corrosion and

materials degradation

Review
Understanding Fibre-Matrix Degradation of FRP
Composites for Advanced Civil Engineering
Applications: An Overview
R. K. Singh Raman 1,2, * , Faye Guo 2 , Saad Al-Saadi 2 , Xiao-Ling Zhao 3 and Rhys Jones 1
1 Department of Mechanical and Aerospace Engineering, Monash University, Clayton, VIC 3800, Australia;
rhys.jones@monash.edu
2 Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia;
faye.guo16@gmail.com (F.G.); saad.al-saadi@monash.edu (S.A.-S.)
3 Department of Civil Engineering, Monash University, Clayton, VIC 3800, Australia;
zhao.xiao.ling@monash.edu
* Correspondence: Raman.Singh@monash.edu




Received: 16 May 2018; Accepted: 13 June 2018; Published: 27 June 2018


Abstract: Common concretes use considerable amounts of fresh water and river sand, and their
excessive use is already seriously implicating the environment. In this respect, seawater and sea sand
concrete (SWSSC) is a very attractive alternative, since it addresses the increasing shortage of fresh
water and dredging of river sand. A major concern with reinforced SWSSC is the severe corrosion of
the steel reinforcements by seawater (that has a very high content of chloride which is very corrosive),
thereby seriously impairing the strength of such concrete. Fibre reinforced polymer (FRP) can be
a suitable alternative to replace steels as reinforcement. However, there has been little systematic
work to understand the degradation kinetics and mechanisms of FRP in the chloride-containing
alkaline SWSSC environment. This review first provides an overview of the degradation of FRP
composites in normal concrete and chloride-containing alkaline SWSSC environments, and then
presents an example of a recent study using scanning electron microscopy (SEM) and Fourier
transform infrared spectroscopy (FTIR) that may provide a pathway to systematic experimental
approach to understanding such degradation. The review also makes a comprehensive assessment of
the influence of environment-assisted degradation on mechanical properties of FRPs.

Keywords: seawater and sea sand concrete (SWSSC); durability; carbon fibre reinforced polymer
(CFRP); glass fibre reinforced polymer (GFRP); basalt fibre reinforced polymer (BFRP)

1. Introduction
Global population is expected to increase to >9 billion by 2050 [1]. As a result, the demand for
infrastructure and construction materials such as concrete is set to increase steeply from the current
annual usage of 5b yard3 [2], which will cause shortage of fresh water and river sand (i.e., the two
main ingredients of conventional concrete). Currently, billions of litres of fresh water are used in
the mixing, curing and cleaning stages of concrete production [3]. On the other hand, use of large
quantities of river sand causes sand-dredging and damages ecosystem (fish-depletion, floods, erosion,
landslides) [4]. In fact, in some areas this is already being addressed, as is evident from the article,
“Mumbai Government Bans River Sand Mining” [5]. The demand of fresh water and river sand will be
further accentuated by the increasing need of additional coastal infrastructures due to the rising sea
level [6], which will require transport of large quantities of river sand and fresh water from inland to
the coastal areas. Therefore, there is a great value in finding substitutes for the fresh water and river

Corros. Mater. Degrad. 2018, 1, 27–41; doi:10.3390/cmd1010003 www.mdpi.com/journal/cmd

