Construction and Building Materials 221 (2019) 351–362

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Construction and Building Materials

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Natural organic antioxidants from green tea form a protective layer to

inhibit corrosion of steel reinforcing bars embedded in mortar
Ivan Pradipta a, Daniel Kong a,⇑, Joash Ban Lee Tan b
a
School of Engineering, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, 47500 Subang Jaya, Selangor, Malaysia
b
School of Science, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, 47500 Subang Jaya, Selangor, Malaysia

h i g h l i g h t s

 Natural antioxidants are potential ‘green’ mixed-type corrosion inhibitors.

 Green tea is rich in natural antioxidants and was chosen as the antioxidant source.
 Green tea extract formed protective layer on rebar (mixed-type corrosion inhibitor).
 Protective layer formation was confirmed visually and with microscopic methods.
 The layer reduced rebar weight loss and was enriched with calcium carbonate.

a r t i c l e i n f o a b s t r a c t

Article history: In our previous work, we have demonstrated that at equal volume, green tea extract (GT) exhibited a
Received 7 December 2018 higher inhibition efficiency (IE) than commercial calcium nitrite corrosion inhibitor, on corrosion of steel
Received in revised form 15 April 2019 reinforcing bar (rebar) embedded in mortar (75–80 vs. 14–24%). GT behaved as a mixed-type corrosion
Accepted 2 June 2019
inhibitor which increased rebar polarization resistance (Rp); indicating that it formed a protective layer
Available online 18 June 2019
on rebar surface. In this paper, the formation of a protective layer was confirmed with visual inspection
and microscopic examinations. In presence of this layer, rebar corrosion was reduced. This is evidenced
Keywords:
by a reduced rebar weight loss and further indicated by a similar chloride permeability between control
Protective layer
Microscopic examinations
and GT concrete, and a similar corrosion rate (CR) between control reinforced mortar and reinforced
EDX mortar incorporating solely the residual solid of GT. The similarities ruled out the plausible higher IE
XRD of GT due to an improved physical barrier of mortar/concrete against corrosion. Analyses with energy-
FTIR dispersive X-ray spectroscopy (EDX), X-ray diffraction spectroscopy (XRD), and Fourier-transform
Weight loss infrared spectroscopy (FTIR) suggested that the layer was enriched with calcium, specifically the calcium
CR carbonate polymorphs. Although the formation of protective layer and increase in Rp were influenced by
Rp the magnitude of antioxidant activity, in this study GT has shown a better IE than CI. This should
Chloride permeability
encourage more studies on the IE of sustainable ‘green’ corrosion inhibitors in concrete.
Antioxidant activity
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction inhibitors under alkaline conditions, such as those seen in concrete

Commercial inorganic corrosion inhibitors such as calcium
nitrite corrosion inhibitor (CI) are easy-to-use and cost-effective
alternative to stainless steel reinforcing bar (rebar) and cathodic
protection for preventing rebar corrosion [1–4]. However, the
potential health and environmental hazards of inorganic corrosion
inhibitors has fostered a reduced use of these inhibitors, and sub-
stitution with less-toxic and more environmentally-friendly
(‘green’) organic corrosion inhibitors [1,3,5–11]. Nonetheless, there
are only limited studies on the efficiency of green corrosion
⇑ Corresponding author.
E-mail address: daniel.kong@monash.edu (D. Kong).
applications [1,12–19]. Thus, we suggested an investigation on the
corrosion inhibition efficiency of natural antioxidants at alkaline
concrete pH.
Natural antioxidants are organic compounds which are abun-
dant in nature [20]. These antioxidants possess multiple polar
atoms and/or electron-rich bonds which may promote the adsorp-
tion of antioxidant molecules on rebar surface, by donating elec-
trons to vacant d-orbitals of iron atoms and forming coordinate
bonds [11,21]. This adsorption confers natural antioxidants a
potential anti-corrosion activity as mixed-type corrosion inhibi-
tors, which form protective layer to inhibit electrochemical reac-
tions of rebar corrosion simultaneously: anodic reaction of iron
oxidation and cathodic reaction of oxygen reduction [22]. Being

https://doi.org/10.1016/j.conbuildmat.2019.06.006
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
352 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362

one of the richest sources of natural antioxidants, green tea has a Table 1
ten-to-thirty-fold higher antioxidant activity than the berries, Volume of calcium nitrite corrosion inhibitor (CI).

