Construction and Building Materials 188 (2018) 569–582

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Self-healing performance of GGBFS based cementitious mortar with

granulated activators exposed to a seawater environment
Hong Gi Kim, Atta-ur-Rehman, Abdul Qudoos, Jae-Suk Ryou ⇑
Civil & Environmental Engineering Department, Room 415, Jaesung Civil Engineering Building, 222 Wangsimni-ro, Seongdong Gu, Seoul, South Korea

h i g h l i g h t s

The self-healing performance of granulated activators (Ca(OH)2, Na2SO4) are studied.

The specimen with granulated Ca(OH)2 presented complete crack closure than Na2SO4.

The major healing products were C-S-H, ettringite, gypsum, brucite, calcium chloride.

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

Article history: Concrete structures exposed to marine environments are susceptible to attack by harmful ions such as
Received 30 August 2017 chloride, sulfate, etc. Ground granulated blast furnace slag (GGBFS) blended cementitious materials are
Received in revised form 8 August 2018 used as a binder in coastal concrete structures. Cracks are generated at young ages due to shrinkage or
Accepted 15 August 2018
other factors, which allow the ingress of harmful ions. Therefore, repair and maintenance of such struc-
Available online 28 August 2018
tures is necessary to increase the service lives of these structures. Autogenous self-healing of the cement
composites has proved to be an effective alternative method. It occurs when water comes in contact with
Keywords:
the unhydrated cement particles and forms additional hydration products. In this study, cement mortar
Granulated activator
Ca(OH)2
was prepared by replacing cement with GGBFS up to 50%. Granules of activators Ca(OH)2 and Na2SO4
Self-healing were made and incorporated at different dosages. Physical and self-healing performance of the mortar
Seawater environment specimens were evaluated via compressive strength, relative dynamic modulus of elasticity, ultrasonic
Vickers micro-hardness pulse velocity and water permeability tests. The healing products were examined via electron micro-
scopy, energy dispersive X-ray spectrometry, and microhardness tests. The results indicated that the
specimens incorporating granulated Na2SO4 showed minimal self-healing performance while the self-
healing efficiency of the specimens with Ca(OH)2 granules was significantly enhanced.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction the durability performance of structures exposed to sea water [2].

Reinforced concrete structures exposed to marine and industrial
environments are susceptible to severe deterioration due to the cor-
rosion of the steel reinforcement. Chloride induced corrosion of
steel is one of the primary reasons for the deterioration of such
structures [1]. The cracks produced in the concrete structures per-
mit the ingress of harmful ions (chloride ions in case of a marine
environment) and initiate the corrosion of structural steel, which
further reduces the service life of marine structures. Therefore, the
cracks produced in such structures should be addressed to increase
⇑ Corresponding author at: Civil & Environmental Engineering Department, Room
404, Jaesung Civil Engineering Building, 222 Wangsimni-ro, Seongdong Gu, Seoul,
South Korea.
E-mail addresses: qudoos.engnr@gmail.com (A. Qudoos), jsryou@hanyang.ac.kr
(J.-S. Ryou).
However, crack repair is difficult when cracks are invisible or not
accessible. In this case, autogenous healing plays an important role
in the filling of small cracks. Autogenous self-healing occurs when
water comes in contact with unhydrated cement particles in the
cement composite to form hydration products, or CO2 in the air
reacts with calcium hydroxide (Ca(OH)2) to form calcium carbonate,
which is responsible for filling the cracks [3–7].
Ground granulated blast furnace slag (GGBFS) has been widely
used as a raw material for alkali-activated composites. It contains
a higher amount of amorphous silica, which makes it an excellent
reactive material. This behavior of GGBFS makes it appropriate for
utilization as a high strength development material in alkali-
activated systems [8,9]. The selection of the alkali-activator is
one of the important factors for alkali-activated GGBFS systems
due to its dosage and chemical reaction. It plays a significant role
in the formation of hydration products and strength development