Corros. Mater. Degrad. 2018, 1 28

sand in production of conventional concrete. The potential use of seawater and sea sand concrete
(SWSSC) is a hugely attractive proposition.
SWSSC is a hugely attractive alternative to traditional concrete, but it also comes with an enormous
challenge of finding a suitable reinforcement material since it will be nearly impossible to use the
traditional reinforcement material, i.e., carbon steels since they will suffer severe corrosion due to
very high chloride contents of seawater and sea sand. ‘Concrete cancer’, which is an enhanced
corrosion of steel reinforcement by Cl− ions causing concrete spallation and cracking even in the case
of the conventional concrete, will only be highly accelerated in the presence of seawater in SWSSC.
Fibre reinforced polymer (FRP) that may suffer very little corrosion in chloride solution/seawater
(in comparison to carbon steels) is a highly suitable alternative material for SWSSC reinforcements.
FRPs also possess competent mechanical properties to carbon steels. Though both glass-fibre
and carbon-fibre reinforced polymers (i.e., GFRPs and CFRPs) are the traditional FRP materials,
glass fibres are considerably cheaper (than carbon fibres) and hence GFRPs are most widely used [7],
even though carbon fibres possess a far superior strength-to-modulus ratio as well as resistance to
environment-assisted degradation [8].
It is important to understand the degradation of FRPs in the alkaline environment of concrete,
particularly in the mixed alkali + chloride environment of SWSSC. There is considerable literature on
the deterioration in mechanical properties of FRPs after pre-exposure to simulated environment of
traditional concrete [7,9–25] as well as a few similar studies after pre-exposure to SWSSC [11,26,27].
There are a few reports also on deterioration in mechanical properties of FRPs under the condition of
simultaneous exposure to the simulated environment of SWSSC and applied load [28,29]. However,
the chemical aspects of the degradation of the FRPs (and more specifically, the fibre–matrix interface)
are poorly understood.
This review first presents a brief overview of the considerable knowledge of the degradation
of FRPs in normal concrete environment as well as relatively limited knowledge of the degradation
of FRP composites in chloride-containing alkaline SWSSC environment, particularly the influence
of environment-assisted degradation of mechanical properties of FRPs under the two conditions.
This review also presents the findings of a recent study that, on the basis of microscopic and
spectroscopic investigation, suggests the role of seawater in retarding the chemical degradation
of certain FRPs in SWSSC, i.e., the beneficial effects of using seawater-FRP combination.

2. Mechanical Properties of FRPs Pre-Exposed to Traditional Concrete Environments

Several studies have reported degradation in mechanical properties of bars of different FRPs
(viz., glass fibre reinforced polymer (GFRP), carbon fibre reinforced polymer (CFRP), and basalt
fibre reinforced polymer (BFRP)) after their pre-exposure to different simulated civil engineering
environments, such as the alkaline environment of normal concrete [7,9–25]. These studies identified
a few factors that influence the mechanical properties. There are several reports on the degradation
of GFRPs such as the factors that influence the degradation, e.g., pH [16], exposure temperature [18],
moisture content of concrete [10,12,14], polymer type [9] and the magnitude of pre-loading [7,13,19],
as well as the GFRP degradation mechanism [20–23]. When exposed to distilled water, simulated
concrete solution or concrete leachate solution, vinylester resin of GFRP is reported to plasticize [30].
However, degradation of both matrix and fibre was found to be accelerated in the alkaline solution.
Similar findings were also reported for epoxy-based BFRP [31], but the reports on degradation of
BFRPs are limited [11,15,24,25]. Wu et al. [11,25] found the retained tensile strength of BFRP bars to
reduce much quicker in the simulated alkaline pore solution than in deionized water, salt, or acid
environment. Serbescu et al. [24] suggested the exposure time to be the most important factor affecting
the degradation of BFRPs. Benmokrane et al. [15] investigated the effect of polymer type on degradation
of BFRP bars and found a basalt/vinyl ester FRP to have to an inferior resistance to the basalt/epoxy
FRP in an alkaline solution.
Corros. Mater. Degrad. 2018, 1 29

