Materials and Structures (2021) 54:121

https://doi.org/10.1617/s11527-021-01719-5 (0123456789().,-volV)
( 01234567
89().,-volV)

ORIGINAL ARTICLE

Influence of seawater on alkali-activated slag concrete

Yubin Jun . Jae Hong Kim . Seong Ho Han . Taewan Kim

Received: 15 December 2020 / Accepted: 2 May 2021 / Published online: 12 May 2021
Ó RILEM 2021

Abstract This study examines the use of natural
seawater as mixing water for alkali-activated slag
concrete and reports the characteristics of alkali-
activated slag concrete with exposure to seawater.
Preliminary experiments were conducted on pastes in
order to measure pH and select optimum activator
content under the experimental conditions. Wet-
sieved pastes from fresh concrete were used to
evaluate the mineralogical and microstructural char-
acteristics of reaction products. Compressive strengths
and chloride contents were measured with the hard-
ened concrete samples. The activators used in alkali-
activated slag concrete were sodium hydroxide (5%
weight of slag) and liquid sodium silicate (5% weight
of slag). The alkali-activated slag samples showed the
carbonation of calcium silicate hydrate (C–S–H),
which resulted in the reduction in strength with time.
The seawater-mixed alkali-activated slag samples
produced additional reaction products, C4AH13, and
chloride-bearing hydrocalumite, and they improved
the strength. The seawater-mixed alkali-activated slag
samples exposed in seawater exhibited improved
Y. Jun  J. H. Kim (&)  S. H. Han
Department of Civil and Environmental Engineering,
Korea Advanced Institute of Science and Technology,
Daejeon 34141, Republic of Korea
e-mail: jae.kim@kaist.ac.kr
T. Kim
Department of Civil Engineering, Pusan National
University, Busan 46241, Republic of Korea
mechanical performance compared to other samples.
C–S–H carbonation did not occur, refinement of the
pore structure was confirmed, and the compressive
strength increased after exposure to seawater. The
release of partial chloride ions, which were bound in
solid phases, occurred; however, such slight leaching
did not affect the strength of the samples. The
investigation within the experimental conditions of
this study showed a positive result regarding the use of
seawater as mixing water in alkali-activated slag
concrete.
Keywords Alternative cement  Seawater  Alkali
activator  Mixing water  Exposure
1 Introduction
Concrete is annually produced about 11 billion tons
worldwide, which requires upwards of 1 billion tons of
fresh water per year [1]. Global climate change has
serious impacts on resources around the world. World
Meteorological Organization reported that more than
half of the world’s population would lack safe
drinking water by 2025 [2]. The construction industry
would face the fresh mixing water supply problem in
near future.
From the viewpoint of replacing fresh water in plain
concrete production, positive and negative opinions
121 Page 2 of 16
toward concrete mixed with seawater were reported.
Etxeberria et al. [3] found that the compressive
strength of concrete produced with seawater increases
compared to freshwater-mixed concrete and the
strength enhancement is observed not only during
the early ages but also in the long term. The chemical
composition of cement has a more significant effect on
the mechanical properties of concrete than the selec-
tion of either freshwater or seawater [3, 4]. Shi et al.
[5] reported that the 28-day strength of seawater-
mixed concrete is higher than that of freshwater-mixed
concrete. The use of supplementary cementitious
materials seems to intensify the positive effect of
seawater. Katano et al. [6] showed that the early
strength and long-term strength of concrete produced
with seawater increases with the incorporation of slag,
fly ash, silica fume, or calcium nitrate. Otsuki et al. [7]
found that blast-furnace slag cement concrete fabri-
cated with seawater exhibited better durability than
concrete produced using ordinary Portland cement and