https://doi.org/10.1016/j.conbuildmat.2018.08.092
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
570 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

of alkali-activated GGBFS composites [10]. Sodium hydroxide and nique to make self-healing granules, and they coated the granules
sodium silicate based alkali-activators are used for the activation using a coating material. Coating is employed to protect the release
of GGBFS [11]. These activators develop high strength due to their of self-healing agent during mixing of the composite ingredients.
high concentration of hydroxide ions (OH). However, their rapid Based on a review of the current literature, it is evident that Ca
setting time, toxicity due to high pH, and relatively high cost (OH)2 and Na2SO4 can be used to promote autogenous self-healing
restrict the wide utilization of these activators [12]. On the other in the GGBFS-based systems. Here, we utilized these activators to
hand, calcium hydroxide has proved to be an efficient activator make self-healing agents in the form of granules made using gran-
due to its pozzolanic reaction with the amorphous silica present ulation and coating techniques. The coating thus protects the reac-
in the cementitious materials [10,12–14]. Additionally, calcium tion of the activator granules during mixing and can be utilized
hydroxide-based activators are less expensive than sodium-based when cracks were generated. The cement was replaced with GGBFS
alkali activators. It has been reported that a Ca(OH)2-activated at different levels, and specimens were made with self-healing
GGBFS composite can be efficiently used as a construction material granules. The self-healing performance of these specimens was
due to its low cost and enhanced durability [15,16]. Apart from investigated in a seawater environment. Additionally, the concrete
this, sodium sulfate (Na2SO4) has also been utilized as a chemical structures exposed to tidal zones are subjected to drying and wet-
activator for Ca(OH)2 containing composites. Na2SO4 induces the ting due to splashing of seawater. This process can enhance the for-
formation of ettringite, which results in enhanced strength [17]. mation of CaCO3 which also contributes to the filling of the cracks.
Powders can be transformed to solids in the form of granules using Therefore, in this study, the samples were dried in air after expo-
granulation techniques. Ryou and Lee [18] used a granulation tech- sure to seawater environment. Microscopic investigation, relative
dynamic modulus of elasticity, ultrasonic pulse velocity, and water
Table 1
permeability tests were employed to evaluate the self-healing per-
Chemical and physical properties of OPC and GGBFS. formance. In addition, the healing products were analyzed via
scanning electron microscopy (SEM), energy dispersive X-ray spec-
Composition Weight (%)
troscopy (EDS), and microhardness tests.
OPC GGBFS
SiO₂ 20.8 34.1
Al₂O3 6.3 16.1 2. Experimental procedure
Fe₂O3 3.2 0.4
CaO 62 42.3 2.1. Materials
MgO 3.3 4.1
SO3 2.2 2.5 Ordinary Portland cement (OPC) conforming to ASTM C150 [19] and GGBFS
Physical properties ——— ——— were used as primary binders in this study. The physical properties and chemical
Specific gravity 3.15 2.89 composition of the cement and GGBFS are presented in Table 1. Natural sand
Blaine (cm2/g) 3200 4893 (absorption = 1.08%, maximum size = 5 mm, and fineness modulus (F.M) = 2.65)
LOI (%) 1.3 0.05 was used as the fine aggregate. Analytical grade Ca(OH)2 and Na2SO4 were used
as activators.

Fig. 1. Procedure for coating the granules.

 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582 571

Fig. 2. Coating thickness measurement.

