110165
Mg during the immersion and galvanic corrosion tests in the SCPSs with
different pHs. The fitting results are listed in Table 5. In the saturated Ca
(OH)2, the capacitive loop radius of Mg increased rapidly (see Figs. 18(a)
and 19(a)), leading to increased Rf (see Table 5). This indicated that the
passivity of the Mg improved with time due to formation of a protective
surface film (see Fig. 12(a) and (b)). Although 1.0 μA cm− 2 is regarded as
a transit point from passivation to corrosion for steel in some cases, it
does not mean that the Mg having an icorr a few μA⋅cm− 2 higher than the
1.0 μA cm− 2 (see Fig. 4(e) and Table 1) is being rapidly corroded,
because higher current density thresholds have also been proposed
before, and all these thresholds are simply used in engineering appli­
cations for convenience.
After the SCPS was carbonated, the radii of the Nyquist plots shrank
rapidly, leading to decreased Rf and Ra (see Figs. 18 and 19 and Table 5).
The Rf/Ra ratio of the Mg changed differently compared with those of
the Al and Zn. Such an evolution of the Rf and Ra indicated that both the
surface film and the Mg substrate could be activated by the SCPS
carbonation (see Fig. 12(a)–(h)). Hence, the Mg could provide more
sufficient cathodic protection, i.e., more negative Egs and higher igs, for
the steel in the SCPS suffered severe carbonation.
The above discussion about the Rf and Ra also suggested that
corrosion of the Al, Zn and Mg in the SCPSs was dominated by the
carbonation of the SCPS, which was barely influenced by the anodic
polarization if they were coupled with the steel since their Rf and Ra
were quite similar during the immersion and galvanic corrosion tests.
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Table 3
The EIS fitting results of the Al after immersion and coupled with the steel at Egs in the different pH SCPSs.
pH t (h) Rs (Ω cm2) Cf (10− 5
F/ Rf (Ω cm2) Cdl (10− 5
F/ Rt (Ω cm2) Ca (10− 5
F/ Ra (Ω cm2) RL (Ω cm2) L (H cm2)
cm2) cm2) cm2)

After 12.63 0.5 54.4 1.66 132.2 3862.00 26.7

immersion 48 286.9 0.96 551.7 2309.57 78.3
96 404.8 0.87 854.1 964.30 137.4
144 653.6 0.80 2092.0 172.91 429.5
11.50 0.5 96.7 1.85 215.6 2752.00 99.6
48 79.3 0.99 229.7 2088.00 136.0
96 100.3 1.05 472.5 1919.41 151.2
144 89.0 1.12 781.1 2296.00 148.9
10.50 0.5 83.2 3.00 421.7 3701.00 206.3
48 83.0 1.08 457.9 1787.41 375.5
96 92.3 1.13 808.4 1430.14 433.2
144 76.9 1.18 1096.0 807.37 181.8
9.50 0.5 53.6 3.58 340.0 1.27 2966.0
48 43.4 1.40 2397.0 0.05 2221.0
96 49.2 1.13 3553.0 0.45 2413.0
144 42.0 1.25 3487.0 0.01 2342.0
At Egs 12.63 0.5 52.4 0.24 11.0 0.37 28.4 572.87 333.2 13.8 0.06807
48 185.1 0.98 768.3 192.33 9290.0
96 247.9 0.95 1169.0 122.06 9436.0
144 287.1 0.94 1573.0 100.86 9103.0
11.50 0.5 108.0 0.51 9.1 0.89 281 353.57 2347.0 94.54 12.22
48 72.8 1.31 42.0 0.91 384.6 539.20 737.5 69.19 4.721
96 121.0 1.42 57.0 0.94 567.7 448.70 1767.0 101.2 3.177
144 46.1 1.75 90.8 0.79 683.4 378.62 1673.0 142 15.24
10.50 0.5 87.4 1.14 93.8 0.52 329.7 644.90 2530.0 95.69 14.66
48 55.7 1.61 81.0 0.82 699.3 427.80 1124.0 172.4 21.13
96 111.9 1.66 116.4 0.82 699.6 393.60 1296.0 172.3 22.9
144 82.5 1.42 66.0 0.92 857.3 393.30 904.2 186.7 22.84
9.50 0.5 50.9 2.87 452.8 0.27 1747.0 4220 1828
48 36.2 1.53 2388.0 0.08 1890.0 1251 763.4
96 42.5 0.95 1881.0 0.19 2057.0 2441 961.3
144 25.0 0.85 1833.0 0.05 2485.0 2414 663