3. Mechanical Properties of FRPs Pre-Exposed to SWSSC

Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 3 of 16

With the huge potential of SWSSC, it is mandatory to understand the durability of the
3. Mechanical Properties of FRPs Pre-Exposed to SWSSC
strengthening rebars of FRPs in the relatively new environment of SWSSC. There are reports comparing
With the
the degradation in huge potential
mechanical of SWSSC,
properties of itFRPs
is mandatory
in normaltoconcrete
understand the durability
or seawater alone. ofWhile
the the
strengthening rebars of FRPs in the relatively new environment of SWSSC.
highly alkaline concrete environment is reported to be highly detrimental, seawater alone is reported There are reports
comparing the degradation in mechanical properties of FRPs in normal concrete or seawater alone.
to have only a marginal effect [10,11,31–33]. Chen et al. [10] found GFRPs to retain 74% of its tensile
While the highly alkaline concrete environment is reported to be highly detrimental, seawater alone
strength after exposure to seawater, 71% after exposure to distilled water and only 64% after exposure
is reported to have only a marginal effect [10,11,31–33]. Chen ◦et al. [10] found GFRPs to retain 74% of
to alkali solution (exposure in each case was for 70 days at 60 C). Whereas, strength retention of CFRP
its tensile strength after exposure to seawater, 71% after exposure to distilled water and only 64%
was 96%
after after exposure
exposure to alkalitosolution
the alkali solution.
(exposure Wucase
in each et al.
was[31]
forreported
70 days atrespectively
60 °C). Whereas, similar strength
strength
retention for GFRP,
retention of CFRP BFRP,
was and CFRPexposure
96% after after 60today theimmersion in alkali,
alkali solution. Wu et seawater, and distilled
al. [31] reported respectivelywater.
The preceding
similar description
strength retention concerns
for GFRP, BFRP, the
and degradation
CFRP after 60ofday FRPs in single
immersion environment
in alkali, seawater, of andalkali,
distilled water.
seawater, or distilled water, whereas SWSSC constitutes a mixed environment of alkali + high
The preceding
chloride content description
of seawater. Very concerns
little isthe degradation
reported on theof FRPs in single in
degradation environment
mechanical of properties
alkali,
of FRPs after pre-exposure to the simulated environment of SWSSC [9–11,16,32–35]. In a high
seawater, or distilled water, whereas SWSSC constitutes a mixed environment of alkali + study by
chloride content of seawater. Very little is reported on the degradation in mechanical properties of
El-Hassan et al. [36], the degradation mechanism of GFRP during exposure to seawater-containing
FRPs after pre-exposure to the simulated environment of SWSSC [9–11,16,32–35]. In a study by El-
concrete for 15 months included hydrolysis of polymer matrix and loss of strength of the fibre–matrix
Hassan et al. [36], the degradation mechanism of GFRP during exposure to seawater-containing
interface,
concretebutfor
the15fibre
months itself was not
included found to
hydrolysis have suffered
of polymer much
matrix and lossattack. As shown
of strength in Figure 1a,b,
of the fibre–matrix
Wanginterface,
et al. [26]but
have
the recently
fibre itselfcarried
was not out a comprehensive
found to have suffered study
much onattack.
the retention
As shown in in
tensile
Figurestrength
1a,b, of
BFRPs and GFRPs after exposure to simulated SWSSC solutions of normal (N)
Wang et al. [26] have recently carried out a comprehensive study on the retention in tensile strength and high performance
(HP) ofconcrete
BFRPs at anddifferent
GFRPs aftertemperatures
exposure to (32,simulated 55 ◦ C).solutions
40, and SWSSC The normal concrete
of normal (N) (N)
andhas highmuch
performance
greater alkalinity(HP) thanconcrete
the high at different temperatures
performance concrete(32,(HP),
40, andas55also
°C). suggested
The normal concrete (N) has It is
in this article.
much
evident fromgreater
Figurealkalinity thanthe
1a,b that thetensile
high performance concrete (HP),
strength retention as also
of both BFRP suggested
and GFRP in this article. It with
decreased
is evident from Figure 1a,b that the tensile strength retention of both BFRP
the increase in temperature, duration of exposure, or the alkalinity of the exposure environment. and GFRP decreased with
the increase in temperature, duration of exposure, or the alkalinity of the exposure environment.
However, the decrease in tensile strength retention was more rapid for BFRP than for GFRP. The rapider
However, the decrease in tensile strength retention was more rapid for BFRP than for GFRP. The
degradation of BFRP is consistent with the greater water uptake and the greater extent of chemical
rapider degradation of BFRP is consistent with the greater water uptake and the greater extent of
attackchemical
of fibreattack
of BFRP (than
of fibre of GFRP),
BFRP (than as described in the succeeding
GFRP), as described section.section.
in the succeeding

Figure 1. Cont.
Corros. Mater. Degrad. 2018, 1 30
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Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 4 of 16

Figure 1. Tensile strength retention of FRP bars after pre-exposure to the simulated solutions of
Figure 1. Tensile strength retention of FRP bars after pre-exposure to the simulated solutions of normal
normal
Figure concrete
1. Tensile(N) and high
strength performance
retention of FRP(HP) forafter
bars different durationsto
pre-exposure at the
different temperatures
simulated solutions(32,
of
concrete
40, (N)55and
and °C): high
(a) performance
BFRP and (b) (HP)
GFRP. for different
(Adapted from durations
[26], with at different
permission from temperatures
Elsevier, (32, 40,
2018). (32,
normal concrete (N) and high performance (HP) for different durations at different temperatures
and 55 ◦ C): (a) BFRP and (b) GFRP. (Adapted from [26], with permission from Elsevier, 2018).
40, and 55 °C): (a) BFRP and (b) GFRP. (Adapted from [26], with permission from Elsevier, 2018).
Figure 2 compares the trends in the influence of temperature, duration of exposure or the
Figure 2 compares
alkalinity
Figurereported inthe
2 compares Wangtrends in the
theettrends
al.’s influence
study withofthe
temperature,
[26]influence
in the limited data duration of exposure
on degradation
of temperature, duration of BFRPorinthe
of exposure alkalinity
another
or the
reported in[11],
study Wang
alkalinity and etthe
reportedal.’s study
trends
in Wang are[26]
et with
found
al.’s tothe
study limited
be[26]
consistent.data
with the on degradation
limited of BFRPofinBFRP
data on degradation another study [11],
in another
and the trends
study [11], are
andfound to be
the trends consistent.
are found to be consistent.