which are notably the other rich sources of natural antioxidants Corrosion Chloride-to-nitrite Volume of inhibitor
[23–28]. Thus, we selected green tea as the source of natural inhibitor ratio (L/m3 concrete)
antioxidants, postulating that it should have a better opportunity CI 0.9 40.14
to prevent rebar corrosion given this extremely high antioxidant 1.2 30.11
activity. The green tea was administered as green tea extract. 1.5 24.10
1.8 20.08
Corrosion inhibition efficiency (IE) of green tea extract (GT) was
compared with the IE of CI, which was incorporated as a positive
control. To our knowledge, there has been no study which reported
Table 2
the IE of GT at alkaline pH of concrete, nor compared the IE with
Volume of green tea extract (GT).
the IE of a commercial corrosion inhibitor (e.g. CI). CI and GT were
added during mortar mixing, to inhibit the corrosion of steel rebars Corrosion inhibitor Volume of inhibitor (L/m3 concrete)
embedded in the mortar (reinforced mortar). Dosages of CI were GT 40.14
selected encompassing four chloride-to-nitrite ratios, and dosages 30.11
24.10
of GT were selected similar to the CI dosages. The similar dosages
20.08
allow a justification on selected GT dosages, an IE comparison
between GT and CI, and an indirect adjustment of GT dosages to
chloride concentration [3,9,29–31]. of 1.22 kg/m3, and concrete density of 2,350 kg/m3. The CI concen-
Our previous investigation has shown that rebars embedded in tration and density were obtained from the specification sheet of
mortar admixed with GT displayed a significantly lower corrosion product used.
rate (CR) than both rebars embedded in control mortar, and mortar
admixed with CI [32]. Therefore, GT exhibited a higher IE than CI.
2.1.3. Dosage of resuspended GT solid
The lower CR was due to an increase in polarization resistance
Residual solid of GT lacks in the active compounds (contained in
(Rp) and a reduction in anodic slope (i.e. rate of iron oxidation).
supernatant) which are hypothesized to be responsible for the
The increase in Rp indicated that GT formed a protective layer on
electron donation and anti-corrosion activity of GT as a mixed-
rebar surface [2,6,33]. Therefore, in this paper, the formation of a
type corrosion inhibitor. Therefore, CR of reinforced mortar which
layer is confirmed with visual inspection and microscopic exami-
incorporated the residual solid of GT (without the supernatant)
nations (optical microscope and scanning electron microscopes).
indicates whether GT reduces CR by improving the physical protec-
Contribution of the layer towards reduction in CR was investigated
tion of mortar against corrosion (i.e. filling up mortar pores and
by comparing rebar weight loss in absence and in presence of the
creating denser mortar matrix), in addition to increasing rebar
layer. On the other hand, the plausible reduction in CR due to an
polarization resistance.
improved physical barrier of mortar/concrete against corrosion
GT was initially prepared according to volume shown in Table 2,
was examined by comparing chloride permeability of control and
and centrifuged to separate the supernatant and residual solid. The
GT concrete. Additionally, composition of the layer was elucidated
supernatant was discarded, and the residual solid was resuspended
by analyses with energy-dispersive X-ray spectroscopy, X-ray
in ultra-pure water (UPW) to the original volume shown in Table 2.
diffraction spectroscopy, and Fourier-transform infrared spec-
troscopy. Lastly, effect of GT’s antioxidant activity on CR and Rp
2.1.4. Preparation of mortar mixture
of GT reinforced mortar was also investigated.
Mortar mixture was prepared with Portland Cement CEM II/B-S
42.5N and fine aggregate according to mix design proportion
2. Experimental studies shown in Table 3. Properties of the fine aggregate are shown in
Table 4. The water/cement ratio (w/c) of 0.54 has been widely used
2.1. Materials and sample preparations for accelerated corrosion by other researchers [40,43–50], and was selected to provide
suitable permeability for completing corrosion investigation
2.1.1. Preparation of CI and GT within the available timeframe of this study (under twelve
Dosages of CI were selected encompassing the chloride-to-
nitrite ratios recommended by manufacturer (1.2 and 1.5) and Table 3
wider range of ratios (0.9 and 1.8). On the other hand, GT was pro- Constituents of mortar mixture.
duced by ultrasonic-assisted extraction of green tea leaves with Constituent Proportion (kg/m3)
hot water at 10% (w/w) for 30 min, and removal of large particles
Cement 420.00
from the aqueous extract by filtration. Upon extraction and filtra- Water 226.51
tion, concentration of GT was determined by oven-drying method Fine aggregate 1084.28
at 100 °C [34]. The concentration ranged from 2.0 to 3.0% (w/w), Water/cement = 0.54
and was used to determine the water content of GT.
The CR of GT and CI reinforced mortar were compared at equal
inhibitor volume (Section 2.1.2) [30,35]. Additionally, CR of rein- Table 4
Properties of fine aggregate.
forced mortar which incorporated residual solid of GT was also
determined (Section 2.1.3). The accelerated corrosion employed Properties Remarks
3.5% sodium chloride (NaCl) solution to simulate seawater Effective size 1.5–3.0 mm
[9,31,36–43]. Uniformity coefficient 1.5 ± 8%
Average fineness modulus 2.19 ± 0.08
Main composition Quartz crystalline silica (approximately 94%
2.1.2. Dosage of CI and GT of total composition)
During mortar mixing, GT was added into mortar at equal Appearance Fine to coarse sand grains with brown/grey
to light grey color
volume to CI (Tables 1 and 2) [30,35]. The CI volume was calculated
Specific gravity Approximately 2.6
based on CI concentration (i.e. total solid) of 30% (w/w), CI density
 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362 353

months). Additionally, no chemical admixture (e.g. superplasti- Table 5

cizer) was added into the mortar for this w/c, since the mortar Constituents of concrete mixture.