3.6. Exacerbation effect of galvanic corrosion damage of Mg induced by
the NDE
For the anodic polarization of the Mg, for example, when it was
coupled with the steel, the current density of the Mg dissolution rate IMg
calculated by the weight loss measurement was always higher than that
calculated by the galvanic corrosion current Ig using Faraday Law. Such
a phenomenon was caused by the NDE due to the accelerated hydrogen
evolution when the Mg was anodically polarized, and the corresponding
equation is related to Ref. [61]:
Ig = IMg − IH
where IH was the hydrogen evolution rate. This equation clearly indi­
cated that practical dissolution of Mg was exacerbated due to the NDE
since the measured Ig must be lower than the IMg . Such exacerbation of
galvanic corrosion damage of Mg could reduce the anodic current effi­
ciency (η) which could be calculated by:
Ig IMg − IH
η= = (9)
IMg IMg
The exacerbation factor (Ef) of the anodic galvanic corrosion damage
was related to the η and in theory, there is:
1 IMg IMg
Ef = = = (10)
η Ig IMg − IH
Fig. 20 shows the Cw of the Mg after immersion and coupled with the
steel for 48 h in the pH 9.50 SCPS. The Mg after immersion showed the
much higher corrosion rates than that after galvanic corrosion tests,
indicating the dissolution rate of the Mg under anodic polarization was
much lower than that at free potential. The corrosion of Mg in this pH
9.50 SCPS was very different from the corrosion behavior in other so­
lutions where Mg showed increased dissolution rates under anodic
dissolution compared with that at the free potential due to the more
effective NDE (i.e., the much higher hydrogen evolution rate) under
anodic polarization [41,62]. The NDE in the carbonated SCPSs was
suppressed. This was also well supported by the anodic polarization
curves in Fig. 4(f) where a current decreasing plateau appeared and no
obvious hydrogen evolution was found on the Mg in this plateau. Such
unusual corrosion of Mg under anodic polarization were also reported in
the literature [56]. It was found that the Mg showed decreased hydrogen
evolution rates under anodic polarization in a bicarbonate solution with
pH of 8.4 by forming the magnesium carbonate. Such unusual decreased
hydrogen evolution was also be well confirmed by the hydrogen evo­
lution in Fig. 20(b) which showed the decreased hydrogen evolution
(8)
(HE) rate with the increased Egs (Fig. 6(e)). The above analysis also
indicated that the η of Mg could be increased and the Ef could be
decreased due to the decreased HE rate if it was coupled with the steel in
the SCPSs based on equations (8)-(10). The calculated η of Mg was about
(74.45 ± 1.96) % after galvanic corrosion tests for 48 h in the pH 9.50
SCPS and this value was much higher than the widely reported 50%
when the Mg used as the sacrificial anodes. It should be noted that the
overall η could be further improved and the Ef could be further
decreased if longer tests were performed since the HE rate was quite low
after galvanic corrosion tests for 48 h, as Fig. 20(b) presented.
3.7. The intelligence of the Mg anode and possible application in CCS
The steel in intact concrete will not be corroded, because a passive
film can be formed on its surface which could effectively protect the
steel from corrosion. However, dissolution and decomposition of the
passive film occurs if the pore solution pH decreased to 9 due to the
carbonation [14,38,46,63,64]. In some cases, the obvious depassivation
occurred even in the higher alkaline SCPS or pore solution [65,66] and
such depassivation of the surface film could induce the corrosion of the
steel. The polarization curves in Fig. 3 indicated that the passivation of
the steel could be maintained in the pH 12.63 and 11.50 SCPSs. The