Figure 2. Comparison of tensile strength retention of BFRP bars in SWSSC and alkaline environments
at different
Figure temperatures
2. Comparison (Adapted
of tensile from retention
strength [26], withofpermission
BFRP barsfrom Elsevier,
in SWSSC and2018).
alkaline environments
Figure 2. Comparison of tensile strength retention of BFRP bars in SWSSC and alkaline environments
at different temperatures (Adapted from [26], with permission from Elsevier, 2018).
In order
at different to understand
temperatures the rolefrom
(Adapted of the extent
[26], withof the degradation
permission of fibres2018).
from Elsevier, during pre-exposures
on theIn order to understand the role of the extent of the degradation of fibres duringinvestigation
tensile strength retention, Wang et al. [26] carried out a thorough microscopic of
pre-exposures
In
onorder to understand
the tensile the roleWang
strength retention, of theetextent
al. [26]of the degradation
carried of fibres
out a thorough during
microscopic pre-exposures
investigation of on
the tensile strength retention, Wang et al. [26] carried out a thorough microscopic investigation of the
cross-sections of the BFRP and GFRP after pre-exposure to normal (N) and high performance (HP)
concrete solutions at different temperatures (32, 40, and 55 ◦ C) for the longest test duration (63 days).
Corros. Mater. Degrad. 2018, 1 31
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 5 of 16

the cross-sections of the BFRP and GFRP after pre-exposure to normal (N) and high performance
For comparison, unexposed samples were also examined. Figures 3 and 4 show the scanning electron
(HP) concrete solutions at different temperatures (32, 40, and 55 °C) for the longest test duration (63
microscopy (SEM) images unexposed
days). For comparison, of the ground and were
samples polished cross-sections.
also examined. Figures 3 and 4 show the scanning
In the case
electron of the unexposed
microscopy (SEM) images BFRP,
of thethe basalt
ground andresin, fibre,
polished and the fibre–resin interface are all
cross-sections.
largely intact,
In theascase
seenofinthe
Figure 3a. The
unexposed a fewthe
BFRP, minor
basaltcracks
resin, seen
fibre,atand
thethe
fibre edges were
fibre–resin attributed
interface are allto the
largely
grinding andintact, as seen
polishing in Figure
process 3a. The afor
employed fewthe
minor cracks seen
specimen at the fibre
preparation. Inedges were
the case ofattributed to
the pre-exposed
the grinding and polishing process employed for the specimen preparation. In the
BFRP, the fibre and fibre–resin interface in the areas near the edge the bar were the first to come in case of the pre-
exposed
contact with theBFRP, the fibre environment
aggressive and fibre–resin interface
and suffer in the areas near
degradation. Thetheattack
edge the bargradually
front were the first to
progressed
come in contact with the aggressive environment and suffer degradation. The attack front gradually
towards the centre of the bar specimen with increase in the duration of exposure on the temperature
progressed towards the centre of the bar specimen with increase in the duration of exposure on the
(as shown in Figure 3b–d). Also, the attack can be seen to intensify with the increasing duration or
temperature (as shown in Figure 3b–d). Also, the attack can be seen to intensify with the increasing
temperature of exposure.
duration or temperature of exposure.

Figure 3. Cont.
Corros. Mater. Degrad. 2018, 1 32
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 6 of 16