had exhibited an acceptable workability. Thus, there was no inter- Constituent Proportion (kg/m3)
ference from other chemical admixture during the evaluation on IE Cement 420.00
of corrosion inhibitors. Water 234.59
During casting of reinforced mortar specimens, additional water Coarse aggregate 611.77
contributed to mortar mixture by the corrosion inhibitors was Fine aggregate 1,083.19
Water/cement = 0.56
taken into account, to maintain a consistent w/c in control mortar
and mortar admixed with the corrosion inhibitors. Water content
of the inhibitor was the difference between total inhibitor weight
per liter (i.e. density) and inhibitor total solid per liter.
identical to those shown in Table 4. On the other hand, the coarse
aggregates were 10-mm crushed gravels. The w/c was adopted
2.1.5. Preparation of steel rebars from the w/c used for accelerated corrosion (0.54), with an addi-
Steel rebars of 12 mm diameter and 130 mm length were cut tional adjustment for the moisture content of coarse aggregate.
from commercial carbon steel rebars [11,31,34]. Prior to use, the Similar to the preparation of mortar mixture, additional water con-
rebars were sandblasted, degreased with acetone, cleaned with tributed to concrete mixture by the inhibitors was taken into
UPW, and wiped dry [31,51]. The rebars were painted with high account during concrete mixing.
performance epoxy paint [11], except at surface areas of
1,886 mm2 (in the middle) and 943 cm2 (at the top), which
2.2.2. Preparation of CI and GT
remained unpainted for exposure to NaCl solution and electrical
Volume of CI and GT being admixed into concrete are shown in
connection [52,53]. The painted steel rebars were aligned at the
Table 6. Only CI and GT volume which showed the highest IE (i.e.
center of PVC pipe molds as illustrated in Fig. 1. The distance
lowest CR) during accelerated corrosion were selected for RCPT.
between the lower end of rebar and lower end of the mold was
30 mm, to prevent the exposure of unpainted-electrical connection
section to NaCl, and to ensure a good access to oxygen [54].
Table 6
Volume of calcium nitrite corrosion inhibitor (CI) or green tea extract (GT) being
2.2. Materials and sample preparations for rapid chloride permeability admixed into concrete.
test (RCPT) Corrosion inhibitor Volume of inhibitor (L/m3 concrete)
Control –
2.2.1. Preparation of concrete mixture
CI 30.11
Concrete specimens for RCPT were prepared according to mix GT 30.11
design shown in Table 5. Properties of the fine aggregate are