14
P.-P. Wu et al.
Fig. 16. Evolution of Nyquist plots for Zn during immersion in the SCPSs with different pHs (a)(b) 12.63, (c) 11.50, (d) 10.50 and (e) 9.50.
higher corrosion rates in the lower pH SCPSs near the corrosion poten­
tial indicated the transformation from passivation to activation of
corrosion and the steel could be corroded in these SCPSs.
Corrosion of the Al in the SCPSs was opposite with the steel: the Al
transformed from rapid dissolution to passivation with the pH of SCPS
decreasing. Such transformation was well supported by the decreased
icorrs and igis and increased Ecorrs and Egis in Figs. 4–5 and the increased
Rf and Ra in Figs. 14 and 15. The Zn showed the passive state in all SCPSs
due to its protective surface film, as Fig. 11 and Figs. 16 and 17 indi­
cated. Only the Mg showed the same transformation from passivation to
corrosion with the steel in the carbonated SCPSs, as polarization tests
and the EIS results in Fig. 4s(e)(f) and 18–19 indicated. Such activation
of the Mg in the corrosive SCPSs caused by the carbonation is important
in regarding to its intelligence when act as the smart sacrificial anode to
detect the carbonation and provide the cathodic protection for the steel.
A smart corrosivity detector and corrosion protector for the steel in
the concrete should has these following features: (ⅰ) be sensitive to the
corrosivity so that the corrosivity of the concrete could be detected; (ⅱ)
providing the sufficient cathodic protection for the steel; (ⅲ) has low
self-corrosion rate so that its service life could be extended and the
protection efficiency could be increased [7,8].
All the electrochemical tests indicated that the Mg was more sensi­
tive than the Al to the corrosivity of the concrete caused by the
carbonation. As discussed above, the Al showed the rapid corrosion
characteristic in the SCPSs with a wide pH range from 12.63 to 9.50 and
15
Composites Part B 243 (2022) 110165
then changed into passive state with the SCPS further carbonated. The
Zn was passive in all SCPSs. For the Mg, corrosion could be gradually
activated due to the increased corrosivity of the SCPS. All these were
well supported by the corroded surface morphologies in Figs. 10–12 and
the EIS results in Figs. 14–19. This indicated that only the Mg could meet
the first requirement of a smart sacrificial anode.
The polarization curves of the steel in Fig. 9(a)–(c) indicated that
passivation of the steel in the pH 12.63 and 11.50 SCPSs cannot be
altered and corrosion of the steel cannot be occurred. In such cases, the
steel does not need protection. The Mg and Zn could only provide very
limited cathodic protection for the steel by slightly cathodically polar­
izing the steel since their igs were quite small. Such lower igs in these two
SCPSs indicated that the dissolution rates of the Mg and Zn were quite
low, which were beneficial to the service lifespan. For the Al, the rapid
corrosion rates in these two pH SCPSs would over-protect the steel since
their Egs were much lower than the hydrogen evolution potential. With
the pH of the SCPS further decreased, the steel has the risky of corrosion.
In such cases, the sacrificial anodes should provide the sufficient
cathodic protection for the steel to prevent the corrosion of the steel. As
Fig. 9(c)–(e) indicated, only the Mg could be further activated and
provide the more sufficient cathodic current for the steel in the SCPSs
with pH values of 10.50–8.50. Hence, only the Mg meets the second
requirement as the smart sacrificial anode.
It could be concluded that only the Zn meet the third requirement
based on its much higher impedance resistance in Fig. 16. For the Al, it
P.-P. Wu et al.
Fig. 17. Evolution of Nyquist plots for Zn at Egs in the SCPSs with different pHs (a) 12.63, (b) 11.50, (c)(d) 10.50 and (e)(f) 9.50.
showed the much higher corrosion rates in the higher alkalinity SCPSs
and did not meet the third requirement. For the Mg, only the slightly
higher dissolution rate in the carbonated SCPSs especially with a pH
lower than 9.50 made it an imperfect smart sacrificial anode. However,
this was actually acceptable since the self-corrosion of Mg could be
decreased if it was coupled with the steel in practical, as section 3.6
discussed. Based on the above discussion, only the Mg meet the
requirement acting as the smart sacrificial anode to detect the carbon­
ation and provide the sufficient cathodic protection for the steel.
It has been reported that the corrosion of steel and the intelligent
protection performance of Mg anode in chloride-contaminated SCPSs
are similar to those in chloride-contaminated concrete [8,9]. Previous
studies have also confirmed that concrete carbonation can be reasonably
simulated in a simulated solution [67,68]. Although what presented in
this paper is only a proof-of-concept in the lab and further verification is
still needed, all the obtained pieces of evidence have supported the
feasibility of Mg as an intelligent anode in carbonated concrete. Hence,
in this paper to rapidly evaluate the intelligent behavior of Mg anode in
carbonated concrete, the concrete carbonation is simply simulated in the
saturated Ca(OH)2 solution by addition of different amounts of NaHCO3
powder. In CCS, the potential CO2 leakage due to steel tubing/casing
corrosion and failure has already been reported [24,27]. However, how
to protect or prevent the tubing/casing steel from carbonation attack in
16
Composites Part B 243 (2022) 110165
the cover concrete has not been seriously considered. Therefore, it is
proposed in this paper that in practical CCS, Mg anodes be embedded in
the cover concrete to cathodically protect the steel tubing or casing, as
schematically illustrated in Fig. 1. When the concrete or the cement is
intact and not carbonated initially, both the steel and Mg are passivated.
Thus, the serve life of the Mg can be prolonged since the dissolution of
the Mg in this case is quite slow. After the concrete or the cement is
carbonated, its corrosivity increases. The steel is de-passivated or acti­
vated at high corrosion risk. Meanwhile, the Mg is also activated and can
automatically provide a sufficient cathodic current to protect the steel
according to the corrosivity of the carbonated concrete or cement.
Hence, by measuring the galvanic corrosion current and potential, the
corrosivity of the cover concrete or cement can be easily known. In this
way, the Mg anode smartly detect the carbonation degree of the concrete
and protect the steel from corrosion.
4. Conclusions
(1) The traditional sacrificial anodes Al and Zn were not sensitive to
carbonation of SCPS. The Al showed rapid corrosion in the SCPSs
with a wide pH range from 12.63 to 9.50, but it became passive in
a lower pH SCPS. The Al could not provide sufficient cathodic
protection for the steel in the low pH SCPSs. The Zn was passive in
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Table 4
The EIS fitting results of the Zn after immersion and coupled with the steel at Egs in the different pH SCPSs.
pH t (h) Rs (Ω cm2) Cf (10− 5
F/cm2) Rf (Ω cm2) Ca (10− 5
F/cm2) Ra (Ω cm2) RL (Ω cm2) L (H cm2)