Figure 3. SEM images of the cross-sections of BFRP: (a) without exposure and (b) after exposure to
Figure 3. SEM images of the cross-sections of BFRP: (a) without exposure and (b) after exposure to
SWSSC for 63 days at 32 °C [26]. SEM images of the cross-sections of BFRP after exposure to SWSSC
SWSSC ◦ [26]. SEM images of the cross-sections of BFRP after exposure to SWSSC
for for 63 days
63 days at: (c)at4032°C C
and (d) 55 °C (Adapted from [26], with permission from Elsevier, 2018).
for 63 days at: (c) 40 ◦ C and (d) 55 ◦ C (Adapted from [26], with permission from Elsevier, 2018).
The trend described above for BFRP was found to be same for GFRP (Figure 4). However, the
The
extenttrend described
of attack above for
was relatively less BFRP waswhich
for GFRP, found
is to be same
consistent forthe
with GFRP (Figure
greater tensile4). However,
strength
the extent of attack
retention of GFRPwas
(asrelatively less for
seen in Figures GFRP,
1 and 2). which is consistent with the greater tensile strength
retention of GFRP (as seen in Figures 1 and 2).
Corros. Mater. Degrad. 2018, 1 33
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 7 of 16

Figure 4. SEM images of the cross-sections of GFRP: (a) without exposure, and (b–d) after exposure
Figure 4. SEM images of the cross-sections of GFRP: (a) without exposure, and (b–d) after exposure
to SWSSC for 63 days respectively at 32, 40, and 55 °C (Adapted from [26], with permission from
to SWSSC 63 days respectively at 32, 40, and 55 ◦ C (Adapted from [26], with permission from
for2018).
Elsevier,
Elsevier, 2018).
4. Moisture Uptake of FRPs and Advanced Characterisation of Degradation of Fibre–Matrix
4. Moisture
InterfaceUptake of FRPs and Advanced Characterisation of Degradation of
Fibre–Matrix Interface
Very recently, authors’ group has carried out further investigation to characterise the
Very recently,
contribution ofauthors’ grouptohas
epoxy matrix FRPcarried out further
degradation duringinvestigation
exposure. In to
thischaracterise the
study, water contribution
uptake of
of epoxy matrix to FRP degradation during exposure. In this study, water uptake of FRPs
was determined during exposure to different test solutions simulating normal concrete (NC),
high performance concrete (HPC), seawater and sea sand normal concrete (SWSSNC), seawater and sea
Corros. Mater. Degrad. 2018, 1 34
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 8 of 16

sand high
FRPsperformance
was determined concrete
during(SWSSHPC). In addition,
exposure to different the solid residue
test solutions simulatinggenerated upon evaporation
normal concrete (NC),
of thehigh
remaining test solutions
performance at theseawater
concrete (HPC), end of the andsix-month exposure
sea sand normal to the
concrete simulated
(SWSSNC), environments
seawater and
sea sand high performance concrete (SWSSHPC). In addition, the solid residue
were examined using attenuated total reflectance–Fourier transform infrared spectroscopy (ATR–FTIR) generated upon
evaporation
to establish of the
whether remaining
the residuestest solutionsspectral
contained at the end of the six-month
evidence for epoxyexposure to the simulated
matrix (which will confirm
environments were examined
leaching of epoxy during exposure). using attenuated total reflectance–Fourier transform infrared
spectroscopy (ATR–FTIR) to establish whether the residues contained spectral evidence for epoxy
Moisture uptakes of different FRPs (CFRP, GFRP, and BFRP) during exposure to different solutions
matrix (which will confirm leaching of epoxy during exposure).
at 60 ◦ C for up to six months are plotted in Figure 5a–c (average weight gains are plotted with the
Moisture uptakes of different FRPs (CFRP, GFRP, and BFRP) during exposure to different
normalised immersion
solutions time
at 60 °C for up (i.e.,
to siximmersion
months are days
plotted1/2)).
in Figure 5a–c (average weight gains are plotted
Moisture
with the normalised immersion time (i.e., immersion days with
uptake (weight gain) of each FRP increased 1/2)). immersion time, however, the weight
gains in DW, HPC, and SWSSHPC (low alkali environments)
Moisture uptake (weight gain) of each FRP increased with plateaued
immersion after 30 however,
time, days, whereas the FRPs
the weight
exposed to in
gains NC,
DW,SWSSNC
HPC, and (the higher alkalinity
SWSSHPC (low alkalienvironments) continuedafter
environments) plateaued to gain weight
30 days, at high
whereas therates
FRPs
for the exposed
entire to NC, SWSSNC
test duration of 180 (the higher
days. Thealkalinity environments)
greater moisture uptakecontinued to gain
in the high weight
alkali at high
environment
rates for the
(NC/SWSSNC) entire test with
is consistent duration of 180 days.
the greater loss inThe greater
tensile moisture
strength uptake
of FRPs in the
in the twohigh alkali
environments,
environment (NC/SWSSNC) is consistent with the greater loss in tensile strength of FRPs in the two
as shown in Figures 1 and 2 [10,26]. In fact, BFRP showed an acceleration in weight gain after ~90 days,
environments, as shown in Figures 1 and 2 [10,26]. In fact, BFRP showed an acceleration in weight
which is also consistent with the much accelerated loss in tensile strength of BFRP in high alkali
gain after ~90 days, which is also consistent with the much accelerated loss in tensile strength of BFRP
environment (Figure 1a).
in high alkali environment (Figure 1a).