freshwater.
However, controversial results were reported by
Mbadike and Elinwa [8], in which the compressive
strengths of freshwater-mixed concrete exceeded
those of salt-water mixes. Kaushik and Islam [9]
found that hydration products with chloride ions
blocked the pores in the concrete and subsequently
improved its early-age strength. The hydration prod-
ucts were incredibly soft to be leached out after
substantial time had passed, which resulted in the
decrease in strength at later ages. Wegian [10]
reported a similar phenomenon: Concrete produced
with seawater showed a higher compressive strength at
early ages, but a negative effect was observed at later
ages. Younis et al. [11] showed that gain in early
strength occurred, but the later strength decreased by
7–10% for seawater-mixed concrete when compared
with freshwater-mixed concrete.
Regarding the use of seawater, the main concern
will be the risk of steel corrosion inside concrete.
Chloride ions in seawater can destroy a passive film on
the steel surface, and as the steel reinforcement
depassivates, corrosion initiates. Therefore, reinforced
concrete structure located in marine environments has
a high risk of corrosion. Undoubtedly, the use of
seawater will promote steel corrosion. Nevertheless,
some studies reported positive results regarding the
use of sea sand and seawater in reinforced concrete.
Ozaki and Sugata [12] reported that concrete
Materials and Structures (2021) 54:121
containing slag, volcanic ash, and sea sand, in which
the concrete had been exposed to seawater for 60
years, did not show severe corrosion of its reinforcing
bars and deterioration of the concrete structures.
Nishida et al. [13] mentioned that the utilization of a
suitable admixture could have a positive effect on the
corrosion of reinforced concrete produced using
seawater and observed that a higher replacement level
of the slag improved the corrosion resistance to
chloride attack.
Although these existing literatures reported a
promising result, one possible solution for the corro-
sion issue is replacing the conventional steel with
noncorrosive reinforcement. Another may be the
application of alkali-activated binders in plain con-
crete. Alkali-activated binder has been introduced as
an eco-friendly construction material to replace Port-
land cement binder due to the low environmental
impact which is associated with the utilization of by-
products such as ground-granulated blast-furnace slag
and coal fly ash. Alkali-activated slag, which is
generally synthesized by mixing slag with alkaline
solution, can possess better mechanical properties as
compared to cement [14–16]. Alkali-activated slags
have been utilized in civil infrastructure such as a
housing slab, sidewalk, precast panel, and retaining
wall [17]. Chloride ions can exist as free ions in the
pore solution or they can be bound by reaction
products. Bound chloride ions become inactive for
the depassivation of steel. It is reported that alkali-
activated slags are capable of binding and immobiliz-
ing chloride [18, 19]. It could expect that the bound
chloride prevents induction of the reinforcement
corrosion. In order to be the safe utilization of
seawater in practical applications, this study opens
up the chances for the seawater to be applied as mixing
water in alkali-activated slag concrete.
In this study, the effect of seawater mixing on
alkali-activated slag concrete and characteristics of
alkali-activated slag concrete exposed in seawater are
investigated. The compressive strength and chloride
contents in hardened samples are measured to report
the properties of the alkali-activated slag concrete.
The microstructural characterization of the alkali-
activated slag binder is conducting using X-ray
diffraction (XRD), mercury intrusion porosimetry
(MIP), and thermogravimetry (TG). A series of the
test results support the use of the alternative cement for
seawater-mixed concrete.
Materials and Structures (2021) 54:121 Page 3 of 16 121