Fig. 1. Reinforced mortar specimen (Adapted and modified from Alghamdi & Ahmad [55]).
354 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362
2.3. Methodologies
2.3.1. Casting reinforced mortar specimens
Procedures for mixing and casting reinforced mortar specimens
were adopted and modified from Gencel et al. [56] and Karahan
and Atis [57]. In brief, a laboratory-scale mixer was used for mortar
mixing. Upon mixing, the fresh mortar mixture was filled into PVC
pipe molds (Fig. 1) in three-equal layers. Each layer was compacted
on a vibrating table for 25 s. Three control specimens and three
specimens for each volume of each corrosion inhibitor were
prepared. After 24 h, the hardened mortar specimens were
de-molded and cured for 28 days in saturated limewater following
ASTM C 511 [57].
2.3.2. Casting concrete specimens
Procedures for mixing and casting concrete specimens were
similar to the previously described procedures for mixing and cast-
ing reinforced mortar specimens, except for the absence of steel
rebars. Moreover, a bigger concrete mixer (20 L capacity) and
cylindrical steel molds (diameter 100 mm and height 200 mm)
were used in place of the smaller laboratory-scale mixer (5 L
capacity) and PVC pipe molds. Three control specimens and three
specimens for each of CI and GT concrete were prepared.
2.3.3. Accelerated corrosion
After 28-day curing, reinforced mortar specimens were sub-
jected to accelerated corrosion, employing a combination of
impressed current and cyclic wetting-drying exposure. The
selected current density was 100 mA/cm2, and the wetting-drying
cycle was four days of wetting and three days of drying
[43,46,58–60]. The current density has been used in other studies
[45,48,49,61–64]. It was originally proposed by Andrade et al.
[65] and further supported by El Maaddawy and Soudki [48].
Setup for the accelerated corrosion is shown in Fig. 2 and was per-
formed at laboratory temperature (26.4 ± 1.7 °C, 70.3 ± 7.5% relative
humidity). The anode was the steel rebar embedded in mortar, the
cathode was AISI 304 stainless steel plate (120  100  10 mm),
and the electrolyte was 3.5% NaCl solution [52]. The reinforced mor-
tar specimen and stainless steel plate were immersed up to 20 mm
from the top of the stainless steel plate, to reduce the corrosion of
the crocodile clip used to hold the plate (Fig. 2). The specimens were
connected in series to subject all specimens to the same applied cur-
rent [48,66]. Nonetheless, mortar pores dry out during the drying
period, which increases mortar resistivity to current flow. Therefore,
applying a current density of 100 mA/cm2 during drying period ele-
vated the total potential of connected specimens above the maxi-
mum potential of the power supply. This triggered the safety
measure of the power supply to automatically shut down the
applied current. Nevertheless, given the significance of cyclic
wetting-drying to simulate an exposure to marine environment
and to give a better representation of corrosion products formed
under natural environment [67], the combination of impressed cur-
rent and cyclic wetting-drying exposure was maintained. However,
the impressed current was only applied during the wetting period,
and the specimens were allowed to corrode naturally during the
drying period. During the drying period, the specimens were
removed from NaCl solution, and the corrosion reaction was sus-
tained by oxygen ingress. A similar setup was used by Malumbela
et al. [47]. The accelerated corrosion study was conducted until
the 12th wetting-drying cycle [32].
2.3.4. Corrosion measurement
2.3.4.1. Electrochemical method. Electrochemical corrosion mea-
surement was performed with linear polarization resistance
(LPR) technique at laboratory temperature (26.4 ± 1.7 °C,
70.3 ± 7.5% relative humidity). The measurement was conducted
with a Metrohm Autolab M204 potentiostat employing a three-
electrode setup [43]. The working electrode (WE) was the steel
rebar embedded in mortar, and the reference electrode (RE) and
counter electrode (CE) were saturated calomel electrode and AISI
304 stainless steel plate (120  100  10 mm). Since the corrosion
measurement was performed at the end of each drying period and
prior to beginning of a new wetting period, the specimen was in
dry condition. Thus, the electrical connection between RE and
WE was established using a sponge wetted with diluted detergent
[43,68]. Prior to LPR measurement, open circuit potential (OCP) of
the rebar was measured. When the OCP value had been stable
(after 10 min, fluctuation less than 10 mV), OCP was determined
and the rebar was polarized with a scan potential of ±20 mV from
OCP and a scan rate of 0.166 mV/s [11,69]. CR and Rp of the rebars
were obtained by analyzing the plots of log current vs. potential
with Nova 1.11 software.
2.3.4.2. Weight loss method. At the end of accelerated corrosion test,
reinforced mortar specimens were broken and embedded steel
rebars were extracted. Rebar weight loss was determined accord-
ing to ASTM G1-90.
2.3.5. Ferric reducing power assay
According to Feng et al. [11], electron donation promotes the
adsorption of a mixed-type corrosion inhibitor on rebar surface.
In our previous investigation, it was indicated that GT behaved
as a mixed-type corrosion inhibitor [32]. Hence, the electron dona-
tion capacity of GT was measured with ferric reducing power
antioxidant assay [11,20].
Procedures for performing the ferric reducing power assay were
adapted from the study by Chan et al. [70]. Antioxidant activity of
the four GT volume used for accelerated corrosion were quantified
by accounting for the dilution factor of each volume in mortar. For
each of the four diluted GT, three different volumes were pipetted
into test tubes, one test tube for each volume, and made up to 1 mL
with UPW. Afterwards, 2.5 mL phosphate buffer (0.2 M and pH 6.6)
and 2.5 mL of 1% (w/v) potassium ferricyanide were added into
each test tube. The aliquot was mixed and incubated at 50 °C for
20 min. The reaction was stopped by adding 2.5 mL of 10% (w/v)
trichloroacetic acid. The 8.5 mL mixture in each test tube was sep-
arated into three test tubes (i.e. three replicates), each containing
2.5 mL solution. Each of the 2.5 mL solution was diluted with
2.5 mL UPW, and subsequently added with 500 mL of 0.1% (w/v)
ferric chloride. The solution was mixed and incubated in the dark
for 30 min prior to absorbance measurement at 700 nm. Ferric
reducing power results were expressed as mg gallic acid equivalent
(GAE). The calibration equation for gallic acid standard was
y = 17.085x where y was the absorbance value at 700 nm and x
was the gallic acid concentration in mg/mL.
2.3.6. Surface examination of rebar
Rebar surface was initially examined visually and further exam-
ined with optical microscope and scanning electron microscope
(SEM). The surface was also subjected to elemental and mineral
analyses with energy-dispersive X-ray spectroscopy (EDX) and
X-ray diffraction spectroscopy (XRD). Additionally, presence of
organic functional groups on the rebar surface was detected with
Fourier-transform infrared spectroscopy (FTIR).
2.3.6.1. Optical microscope. Extracted rebars were observed with
ZEISS Stemi 2000 stereo microscope complemented with Zen
software. Magnification of the objective and camera adapter were
1.0x and 0.5x.
2.3.6.2. SEM and EDX. Rebar surface was examined and analyzed
with Hitachi SU8010 field emission scanning electron microscope
 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362 355

Fig. 2. Accelerated corrosion employing a combination of impressed current and cyclic wetting-drying. The specimens were removed from sodium chloride solution during
drying period (Adapted and modified from Guneyisi & Gesoglu [52] and Fayala et al. [43]).