(a)

Figure 5. Cont.
Corros. Mater. Degrad. 2018, 1 35
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 9 of 16

(b)

(c)
Figure 5. Moisture uptake of (a) CFRP (b) GFRP (c) BFRP during exposure to different testing
Figure 5. Moisture uptake of (a) CFRP (b) GFRP (c) BFRP during exposure to different testing solutions
solutions at 60 °C for up to six months (Adapted from [37,38], with permission from Elsevier, 2018).
at 60 ◦ C for up to six months (Adapted from [37,38], with permission from Elsevier, 2018).
Moisture uptake by each FRP type was minimum in the low alkali environments (HPC and
Moisture
SWSSHPC), uptake by each
and between theFRP type was minimum
two environments, in thethat
it is interesting lowthe
alkali environments
moisture uptake was (HPC
lower and
SWSSHPC),
when seawater was present (i.e., SWSSHPC < HPC). In fact, even between the two high alkali was
and between the two environments, it is interesting that the moisture uptake
lower when seawater was present (i.e., SWSSHPC < HPC). In fact, even between the two high alkali
environments (i.e., NC and SWSSNC), the water uptake was lower when seawater was present (i.e.,
SWSSNC < NC). These observations suggested the beneficial role of the presence of seawater and sea
sand in resisting water uptake/degradation. The exception was BFRP that suffered considerably greater
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 10 of 16

environments
Corros. (i.e.,
Mater. Degrad. NC1
2018,and SWSSNC), the water uptake was lower when seawater was present (i.e., 36
SWSSNC < NC). These observations suggested the beneficial role of the presence of seawater and sea
sand in resisting water uptake/degradation. The exception was BFRP that suffered considerably
water
greateruptake
waterinuptake
SWSSNC in than in NC,
SWSSNC particularly
than after 90 daysafter
in NC, particularly of exposure,
90 daysindicating damaging
of exposure, role
indicating
of sweater in this case.
damaging role of sweater in this case.
Figure
Figure 66 shows
shows the
the FTIR
FTIR absorption
absorption spectra
spectra of
of unexposed
unexposed FRPsFRPs (i.e.,
(i.e., reference)
reference) and
and the
the residues
residues
of the SWSSC solutions after exposure of FRPs for 84 days at 55 ◦ C [27]. The bands of the reference
of the SWSSC solutions after exposure of FRPs for 84 days at 55 °C [27]. The bands of the reference
spectrum
spectrum areare identified
identified inin the
the literature
literature [39–43]. The bands
[39–43]. The bands present
present in
in the
the spectrum
spectrum for
for the
the FRP
FRP
reference are also present in the spectra for the two residues, confirming the leaching
reference are also present in the spectra for the two residues, confirming the leaching of FRP matrixof FRP matrix
into
into the
the simulated
simulated SWSSC
SWSSC solutions
solutions during
during exposure.
exposure.

Figure 6. Representative FTIR spectra for FRPs and those for the residues collected after exposure to
Figure 6. Representative FTIR spectra for FRPs and those for the residues collected after exposure
the simulated normal (NC) and high performance (HP) SWSSC solutions. (Adapted from [27], with
to the simulated normal (NC) and high performance (HP) SWSSC solutions. (Adapted from [27],
permission from Elsevier, 2018).
with permission from Elsevier, 2018).