2 Experimental program

2.1 Materials

Ground-granulated blast-furnace slag (GGBFS) was

obtained from a blast furnace of Hyundai Steel Co.,
Ltd., located in Dangjin, Korea. The oxide composi-
tion of the GGBFS was determined through X-ray
fluorescence as reported in Table 1. In addition, Fig. 1
shows the XRD patterns of the raw GGBFS with
reference peaks of the identified phases. The GGBFS
contained anhydrite, quartz, gypsum, calcite, aker-
manite, and anorthite, and its density was 2800 kg/m3.
Seawater collected from the southeast coast of Korea
(Songdo, 35°043200 N and 129°010100 E) was used in
this study. The pH of the seawater was 8.4, and Table 2
reports the ion concentrations dissolved in seawater.
The cations were measured through inductively cou-
pled plasma atomic emission spectroscopy, and the
anions were quantified through ion chromatography.
Sodium hydroxide (NaOH pellet with a reagent grade
higher than 98% purity) and sodium silicate (liquid
Na2SiO3 of Rw (SiO2/Na2O) = 2.5 and 62.9% H2O by
mass) were used as alkaline activators, and both
compounds were acquired from Sigma-Aldrich, Inc.

2.2 Paste samples Fig. 1 XRD patterns of raw ground-granulated blast-furnace

slag

In this study, preliminary experiments were conducted

Table 2 Ion concentrations of seawater (ppm)
on paste samples in order to find optimal mixing ratio
of alkali activator. Table 3 reports the mix proportion Ca2? K? Mg2? Na? Cl- SO42- Salinity
of alkali-activated GGBFS paste together with the
320 360 850 7400 15.000 3.300 27.230
optimal mix proportion. The alkaline solution was
prepared by dissolving NaOH pellets in tap water and
then adding liquid Na2SiO3. The water-to-binder ratio
(w/b) was fixed at 0.5. The pastes were mixed conditions for 28 days: a humidity chamber (23 °C and
according to ASTM C305 [20]. After mixing, the 80 ± 5% RH) and plastic storage containers filled
fresh paste was cast in 25 mm cube molds and cured in with seawater. The storage containers were placed in a
a humidity chamber at 23 °C and 80 ± 5% relative room at a constant temperature of 23 °C.
humidity (RH). After 28 days of curing, paste samples The compressive strengths were measured at 28 and
for each mixture were placed under two different 56 days using a universal testing machine (PWS-

Table 1 Chemical composition of ground-granulated blast-furnace slag (oxides in wt.%)

SiO2 Al2O3 CaO Na2O K2O MgO MnO TiO2 SO3 Fe2O3 Other oxides

33.58 13.88 41.89 0.33 0.63 3.06 0.29 0.82 4.18 1.04 0.21
Other oxides included SrO, BaO, P2O5, ZrO2, Y2O3, and Cr2O3
121 Page 4 of 16 Materials and Structures (2021) 54:121

Table 3 Mixture proportion of alkali-activated GGBFS paste

Sample ID w/b Mixing water (g) Activator (g) GGBFS (g) After 28 days of curing
Tap water NaOH pellet Liquid Na2SiO3

P-30 0.5 300 30 30 600 Humidity chamber

Immersion in seawater
P-40 40 40 Humidity chamber
Immersion in seawater
P-50 50 50 Humidity chamber
Immersion in seawater
The molarity of NaOH is 0.75, 1.0 and 1.25 M for P-30, P-40 and P-50, respectively, where the water amount in liquid Na2SiO3 is
excluded

400A, Woo Jin Co.) at a loading rate of 1.0 kN/s. Each
strength result was obtained as an average value of five
replicated samples. After each compressive strength
test, the fractured specimens were finely powdered to
measure pH in the paste samples. The powder was
diluted with deionized water at a water-to-powder
ratio of 3, and stirred for 10 min [21, 22]. The pH of the
diluted solution was measured using a digital pH meter
(Testo SE).
2.3 Concrete samples
Table 4 lists the mix proportion of the alkali-activated
GGBFS concrete sample. The samples were produced
by the activator of NaOH solution and liquid Na2SiO3
at 5% of the GGBFS content. The activator content
giving the highest strength in the preliminary test was
applied for the concrete samples. A total of 21 kg of
NaOH pellets was dissolved in mixing water (tap
water or seawater) of 214 kg, and next, a total of 21 kg
of liquid Na2SiO3 was added. The water-to-binder
ratio was 0.5, and the water content for producing 1 m3
of concrete was 214 kg. The sand-to-aggregate ratio
was 40.3% by mass. The fine aggregate was natural
river sand with a fineness modulus of 2.85 and a
density of 2,600 kg/m3, while the coarse aggregate
was crushed stone with a maximum size of 20 mm,
fineness modulus of 7.10, and density of 2,700 kg/m3.
Concrete mixing was performed in accordance with
ASTM C192 [23]. The slump measured after mixing
was approximately 150 mm for all the samples.
The freshly mixed samples were cast in 100 mm
diameter cylinders, each with a height of 200 mm.
Some of the paste were wet-sieved through a 45 lm

Table 4 Mixture proportion of non-cement concrete samples

Sample Mixing water (kg/ GGBFS Sand (kg/ Gravel (kg/ NaOH Na2SiO3 After 28 days of Paste wet-
ID m3) (kg/m3) m3) m3) (kg) (kg) curing extracted
Tap Seawater
water