(FE-SEM) equipped with EDX. Hitachi S3400N-II variable pressure
scanning electron microscope (VP-SEM) was employed for the
examination of the surface at lower magnification. The accelerating
voltage was 15 kV.
2.3.6.3. XRD. Homogenous (i.e. non-localized) layer was scraped
from rebar surface with a scalpel, and analyzed in powder form
with Bruker D8 Discover X-ray diffractometer [71]. The 2h ranged
from 5 to 90°. Cu-Ka radiation source and Lynxeye detector were
employed for the analyses (40 kV, 40 mA, 0.15418 nm) [71,72].
The peaks were identified with data files from Joint Committee
on Powder Diffraction Standards- International Centre for Diffrac-
tion Data (JCPDS-ICDD) and confirmed with published literatures.
2.3.6.4. FTIR. Rebar surface was analyzed with Nicolet iS10 FTIR
equipped with ATR Smart iTR Diamond. The resolution was 4 cm 1
and the number of scans were 64 [73,74]. The wavenumber
ranged from 525 to 4,000 cm 1 [74]. Background spectrum was
collected prior to the collection of every rebar spectrum, and was
subtracted from the rebar spectrum to eliminate the effect of
accumulated carbon dioxide and water vapor during spectra
collection [73].
2.3.7. RCPT
After day moist curing, concrete specimens were subjected to
RCPT according to ASTM C1202 [75]. Prior to testing, the cylindrical
concrete specimens of 100 mm diameter and 200 mm height were
356 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362
cut into discs of 100 mm diameter and 50 mm height. The discs
were fitted into cells of PROOVE’it RCPT instrument, and potential
difference of 60 V was applied across the discs for 6 hours. Magni-
tude of electrical charge passed through the discs after 6 hours was
used to determine the chloride permeability of the concrete spec-
imens according to ASTM C1202.
2.3.8. Statistical analyses
Results are expressed as mean ± standard deviation of three
samples. Results on CR are presented in figures with error bars,
to represent the mean and standard deviation of the three samples.
On the other hand, results on antioxidant activity, elemental anal-
yses, and rebar weight loss are presented in tables. Significant dif-
ferences in the results were evaluated with one-way analysis of
variance (one-way ANOVA) followed by Tukey HSD post hoc test
using SPSS 20 software [76]. Within single set of data, the signifi-
cant differences are represented by superscripted letters after pre-
sented values. The superscripted letters ‘a’ until ‘e’ represent
different statistical groupings, and each group is significantly dif-
ferent based on p-value of 0.05. Therefore, values followed by dif-
ferent superscripted letters are significantly different from each
other.
3. Results and discussion
The following sections present the results on CR, chloride per-
meability, antioxidant activity, examination of rebar surface, and
rebar weight loss.
3.1. Effect of corrosion inhibitors on CR
Effect of CI, GT, and resuspended GT solid on CR are described in
Sections 3.1.1 and 3.1.2.
3.1.1. Effect of CI and GT
Fig. 3 shows the CR of control reinforced mortar specimens and
reinforced mortar specimens admixed with CI or GT. As shown in
Fig. 3, GT specimens showed a lower CR than control and CI
specimens, thus demonstrating a higher IE of GT than CI. The lower
500
450
400
Corrosion rate (µm/year)
350
300
250
200
150
100
50
0
1 2 3 4
Wetting-drying cycle no.
Fig. 3. Mean ± standard deviation in corrosion rate (n = 3) of control reinforced mortar and reinforced mortar admixed with calcium nitrite corrosion inhibitor (CI) or green
tea extract (GT). Values presented in the brackets are the 28-day compressive strength of the mortar.
CR was more prominent at higher GT volume (40 and 30 L/m3
concrete).
3.1.2. Effect of resuspended GT solid
Fig. 4 shows the CR of control reinforced mortar specimens and
reinforced mortar specimens admixed with residual GT solid. It can
be observed that there was no significant difference in the CR of
the control specimens and the specimens which incorporated
residual GT solid. As mentioned in Section 2.1.3, the residual solid
lacks in the active compounds contained in supernatant, which are
hypothesized to be responsible for anti-corrosion activity of GT.
Therefore, the solid only plausibly improves the physical barrier
of mortar by filling up mortar pores and creating denser mortar
matrix. Hence, the similar CR observed in Fig. 4 suggests a similar
protective quality of mortar in control and GT mortar. Therefore,
the active compounds contained in supernatant were responsible
for anti-corrosion of GT by donating electrons as a mixed-type cor-
rosion inhibitor.
3.2. RCPT
Magnitude of electrical charge passed through control concrete
and concrete admixed with CI or GT after 6 hours are presented in
Table 7. As shown in Table 7, all concrete specimens exhibited a
‘High’ permeability to chloride ion according to ASTM C1202 (elec-
trical charge >4000 Coulumb) [77]. However, the magnitude of
electrical charge passed through GT concrete was not significantly
different from the magnitude of charge passed through control
concrete. This indicates a similar chloride permeability of the con-
trol and GT concrete. Thus, the similar chloride permeability fur-
ther supported that the lower CR of GT reinforced mortar
observed in Fig. 3 was not due to an improved physical barrier of
mortar/concrete against corrosion.
3.3. Relationships among antioxidant activity, CR, and Rp
Effect of GT’s antioxidant activity on CR and Rp of GT reinforced
mortar are presented in Table 8. As shown in Table 8, antioxidant
activity of GT affects the CR and Rp of GT reinforced mortar.
Control
(14.91 ± 1.53 MPa)
CI- 40 L/m³ concrete
(19.72 ± 0.78 MPa)
CI- 30 L/m³ concrete
(20.27 ± 4.12 MPa)
CI- 24 L/m³ concrete
(21.46 ± 3.21 MPa)
CI- 20 L/m³ concrete
(18.52 ± 2.96 MPa)
GT- 40 L/m³ concrete
(23.01 ± 1.11 MPa)
GT- 30 L/m³ concrete
(18.05 ± 2.21 MPa)
GT- 24 L/m³ concrete
(19.28 ± 1.38 MPa)
GT- 20 L/m³ concrete
(18.99 ± 2.84 MPa)
5 6 7 8 9 10 11 12
 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362 357