The SEM
The SEM images
images in in Figures
Figures 33 and
and 44 provide
provide convincing
convincing evidence
evidence ofof degradation
degradation of of fibre
fibre and
and
fibre–epoxy interface
fibre–epoxy interface due
due to
to exposure
exposure toto SWSSC
SWSSC environment.
environment. However,
However, it it may
may notnot be
be convincingly
convincingly
concluded whether matrix suffered degradation due exclusively to exposure
concluded whether matrix suffered degradation due exclusively to exposure since it could be since it could be argued
argued
that the degradation of the fibre–matrix interface seen in Figures 3 and 4 [26] might
that the degradation of the fibre–matrix interface seen in Figures 3 and 4 [26] might have been caused have been caused
(or accentuated)
(or accentuated) just just by
by the
the grinding
grinding ofof the
the samples
samples that
that is
is employed
employed for for revealing
revealing the the cross-section
cross-section
of the pre-exposed samples. To address this, the authors also employed an
of the pre-exposed samples. To address this, the authors also employed an alternative approach alternative approach for
examining the cross-section of the pre-exposed FRP samples, in order to
for examining the cross-section of the pre-exposed FRP samples, in order to circumvent the likely circumvent the likely
mechanical damage
mechanical damage of of the
the fibre–matrix
fibre–matrix interface
interface during
during sample
sample preparation
preparation by by grinding/polishing.
grinding/polishing.
In this alternative approach, the specimens were exposed to liquid nitrogen
In this alternative approach, the specimens were exposed to liquid nitrogen that embrittled the that embrittled the FRPs
FRPs
and facilitated
and facilitated brittle
brittle fracture
fracture along
along fibre–matrix
fibre–matrix interface
interface under
under anan applied
applied load.
load. The
The liquid
liquid nitrogen
nitrogen
fracturing enabled observation of a mechanical damage-free
fracturing enabled observation of a mechanical damage-free interface by SEM.interface by SEM.
As shown
As shown in inthe
therepresentative
representativeSEM SEMimages
images forfor BFRP
BFRP andand GFRP
GFRP immersed
immersed in SWSSC
in SWSSC at◦60
at 60 °C
C for
for days
180 180 days
(Figure(Figure 7), extensive
7), extensive fibre degradation
fibre degradation resulted,resulted, suchplate-shape
such as pits, as pits, plate-shape
corrosion corrosion
products,
products, ring-shape cracks, and corrosion shells with a porous structure.
ring-shape cracks, and corrosion shells with a porous structure. Such fibre degradation Such fibre degradation
caused the
interface debonding that facilitated water penetration/moisture uptake. The study also confirmed the
Corros. Mater. Degrad. 2018, 1 37
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 11 of 16

caused the interface debonding that facilitated water penetration/moisture uptake. The study also
extent of degradation
confirmed to of
the extent increase with the
degradation alkalinity
to increase ofthe
with thealkalinity
environment
of the(i.e., NC, SWSSNC
environment caused
(i.e., NC,
greater degradation than HPC, SWSSHPC).
SWSSNC caused greater degradation than HPC, SWSSHPC).

(a)

Figure 7. Cont.
Corros. Mater. Degrad. 2018, 1 38
Corros. Mater. Degrad. 2018, 1, x FOR PEER REVIEW 12 of 16

(b)
Figure 7. SEM
Figure images
7. SEM imagesofof(a)
(a) BFRP (b)GFRP
BFRP (b) GFRP exposed
exposed to SWSSC
to SWSSC at 60 °C for ◦180
at 60 C for
days180 days (Adapted
(Adapted from
from [38],
[38],with
withpermission
permissionfrom Elsevier,
from 2018).
Elsevier, 2018).

Other Other studies

studies havehave also
also reportedcorrosion
reported corrosion shell
shell formation
formationandand pitting of glass
pitting or basalt
of glass fibresfibres
or basalt
due
due to to exposure
exposure to alkaline
to alkaline environment,asasaaresult
environment, result of
of the
thereaction
reactionofof
alkali-ions with
alkali-ions silicate
with in fibres
silicate in fibres
(Equation
(Equation (1)) (1)) [44–47].
[44–47]. Further
Further destruction and
destruction and dissolution
dissolution ofofsilicate network
silicate networkof fibres progresses
of fibres progresses
following Equation (2) [45–49].
following Equation (2) [45–49].
≡ 𝑆𝑖 − 𝑂𝑅 + (𝐻 + + 𝑂𝐻 −
) → ≡ 𝑆𝑖 − 𝑂𝐻 + 𝑅𝑂𝐻 (1)
≡ Si − OR + H + + OH − → ≡ Si − OH + ROH (1)
≡ 𝑆𝑖 − 𝑂 − 𝑆𝑖 ≡ +(𝑅+ + 𝑂𝐻 − ) → ≡ 𝑆𝑖 − 𝑂𝐻 + 𝑅𝑂 − 𝑆𝑖 (2)
+ −