C-TW- 214 – 420 655 970 21 21 Humidity P-TW-HC

HC chamber
C-TW- 214 – 420 655 970 21 21 Immersion in P-TW-SW
SW seawater
C-SW- – 214 420 655 970 21 21 Humidity P-SW-HC
HC chamber
C-SW- – 214 420 655 970 21 21 Immersion in P-SW-SW
SW seawater
The symbol of each sample ID represents the sample type (concrete: C), mixing water (tap water: TW, or seawater: SW), and
exposure condition (humidity chamber: HC, or seawater: SW), in this order
Materials and Structures (2021) 54:121 Page 5 of 16 121

sieve (42.5 lm opening), and the pastes that passed were used for phase identification. MIP was performed
through the sieve were cast in cylindrical molds, each using an AutoPore IV 9500-type mercury porosimeter
with a 25.4 mm diameter and 25.4 mm height. The (Micromeritics Instrument) capable of generating
wet-sieved pastes were prepared for microstructural pressure within the range of 0.1 to 60,000 psi
and mineralogical analyses (XRD, MIP, and TG). (0.0007 to 414 MPa). For TG analysis, temperature
All the samples (concrete and paste wet-sieved range from room temperature to 950 °C was applied at
from the concrete samples) mixed with tap water or a heating rate of 10 °C/min in a nitrogen atmosphere
seawater were cured in a humidity chamber at 23 °C using an SDT Q600 instrument (TA Instruments).
and 80 ± 5% RH for 28 days. Half of the samples for
each type of mixing water were kept in a humidity
chamber, and the other half were immersed in 3 Results
seawater for 56 days (Table 4). For example, the
C-TW-HC sample represents the concrete sample 3.1 Alkali-activated GGBFS paste
(denoted C) mixed with tap water (denoted TW) and
placed in a humidity chamber (23 °C and 80 ± 5% In alkali activation of GGBFS, the pH of the pore
RH) for 56 days (denoted HC) after 28 days of curing. solution plays an important role in its hydration [32].
The paste extracted from fresh concrete is denoted as Previous studies reported that the pH of diluted pastes
P, i.e., the P-TW-HC sample represents a paste sample can monitor the process of the alkali activation
of C-TW-HC. [21, 22, 33]. In this study, the pH values of diluted
Compressive strength values of concrete samples pastes are shown in Fig. 2. A higher pH values
were obtained in triplicate for each mixture after 28, generally lead to better GGBFS activation [34], due to
56, and 84-day following ASTM C39 standards [24]. the ability of OH- to provoke GGBFS and accelerate
After the strength values were determined, the frac- its dissolution [35]. A successive increase in the pH
tured specimens were subjected to acid- and water- with time is believed to be caused by the further
soluble chloride tests. Acid- and water-soluble chlo- dissolution of Ca, Na, K, and Mg from the GGBFS
rides in the concrete were measured according to [21]. In this study, the pH values of the paste samples
ASTM C1152 [25] and ASTM C1218 [26], respec- generally increased under all the exposure conditions
tively. Chlorides can exist either in a pore solution after curing, except for the P-50 sample after immer-
(free chloride) or reaction product (bound chloride). sion in seawater. This trend implied that the dissolu-
Free chloride in an uncombined form in the pore tion of slag continuously occurred even after 28 days
solution was water-soluble, and some of the chlorides
could be captured by the hydration products. The
bound chloride content could be calculated by sub-
tracting the free chloride content from the total
chloride content (acid-soluble content) [27–29].
At 28, 56, and 84 days, for XRD and TG tests,
cylinder samples (25.4 mm diameter and 25.4 mm
height) were fractured using a universal test machine
and subsequently powdered. Cross sections with a
thickness of 3 mm along the length of cylinder samples
were prepared for MIP using a precision saw. All the
samples used for the XRD, MIP, and TG tests were
immersed in isopropanol to stop further hydration.
XRD patterns were obtained using a Rigaku high-
power X-ray diffractometer with Cu-Ka radiation
(k = 1.5418 Å) and scanning from 5° to 60° at a sweep
speed of 1°/min. The International Centre for Diffrac-
tion Data (ICDD) Powder Diffraction File [30] and the Fig. 2 pH values of diluted pastes after exposure under
Inorganic Crystal Structure Database (ICSD) [31] different conditions
121 Page 6 of 16 Materials and Structures (2021) 54:121