500

450

400
Corrosion rate (µm/year)
350
Control
300
Resuspended GT solid- 40 L/m³
concrete
250
Resuspended GT solid- 30 L/m³
concrete
200
Resuspended GT solid- 24 L/m³
concrete
150
Resuspended GT solid- 20 L/m³
concrete
100

50

0
1 2 3 4 5 6 7 8 9 10 11 12
Wetting-drying cycle no.

Fig. 4. Mean ± standard deviation in corrosion rate (n = 3) of control reinforced mortar and reinforced mortar admixed with residual solid of green tea extract (GT) being
resuspended in water.

Table 7 Nonetheless, accurate correlation coefficients among those param-

Electrical charge passed through concrete after 6 hours. eters could not be drawn due to the larger variations in CR and Rp
Corrosion inhibitor Volume of inhibitor Electric charge than variation in antioxidant activity. This discrepancy might be
(L/m3 concrete) (Coulumb) the effect of the difference in working pH: accelerated corrosion
Control – 5114 ± 586a at alkaline pH of mortar and antioxidant assay at normal pH.
Calcium nitrite corrosion inhibitor 30 8628 ± 995b As shown in study by Muzolf et al. [78], pH affected electron-
Green tea extract 30 5177 ± 569a donating ability: at pH higher than the pKa of potent antioxidant
Values are expressed as mean ± standard deviation of three samples. Within the compounds in GT (epicatechin, epigallocatechin, epicatechin gal-
same column, values followed by different superscripted letters are significantly late, and epigallocatechin gallate), the compounds are deproto-
different from each other based on Tukey HSD test with p-value of 0.05 nated. The deprotonation increases the electron donation capacity
of the compounds, and thereby enhancing antioxidant activity with
Table 8
Effect of green tea extract (GT) antioxidant activity on polarization resistance and increasing pH. Unfortunately, to our knowledge, there is yet an ana-
corrosion rate of GT reinforced mortar. lytical method to quantify the electron donation capacity of crude
plant extract at alkaline pH of concrete (pH 12–13) [78–81]. Increas-
Ferric reducing power Corrosion rate Polarization resistance
(mg GAE) (mm/year) (X) ing working pH of ferric reducing power assay to pH 12–13 reduced
the absorbance values of gallic acid standard, indicating that the
109.51 ± 4.30a 45.18 ± 6.80a 221.18 ± 29.85a
84.27 ± 2.75b 46.37 ± 3.34a 211.14 ± 7.16a
assay was not suitable to measure antioxidant activity at such a high
75.91 ± 1.87c 54.48 ± 11.78a 214.75 ± 16.11a pH. Therefore, the ferric reducing power values presented in Table 8
66.49 ± 3.91c 60.14 ± 12.07a 190.50 ± 38.26a were measured at original working pH of the assay. Nonetheless,
25.44 ± 0.82d 134.25 ± 41.15b 76.18 ± 11.10b despite the absence of accurate correlation coefficients, it can be
21.47 ± 0.52e 195.88 ± 42.16b 64.49 ± 5.85b
observed that the magnitude of antioxidant activity influenced the
Values are expressed as mean ± standard deviation of three samples. Within the ability of GT to increase Rp and reduce CR: the higher is the electron
same column, values followed by different superscripted letters are significantly donation capacity of GT measured with ferric reducing power assay,
different from each other based on Tukey HSD test with p-value of 0.05. Abbrevi-
the higher is the Rp and the lower is the CR.
ation: GAE = gallic acid equivalent.