After immersion 12.63 0.5 43.2 5.89 31.0 624.90 1173.0

48 44.3 0.67 160.9 46.17 807.9
96 76.6 3.49 279800.0
144 83.3 4.67 263800.0
11.50 0.5 86.0 2.23 27280.0
48 79.9 1.31 123800.0
96 104.8 1.18 272400.0
144 77.4 1.13 586800.0
10.50 0.5 67.5 1.89 64470.0
48 66.2 1.07 353500.0
96 76.5 1.01 443100.0
144 73.3 0.98 486000.0
9.50 0.5 40.9 43.03 30.6 859.85 166.2
48 35.7 0.39 44050.0 0.72 141300.0
96 61.7 0.41 45140.0 1.11 114600.0
144 35.4 0.39 67760.0 1.68 104300.0
At Egs 12.63 0.5 45.5 1.58 15680.0 99.74 2093
48 45.5 2.03 35730.0 48.77 9130
96 89.2 1.99 42030.0 36.69 13390
144 63.8 1.65 46720.0 17.60 29500
11.50 0.5 105.4 0.91 128700.0
48 111.6 2.20 485200.0
96 99.8 1.86 618700.0
144 108.0 2.32 687600.0
10.50 0.5 86.0 0.80 4034.0 0.04 448.5 175.3 383.4
48 87.0 0.82 35180.0 1.22 20840.0
96 93.3 0.91 93320.0
144 114.3 0.70 92360.0
9.50 0.5 57.5 0.68 251.0 287.01 160.5
48 43.6 1.14 138100.0 0.08 283000.0
96 36.8 1.46 510100.0
144 29.8 1.15 656400.0

Fig. 18. Evolution of Nyquist plots for Mg during immersion in the SCPSs with different pHs (a) 12.63, (b) 11.50, (c) 10.50 and (d) 9.50.