of curing and additional reaction products subse-

quently contributed to an increase in the strength. In
the case of P-50, the pH value was reduced after its
immersion in seawater. The decreased pH could
indicate that the dissolved ions that remained in the
diluted samples were relatively fewer [21]. It implies
that the hydration in the P-50 sample after immersion
in seawater for 28 days can still proceed, however
afterward any further hydration is not likely to occur.
Figure 3 shows the compressive strength values of
the paste samples under different exposure conditions
of the humidity chamber and seawater. All the paste
samples exhibited higher strengths at 56 days, com-
pared to the control samples. The increased strength
depends on the exposure conditions. For the P-30
sample, the strength development after immersion in Fig. 4 Variation of compressive strength with time for concrete
seawater (P-30-SW) was better than that of the sample samples
placed in a humidity chamber (P-30-HC). For P-40,
the strength of P-40-SW (37.84 MPa) was slightly was mixed with tap water and exposed in a humidity
higher than that of P-40-HC (36.25 MPa). The P-50 chamber) decreased with time. The compressive
sample showed the opposite trend of those of the P-30 strength of C-SW-HC (seawater-mixed concrete)
and P-40 samples. In this study, the mixture proportion was always higher than that of the control sample of
of paste sample (P-30) that showed better strength in C-TW-HC. The C-SW-HC strength even increased at
seawater was applied to the mix design of alkali- 84 days, despite a slight decrease at 56 days. When the
activated concrete. concrete samples were immersed in seawater after 28
days of curing (C-TW-SW or C-SW-SW sample),
3.2 Alkali-activated GGBFS concrete their compressive strength values increased with time.
The immersion in seawater increased the compressive
Figure 4 shows the compressive strength values of strength, and the effect was consistent regardless of the
alkali-activated slag concrete samples. The compres- mixing water type. C-TW-SW was compared with
sive strength of C-TW-HC (the control sample, which C-TW-HC for concrete mixed with tap water, and

Fig. 3 Compressive strength test results of a P-30, b P-40, and 28 days after 28 days of curing, and P-##-SW: exposed in
c P-50 paste samples under different exposure conditions; P-##: seawater for 28 days after 28 days of curing
28 days of curing, P-##-HC: exposed in humidity chamber for
Materials and Structures (2021) 54:121 Page 7 of 16 121

C-SW-SW was compared with C-SW-HC for seawa-

ter-mixed concrete.
Figure 5 shows the bound chloride concentration
with time. The bound chloride concentration in control
C-TW-HC sample was maintained at an almost
constant value of 0.004%. In the case of C-TW-SW,
the bound chloride increased up to approximately
0.059% after 28 days of immersion in seawater and
then decreased to 0.034% with time. For C-SW-HC,
the initial bound chloride concentration in the sample
was 0.116%, which decreased to 56 days. The amount
of bound chloride in C-SW-SW gradually decreased
with time.

3.3 Microstructural investigation of alkali-

activated GGBFS concrete

Pastes were extracted from fresh concrete after mixing

(P-TW-HC from C-TW-HC, P-TW-SW from C-TW-
SW, P-SW-HC from C-SW-HC, and P-SW-SW from
C-SW-SW) to evaluate the characteristics of the
reaction products without aggregates (i.e., sand and
gravel). Despite the extraction, some aggregates
remained. Figure 6 shows the XRD patterns of the
aggregates in paste samples, and it is illustrated using a
representative sample (P-TW-HC). The crystalline
phases that were common to all the hardened samples
were quartz, akermanite, and anorthite, and thus,
reflected the nature of raw GGBFS (Fig. 6).
The XRD patterns below (Figs. 7a, 8a, 9a, and 10a)
provide XRD diffraction patterns of reaction products

Fig. 6 XRD patterns of aggregates and raw GGBFS in

hardened paste samples

formed in samples except the phases shown in Fig. 6.