Fig. 5. Steel reinforcing bar extracted from control mortar and mortar admixed with 30 L/m3 concrete of calcium nitrite corrosion inhibitor (CI) or green tea extract (GT).
358 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362

3.4. Surface examination of rebar 3.4.1. Visual inspection

Fig. 5 shows an example of three steel rebars extracted from
Visual inspection, optical microscope examination, SEM comple- each mortar group (control, CI, and GT mortar). In each mortar
mented with EDX, XRD, and FTIR analyses of steel rebars extracted group, a similar finding was observed on the three rebars. There-
after accelerated corrosion are presented in the next sections. fore, only one rebar from each mortar group is presented in

Fig. 7. Scanning electron microscope image of steel reinforcing bar extracted from
Fig. 6. Optical microscope image of steel reinforcing bar extracted from (a) control (a) control mortar, (b) mortar admixed with calcium nitrite corrosion inhibitor at
mortar, (b) mortar admixed with calcium nitrite corrosion inhibitor at 30 L/m3 30 L/m3 concrete, and (c) mortar admixed with green tea extract at 30 L/m3
concrete, and (c) mortar admixed with green tea extract at 30 L/m3 concrete. concrete.
 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362 359

Fig. 5. Moreover, only rebars extracted from mortar added with CI
or GT at 30 L/m3 concrete are presented, because this volume
showed the highest IE during accelerated corrosion. Nonetheless,
a similar result was observed on the rebars extracted from mortar
added with the other volume of CI or GT.
As shown in Fig. 5, rebar extracted from GT mortar had the least
corrosion damage (i.e. largest uncorroded area), in agreement with
the lower CR of GT reinforced mortar presented in Fig. 3. A white
layer was observed on the uncorroded area of this rebar, and this
layer was also observed on rebar extracted from CI mortar. Further
examination of the layer with microscopic methods and analyses
of the layer with EDX, XRD, and FTIR are presented in the next
sections.
3.4.2. Optical microscope examination
Optical microscope images of the white layer observed on the
uncorroded area of rebars extracted from GT and CI mortar are pre-
sented in Fig. 6. Fig. 6 also compares the rebars with rebar
extracted from control mortar: rebar from control mortar is mostly
covered with brownish-black corrosion product. More importantly,
the rebar does not exhibit the white layer observed on rebars from
GT and CI mortar.
3.4.3. SEM-EDX
The white layer on the surface of rebars extracted from GT and
CI mortar was further examined with VP-SEM, and analyzed with
FE-SEM equipped with EDX to elucidate the elemental composition
of the layer. The VP-SEM images are shown in Fig. 7 and the ele-
mental analyses are presented in Table 9.
As shown in Table 9, oxygen constitutes 40–60% of all rebar sur-
face (except for untested rebar surface), suggesting the formation of
iron oxides [72]. Moreover, Table 9 suggests that the white layer on
rebar extracted from GT mortar was enriched with calcium, as evi-
denced by the significantly lower calcium content on rebar extracted
from control mortar, on which the white layer was absent. Further-
more, the calcium was derived from mortar, as calcium was not
detected on the surface of untested rebars. The presence of this
calcium-enriched layer significantly reduced the iron content on
rebars extracted from GT mortar than on rebars extracted from con-
trol mortar and untested rebars. The white layer on rebar extracted
from CI mortar was similarly enriched with calcium.
3.4.4. FTIR and XRD
Calcium enrichment of the white layer on rebar extracted from
GT mortar was further confirmed with XRD and FTIR analyses
(Figs. 8 and 9). XRD spectra shown in Fig. 8 indicate that the white

Table 9
Elemental analyses on surface of steel reinforcing bars extracted from control mortar and mortar admixed with calcium nitrite corrosion inhibitor (CI) or green tea extract (GT).

Corrosion inhibitor Volume of inhibitor (L/m3 concrete) Percentage weight

Oxygen Chloride Calcium Iron
Control – 41.52 ± 5.98a 3.60 ± 2.84a 1.94 ± 1.49a 52.94 ± 4.10a
CI 30 44.60 ± 6.38a 4.49 ± 0.67a 20.38 ± 7.60b 30.54 ± 12.33bc
GT 30 59.11 ± 10.26bc 3.52 ± 0.98a 22.98 ± 5.43b 14.39 ± 11.06bd
Untested/original – 11.16 ± 3.75bd – – 88.83 ± 3.75be

Values are expressed as mean ± standard deviation of three samples. Within the same column, values followed by different superscripted letters are significantly different
from each other based on Tukey HSD test with p-value of 0.05.

Fig. 8. XRD spectra of steel reinforcing bar extracted from control mortar and mortar admixed with calcium nitrite corrosion inhibitor or green tea extract.
360 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362

Fig. 9. FTIR spectra of steel reinforcing bar extracted from control mortar and mortar admixed with green tea extract.