the carbonated SCPSs and could not provide sufficient cathodic carbonation and provide sufficient cathodic protection for the
protection for the steel. steel.
(2) The corrosion of Mg could be activated by carbonated SCPS. It (3) The Negative Difference Effect of Mg in the carbonated SCPS
could act as a smart sacrificial anode in the SCPS to detect the could be suppressed if the Mg was coupled with steel, and thus

17
P.-P. Wu et al. Composites Part B 243 (2022) 110165

Fig. 19. Evolution of Nyquist plots for Mg during galvanic corrosion in the SCPSs with different pHs (a) 12.63, (b) 11.50, (c) 10.50 and (d) 9.50.

Table 5
The EIS fitting results of the Mg after immersion and coupled with the steel at Egs in the different pH SCPSs.
pH t (h) Rs (Ω cm2) Cf (10− 5
F/cm2) Rf (Ω cm2) Ca (10− 5
F/cm2) Ra (Ω cm2)

After immersion 12.63 0.5 38.2 1.19 13980.0 0.01 10920.0

48 41.3 1.19 391200.0
96 42.9 1.19 579000.0
144 48.2 1.22 793200.0
11.50 0.5 79.6 1.19 3082.0 190.98 1030.0
48 123.0 1.37 14740.0 0.02 10150.0
96 112.8 1.34 11590.0 97.82 2132.0
144 140.9 1.22 8779.0 33.54 2885.0
10.50 0.5 97.0 2.03 503.2 329.80 382.0
48 110.2 4.25 1159.0 257.13 232.7
96 102.3 3.66 1879.0 131.10 270.3
144 104.3 4.10 1645.0 85.54 322.4
9.50 0.5 50.0 1.15 23.7 1285.49 16.4
48 60.0 1.20 99.9 779.15 43.0
96 62.6 4.74 294.9 1255.00 50.7
144 57.8 1.56 155.0 1.62 752.0
At Egs 12.63 0.5 47.6 1.12 25140.0 14.52 8036.0
48 50.8 2.21 682800.0
96 55.6 2.49 1115000.0
144 61.2 2.71 1619000.0
11.50 0.5 69.8 1.19 5374 19.84 37140.0
48 113.0 2.30 16280 0.47 76290.0
96 101.4 1.30 2112 3.87 172900.0
144 162.5 0.96 1055 5.73 127900.0
10.50 0.5 94.6 4.51 237.8 14.93 4579.0
48 82.9 6.81 508 10.44 6350.0
96 98.5 8.32 1882 18.18 1941.0
144 105.4 7.06 3071 17.34 3562.0
9.50 0.5 45.8 1.14 26.9 655.48 97.7
48 105.2 0.83 145.3 100.20 197.3
96 138.8 1.86 2393.0 0.96 9728.0
144 109.9 2.62 2369.0 0.44 8413.0

the anodic current efficiency of the Mg could be improved in the of the concrete or cement and protect the steel tubing or casing
carbonated SCPS. from the corrosion attack in the carbonated cement or concrete.
(4) In practical CCS, Mg anodes may be embedded in the cover Before the concrete or cement is carbonated, the steel tubing/
concrete or cement to intelligently detect the carbonation degree casing is passivated and does not need protection, and the Mg is

18
P.-P. Wu et al.
Fig. 20. (a) The Cw of the Mg after immersion and coupled with the steel in the pH 9.50 SCPS and (b) the HE and HE rate during the galvanic corrosion tests.
also passive and does not provide protection. After the concrete
or the cement is carbonated and the steel needs to be protected,
the Mg is activated to automatically provide an adequate current
according to the corrosivity of the concrete to cathodically pro­
tect the steel.
Author statement
Pengpeng Wu: Investigation; Methodology, Data curation, Formal
analysis, Writing -original draft, Guang-Ling Song: Funding acquisi­
tion, Project administration, Supervision, Conceptualization, Formal
analysis, Investigation; Methodology, Writing – review & editing, Yi-
Xing Zhu: Formal analysis, Methodology, Yajun Deng: Formal analysis,
Methodology, Da-Jiang Zheng: Methodology, Resources, Software.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The research is supported by the National Natural Science Founda­
tion of China (key project grant No.51731008 and general project grant
No.51671163).
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