Fig. 5 Bound chloride concentration in concrete samples with
time
In Fig. 7a, P-TW-HC was composed of calcium
silicate hydrate (C-S–H) (4CaO 5SiO2 5H2O) (ICDD
no. 03–0239) with the main diffraction peaks appear-
ing at 20.985° and 29.160° 2h (d[Å]/relative inten-
sity(%): 4.23/100 and 3.06/100), and calcite (ICSD
code 040,112) with a diffraction peak at 29.364° 2h
121 Page 8 of 16 Materials and Structures (2021) 54:121

Fig. 7 Characterization of
the P-TW-HC sample:
a XRD pattern, b TG-DTG
curves, and c pore-size
distribution
Materials and Structures (2021) 54:121 Page 9 of 16 121

Fig. 8 Characterization of
the P-TW-SW sample:
a XRD pattern, b TG-DTG
curves, and c pore-size
distribution
121 Page 10 of 16 Materials and Structures (2021) 54:121

Fig. 9 Characterization of
the P-SW-HC sample:
a XRD pattern, b TG-DTG
curves, and c pore-size
distribution
Materials and Structures (2021) 54:121 Page 11 of 16 121

Fig. 10 Characterization
results of the P-SW-SW
sample: a XRD pattern,
b TG-DTG curves, and
c pore-size distribution
121 Page 12 of 16
(d[Å]/relative intensity(%): 3.039/100). The dotted
box B in Fig. 7a shows that diffraction peaks
overlapped C–S–H and calcite from 29° to 30° 2h. A
comparison with the reference patterns revealed that
the C–S–H peak in P-TW-HC increased at 56 days and
later decreased at 84 days, while the calcite peak
increased with time. Figure 7b shows the TG weight
loss curve and the weight loss derivative (DTG) curve
of P-TW-HC. According to previous TG and DTG
studies, a weight loss below 200 °C indicates the loss
of combined water through the dehydration of C-S–H
[36], and a weight loss between 600 and 750 °C
indicates the presence of calcite [37]. As shown in
Fig. 7b, the DTG peak of C–S–H increased at 56 days
and subsequently decreased at 84 days, while the DTG
peak of calcite increased with time, which was
consistent with the XRD results. Figure 7c depicts
the pore size distribution curves of the P-TW-HC with
time. Pores with size diameters of approximately 1 lm
(see dotted ellipse A in Fig. 7c) were detected in
P-TW-HC at 56 and 84 days.
Figure 8a and b show the XRD and TG results of
P-TW-SW exposed to seawater after curing. The
reaction products were C-S–H and calcite, which were
the same as those of P-TW-HC. A slight change in
C-S–H peaks with time was observed for XRD and
TG, while the calcite peak increased at 56 days and
then, slightly decreased at 84 days. Figure 8c shows
the pore-size distribution curves of P-TW-SW with
time. Pores with a size of approximately 1 lm, which
were observed in P-TW-HC (Fig. 7c), disappeared
significantly (see the areas marked by ‘A’ in Fig. 8c).
Note that peaks of chloride-bearing crystalline
phases were not present in XRD patterns of P-TW-
SW, but bound chloride was present in its concrete
sample (C-TW-SW) (Fig. 5). This implies that even
though it is difficult to distinguish by XRD, a reaction
product bound chloride exists. Previous studies have
shown that chloride can be bound by C-S–H and
calcium aluminate hydrate (C-A-H) [27, 29, 38]. Thus,
the bound chloride content in the sample is attributed
to some C–S–H phases. The bound chloride generated
in C-TW-SW at 56 days decreased at 84 days (Fig. 5),
and it appeared that this decrease resulted in a change
in the pore-size distribution. The pore-size distribution
of P-TW-SW showed more of finer pores at 56 days,
and then shifted toward coarser sizes at 84 days. This
behavior probably implied that the generated bound
chloride contributed to pore refinement, and the
Materials and Structures (2021) 54:121
existing pores within the sample increased in size
owing to the release of chloride ions from the bound
chlorides. However, the change in pore size owing to
the release of bound chlorides did not contribute to the
strength loss. Its concrete sample, C-TW-SW, showed
similar strength development between 56 and 84 days.
Figure 9a and b show the XRD and TG results of
P-SW-HC mixed with seawater. The XRD analysis
revealed that the crystalline reaction products were C–
S–H, calcite, C4AH13 (ICDD no. 11–0203), and
hydrocalumite (ICSD code 63251) (Fig. 9a). It was
observed in this study that hydrocalumite was a
reaction product because of the presence of chloride
ions in seawater. Hydrocalumite existed in the form of