layer on rebar from GT mortar was enriched with three major cal- Table 10
cium carbonate polymorphs namely calcite, aragonite, and vaterite Weight loss of steel reinforcing bars.
[82–85]. The main peak of aragonite, vaterite, and calcite are indi- Corrosion inhibitor Volume of inhibitor Weight loss
cated by peak 1–3. Although the main peak of aragonite and vater- (L/m3 concrete) (%)
ite (peak 1 and 2) [84–88] overlap with the peaks of corrosion Control – 2.94 ± 0.40a
products [38,72,89–91], main peak of calcite (peak 3) was attribu- Calcium nitrite corrosion 40 2.88 ± 0.32a
ted to calcite alone (JCPDS PDF 00-005-0586 and Ref. inhibitor (CI) 30 2.68 ± 0.38ac
[84,87,88,92,93]) and was not detected on rebar extracted from 24 2.62 ± 0.25ad
20 2.88 ± 0.23a
control mortar. Nevertheless, the presence of the three calcium
Green tea extract (GT) 40 2.09 ± 0.18bcd
carbonate polymorphs on rebar extracted from GT mortar was also 30 1.82 ± 0.16b
suggested by the FTIR spectra shown in Fig. 9. 24 2.24 ± 0.17a
The FTIR absorption bands corresponding to the three poly- 20 2.39 ± 0.20a
Resuspended residual solid 40 2.76 ± 0.23a
morphs are 1,405 and 711 cm 1 for calcite, 961 and 871 cm 1 for
of green tea extract 30 2.55 ± 0.27a
aragonite and vaterite, and 871 cm 1 for calcite and vaterite 24 2.59 ± 0.36a
[73,74,86,88,94,95]. The aforementioned bands represent different 20 2.62 ± 0.32a
vibrations of carbonate ions: asymmetrical stretching vibration
Values are expressed as mean ± standard deviation of three samples. Within the
(m3) at 1,405 cm 1, symmetrical stretching vibration (m1) at same column, values followed by different superscripted letters are significantly
961 cm 1, out-of-plane bending vibration (m2) at 871 cm 1, and different from each other based on Tukey HSD test with p-value of 0.05.
in-plane bending vibration (m4) at 711 cm 1 [73]. On the other
hand, the band at 1,641 cm 1, 2,337–2,361 cm 1, and 3,402 cm 1 with the absence of significant difference in CR as presented in
correspond to the vibration of O–H bending, CO2, and O–H stretch- Fig. 4, Table 10 shows the absence of significant difference in
ing respectively [92,96,97]. weight loss between rebars from control mortar and rebars
Overall, XRD and FTIR analyses illustrated that GT induces the extracted from mortar admixed with resuspended GT solid.
formation of protective layer on rebar, which is enriched with cal- Therefore, in overall, the presence of the calcium carbonate-
cium carbonate polymorphs (calcite, aragonite, and vaterite). The enriched layer reduces rebar corrosion as evidenced by the reduced
corrosion inhibition by this layer is illustrated in next section, by rebar weight loss.
comparing rebar weight loss in absence and in presence of this
layer. 3.6. Overall effects of GT on rebar corrosion

3.5. Rebar weight loss
Weight loss of rebars extracted from control mortar and mortar
admixed with corrosion inhibitors (CI, GT, and resuspended GT
solid) are presented in Table 10. As shown in Table 10, in agree-
ment with Fig. 3, rebars extracted from GT mortar had lower
weight loss than the rebars extracted from control and CI mortar.
In particular, the rebars extracted from mortar added with GT at
30 L/m3 concrete showed a significantly lower weight loss than
the rebars from control and CI mortar. On the other hand, in line
We have observed that rebars embedded in GT mortar had
lower CR than the rebars embedded in control and CI mortar.
The lower CR was not due to an improved physical barrier of mor-
tar/concrete against corrosion, since control and GT concrete had a
similar chloride permeability, and reinforced mortar incorporating
solely residual solid of GT had a similar CR to control reinforced
mortar. Instead of improving the physical barrier of mortar/
concrete GT reduced CR by forming a layer enriched with calcium
carbonate. This layer inhibited rebar corrosion, as suggested by a
decreased rebar weight loss in presence of this layer.
 I. Pradipta et al. / Construction and Building Materials 221 (2019) 351–362
4. Conclusion
In this paper, the formation of protective layer on rebar from GT
mortar was confirmed with visual inspection and microscopic
examinations (optical microscope and SEM). In presence of this
layer, rebar weight loss was reduced, and analyses with EDX,
XRD, and FTIR suggested that this layer was enriched with calcium,
precisely the calcium carbonate polymorphs (calcite, aragonite,
and vaterite). Corrosion inhibition by this layer was further
demonstrated by a similar chloride permeability between control
and GT concrete, and a similar CR between control reinforced mor-
tar and reinforced mortar which was added with residual solid of
GT. These similarities ruled out the plausible reduction in CR due
to an improved physical protection of mortar/concrete against cor-
rosion. Although the formation of protective layer and increase in
Rp were influenced by the magnitude of antioxidant activity, in
this study GT has demonstrated a better IE than CI especially at
the higher range of volume. This should encourage more studies
on the use of sustainable ‘green’ corrosion inhibitors in concrete.
For example, a future study can investigate the IE of more
cost-effective sources of antioxidants. These materials can be
derived from various agricultural by-products such as fruit peels,
fruit seeds, and solid wastes from cereal grain processing (for
instance corncob, rice bran, and wheat husk) [98–102].
Acknowledgement
The authors would like to thank Advanced Engineering Platform
of Monash University Malaysia for funding this research.
Declaration of interest
The authors do not have any conflict of interest.
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