In contrast to ≡their
Si −extensive
O − Sidegradation
≡ + R +inOH SWSSC → ≡ Si7),
(Figure −fibres
OH +inRO − and
BFRP Si GFRP suffered (2)
insignificant degradation in distilled water at 60 °C (Figure 8).
In contrast
Fibres andto their extensiveindegradation
fibre–matrix in SWSSC
CFRP appeared (Figure
unattacked, 7), fibres
clean in BFRP
and smooth andexposure
after GFRP suffered
to
insignificant degradation in distilled water at 60 ◦ C (Figure 8).
SWSSNC
Corros. Mater.orDegrad.
NC at2018,
60 °C
1, x for
FOR180 days
PEER (Figure 9).
REVIEW 13 of 16

(a) (b)
8. SEM images ◦ C for 180 days (Adapted
Figure
Figure 8. SEM imagesofof(a)
(a)BFRP and(b)
BFRP and (b)GFRP
GFRP exposed
exposed to at
to DW DW at for
60 °C 60 180 days (Adapted from
from [38],
[38],with
withpermission
permissionfromfrom Elsevier,
Elsevier, 2018).
2018).
Corros. Mater. Degrad. 2018, 1 39

(a) (b)
Fibres and fibre–matrix in CFRP appeared unattacked, clean and smooth after exposure to
Figure 8. SEM images of (a) BFRP and (b) GFRP exposed to DW at 60 °C for 180 days (Adapted from
SWSSNC [38],
or NC at 60 ◦ C for 180 days (Figure 9).
with permission from Elsevier, 2018).

(a) (b)
Figure 9. SEM images for 180-day exposed CFRP and then fractured in liquid N2: (a) SWSSC and (b)
Figure 9. SEM images for 180-day exposed CFRP and then fractured in liquid N2: (a) SWSSC and (b)
NC (Adapted from [38], with permission from Elsevier, 2018).
NC (Adapted from [38], with permission from Elsevier, 2018).
5. Conclusions
5. Conclusions
Seawater and sea sand concrete (SWSSC) possesses a great potential as an alternative to
Seawater and sea sand concrete (SWSSC) possesses a great potential as an alternative to traditional
traditional concrete since it can significantly address the huge problem of use of fresh water and
concrete since of
dredging it can
riversignificantly
sand that areaddress the huge
used in huge problem
quantities of use of fresh
in production water and
of traditional dredging of river
concrete.
sand that However,
are used in huge quantities in production of traditional concrete.
material of reinforcement for SWSSC needs to be highly corrosion resistant because
However, material
the traditional of reinforcement
reinforcement for suffer
of steel will SWSSC needs to behigh
unacceptably highly corrosion
corrosion resistant
rate due because
to very high the
traditional reinforcement
chloride of steel will suffer unacceptably high corrosion rate due to very high chloride
contents of seawater.
contents ofThis article discusses the use of fibre-reinforced polymer (FRP) as a suitable alternative
seawater.
reinforcement
This in SWSSC. The
article discusses the article
use of provides an overviewpolymer
fibre-reinforced of the reported
(FRP)literature on degradation
as a suitable alternative
reinforcement in SWSSC. The article provides an overview of the reported literature degradation
of different FRP types in normal concrete, and provides a comparison with SWSSC. The on degradation
of FRPs (described in terms of water uptake) is reported to be considerably different in the normal
of different FRP types in normal concrete, and provides a comparison with SWSSC. The degradation
concrete and chloride-containing alkaline SWSSC environments. More importantly, the article also
of FRPs (described in terms of water uptake) is reported to be considerably different in the normal
identifies the gross lack of systematic work to understand the degradation kinetics and mechanisms
concrete andinchloride-containing
of FRP the chloride-containing alkaline
alkalineSWSSC
SWSSC environments.
environment. It isMore importantly,
interesting that thethe article also
seawater-
identifies the gross lack of systematic work to understand the degradation
FRP combination has a beneficial effect in resistance of FRP to degradation. kinetics and mechanisms of
FRP in the chloride-containing alkaline SWSSC environment. It is interesting that the seawater-FRP
combination has a beneficial effect in resistance of FRP to degradation.

Author Contributions: This review was conceptualized by R.K.S.R. who also undertook the major part of writing,
with considerable assistance from F.G. and S.A.-S., X-L.Z. and R.J. contributed to this article with their extensive
expertise in composite research.
Funding: The authors wish to acknowledge the financial support provided by the Australian Research Council
(ARC) through an ARC Discovery Grant (DP160100739).
Conflicts of Interest: The authors declare no conflict of interest.

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