a chloride-bearing phase [19, 39], C1H43.2Al4Ca8Cl2-
O36.6. In the DTG curves (Fig. 9b), the weight loss
between 130 and 170 °C was attributed to the presence
of C4AH13 [40], which had an overlapping tempera-
ture range of C–S–H [36]. The weight losses near 157
and 322 °C were influenced by the presence of
hydrocalumite [41]. As the weight losses partially
overlapped with each other, it was difficult to compare
the reaction products quantitatively on time during
TG/DTG. Considering the XRD patterns of the
reaction products, no visible change in the C4AH13
and hydrocalumite peaks with time were observed.
The P-SW-HC also had pores with sizes between 0.4
and 1.3 lm (see the areas marked by ‘A’ in Fig. 9c),
which was similar to those of the P-TW-HC sample.
Figure 10a and b show the XRD and TG results for
the P-SW-SW sample. The reaction products in P-SW-
SW were C–S–H, calcite, C4AH13, and hydrocalumite.
The hydrocalumite was confirmed to exist in the
chloride-bearing phase, similar to that of the P-SW-
HC sample. The bound chloride in its concrete sample
(C-SW-SW) could be likely attributed to the chloride
binding by C–S–H, C4AH13, and hydrocalumite. It
was observed that the bound chloride content of the
C-SW-SW sample decreased with time (Fig. 5), and
the compressive strength of the C-SW-SW increased
with time. Hence, the decrease in the bound chloride
did not influence the decrease in strength. Although
evident differences were not observed in the reaction
products over time, P-SW-SW showed a decrease in
the pores between 0.015 and 0.1 lm and an increase in
the pores smaller than 0.01 lm over time. Thus, P-SW-
SW experienced pore-size refinement (Fig. 10c).
Materials and Structures (2021) 54:121
4 Discussion
The compressive strength of control C-TW-HC sam-
ple decreased with time. That of C-SW-HC (seawater-
mixed concrete) sample decreased at 56 days and later
increased at 84 days. Earlier studies [42, 43] reported
that shrinkage in alkali-activated slag concrete causes
microcracking, which results in reducing the com-
pressive strength. Here, it seems that the strength
reduction is not resulted from the shrinkage. The
samples were not air-exposed (less than 50% RH), and
the curing humidity condition was kept at 23 °C and
80 ± 5% RH for entire curing. Moisture loss due to
external drying did not occur. In addition, it is known
that pores larger than 50 nm have a more significant
effect on strength than pores with smaller sizes, and
pores smaller than 50 nm affect the drying shrinkage
and creep deformation [44]. Both samples (C-TW-HC
and C-SW-HC) generally showed the decrease in
pores smaller than 50 nm at 84 days, while pores with
sizes of 0.4–1.3 lm were observed.
The strength decrease in C-TW-HC, observed in
this study, was due to the carbonation of C-S–H. A
previous study reported that the CaCO3 crystals owing
to the carbonation in hardened sample increase
porosity, resulting in the decrease in strength [15]. It
was reported that both calcite and silica gel were
formed during the carbonation of C-S–H, as follows:
C–S–H ? CO2 ? CaCO3 ? SiO2xH2O [45]. The
increase in calcite, along with the decrease in C-S–
H, with time was observed in microstructural analysis
of C-TW-HC. In addition, the weight loss between 400
and 500 °C occurred at the age of 56 and 84 days
(Fig. 7b); this weight loss indicated the presence of
silica gel [46]. Thus, the carbonation of C–S–H
occurred in C-TW-HC. It should be noted that pore
size refinement with time to some extent and simul-
taneously pores between 0.4 and 1.3 lm occurred. The
change in pores in the sample matrix is also due to the
carbonation; the pore size refinement could be
attributed to the precipitation of CaCO3 converted
from C-S–H, and pore between 0.4 and 1.3 lm is
thought to be void between the precipitated CaCO3
crystals.
C-SW-HC also showed the increase in calcite and
the porosity increase at around 1 lm (at 56 days) while
they displayed little change after 84 days. Here, the
calcite was not attributed to the carbonation of C–S–H
because C-S–H displayed a little change in peak
Page 13 of 16 121
intensities with time in the XRD patterns. In addition,
the presence of silica gel was not identified in the TG
analysis.
It should be noted that the new phases formed in the
seawater-mixed samples were chloride-bearing hydro-
calumite and C4AH13 (calcium aluminate hydrate).
C4AH13 was not detected in the alkali-activated
C-TW-HC. C4AH13 found in alkali-activated slag
showed a high aluminum content (13.88% Al2O3)
[47, 48]. The detection of C4AH13 in C-SW-HC
indicates that seawater could influence the activation
of the slag [49]. The formation of C4AH13 may imply
that free calcium ions have been more present in
C-SW-HC than C-TW-HC. Thus, it suggests that the
calcite might have been formed in the course of the
carbonation reaction between free Ca2? and perme-
ated CO2. The decreased pore size owing to reaction
products at 84 days improves impermeability to CO2
ingress, which results in no further carbonation in
C-SW-HC. Regardless of the mixing water type, the
carbonation of C–S–H or the formation of calcite
hardly appeared to occur in C-TW-SW and C-SW-SW
that were immersed in seawater after 28 days of
curing, compared to C-TW-HC and C-SW-HC. This is
due to a lower diffusion of CO2 in water than in air, as
reported in [50].
C-SW-SW exhibited higher strength than the other
samples (C-TW-HC, C-TW-SW, and C-SW-HC). A
previous study reported that the strength of alkali-
activated slag pastes mixed with and immersed in
seawater continuously increased over a year [51]. This
was owing to the continuous activation of slag, which
resulted in the formation of C–S–H and C-A-S–H and
good durability. Although the continuous activation
by seawater was not clearly explained in the existing
literature, the increase in strength with time was
similar. In this study, the results for the pH of the
diluted paste showed that the sample immersed in
seawater continued to be activated even after curing. It
was found that the degree of activation of the slag was
more significant in the sample immersed in seawater
than in the humidity chamber.
5 Conclusions
From the investigation presented above, the following
conclusions can be drawn:
121 Page 14 of 16
1. The compressive strength of control alkali-acti-
vated slag concrete, produced using tap water,
slightly decreased with time when it was cured in a
humidity chamber. This was due to the carbona-
tion of C–S–H. The carbonation of C–S–H caused
the formation of calcite and silica gel, and pore
size refinement with time to some extent and
simultaneously pore in between 0.4 and 1.3 lm
occurred.
2. Seawater-mixed alkali-activated slag concrete,
which was exposed in a humidity chamber, also
showed the pore development in between 0.4 and
1.3 lm. That was attributed to the carbonation
reaction between free calcium ions by the activa-
tion of the slag and permeated carbon dioxide.
3. The differences in reaction products, when tap
water was replaced by seawater as a mixing water,
were C4AH13, and chloride-bearing hydrocalu-
mite. Seawater-mixed alkali-activated slag con-
crete consequently exhibited a higher strength
than tap water-mixed concrete.
4. When tap water-mixed alkali-activated slag con-
crete was exposed to seawater, chloride-bearing
crystalline phases were not detected in XRD,
while some chlorides in pore solution were bound
to the reaction product, C–S–H. The change in
pore size owing to the release of bound chlorides
with time was identified, but it was not related to
any loss of strength.
5. When alkali-activated slag concrete was cured in a
humidity chamber, the significant formation of
calcite at 56 days was found in both tap water- and
seawater-mixed samples. It was attributed to the
carbonation of C–S–H or the reaction between
free calcium ion and carbon dioxide. The carbon-
ation hardly occurred in alkali-activated slag
concrete that was immersed in seawater.
6. Seawater-mixed concrete exposed in seawater
showed improved strength than the other samples.
7. Although our experimental investigations showed
positive results regarding the use of seawater as a
mixing water in alkali-activated slag concrete, it
still remains areas requiring further study.
Acknowledgements This research was supported by the Basic
Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of
Education (NRF-2020R1I1A1A01072504).
Materials and Structures (2021) 54:121
Declarations
Conflict of interest The authors declare no conflict of interest.
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