Table 2 The granules were then dried in an oven at 60 °C. The granules obtained were cylin-
Physical and chemical properties of PVA coating film. drical in shape with diameters and lengths ranging from 1 to 1.5 mm and 1.5–
3.5 mm, respectively. Finally, the granules were coated with a poly vinyl alcohol
Appearance Clear and pale yellow (PVA) film using a pan-coating method to protect the activator during mixing
Boiling Point Not Applicable [18]. PVA sheet was dissolved in water at a ratio of 1:11 to produce a coating solu-
Melting Point 150–230 °C tion that was sprayed on the surface of the granules in a coating machine. Fig. 1
Density 1.2–1.3 g/cm3 depicts the procedure used for coating the granules. PVA films possess excellent
Specific Heat 1.9  103 J/kg °C [0.45 kcal/kg °C water solubility and adhesive properties. This procedure was repeated twice to
Combustion Heat 1.1  105 J/mol [5700 kcal/kg] get enough coating on the surface of the granules as mentioned in Ref. [18]. The
Solubility in Water Soluble coating thickness was measured via microscopy as shown in Fig. 2. The properties
Flash Point Assumed to be the same as PVA > 70 °C of the PVA film are summarized in Table 2.
(Seta method)
Auto-ignition Temperature Assumed to be the same as PVA > 370 °C 2.3. Mix proportions and fabrication of mortar specimens
Self-reactivity Not Applicable
The mortar mix proportions used in this study are presented in Table 3. Cement
was replaced with GGBFS at three replacement levels, i.e., 30%, 40%, and 50%. These
replacement levels were selected based on the results of the compressive strength
2.2. Granulation and coating of activators test conducted on the mortar samples up to 28 days curing in water. GGBFS replace-
ment level varied up to 70% by mass of the binder while addition of 10% Ca(OH)2
The granulation technique used in this study involves making of a paste sample granules was fixed for each mix at this stage. The type of activator was not given
of the powder activators and passing it through a granulation machine. A solution of much attention as both activators were coated after granulation to protect the
ethanol and water at a ratio of 10:1 was used to make the activator paste. The pow- interaction before the introduction of cracks. Three dosages i.e. 10%, 13%, and 15%
der activator was placed in a pan, and solution was added carefully to obtain a stif- of granulated activators were used in this study. A water to binder ratio of 0.37
fer paste. The paste was subsequently fed to a granulation machine to produce was used for all the mixes. The mortar ingredients were dry mixed for 60 s followed
granules. The details related to the granulation machine are given elsewhere [20]. by the addition of water. After the addition of water, a further mixing of 90 s was

Table 3
Mix proportions of the mortars (SG = GGBFS, Ca = Ca(OH)2, Na = Na2SO4 and number is percentage).

Mortar mix Water (g) Cement (g) GGBFS (g) Aggregate (g) Granulated alkali-activator (g)
SG30 933.82 1734.21 800.4 8003.99 0
SG30-Ca 10 933.82 1734.21 800.4 8003.99 266
SG30-Ca 13 933.82 1734.21 800.4 8003.99 347
SG30-Ca 15 933.82 1734.21 800.4 8003.99 400
SG30-Na 10 933.82 1734.21 800.4 8003.99 266
SG30-Na 13 933.82 1734.21 800.4 8003.99 347
SG30-Na 15 933.82 1734.21 800.4 8003.99 400
SG40 933.82 1467.41 1067.21 8003.99 0
SG40-Ca 10 933.82 1467.41 1067.21 8003.99 266
SG40-Ca 13 933.82 1467.41 1067.21 8003.99 347
SG40-Ca 15 933.82 1467.41 1067.21 8003.99 400
SG40-Na 10 933.82 1467.41 1067.21 8003.99 266
SG40-Na 13 933.82 1467.41 1067.21 8003.99 347
SG40-Na 15 933.82 1467.41 1067.21 8003.99 400
SG50 933.82 1200.6 1334.01 8003.99 0
SG50-Ca 10 933.82 1200.6 1334.01 8003.99 266
SG50-Ca 13 933.82 1200.6 1334.01 8003.99 347
SG50-Ca 15 933.82 1200.6 1334.01 8003.99 400
SG50-Na 10 933.82 1200.6 1334.01 8003.99 266
SG50-Na 13 933.82 1200.6 1334.01 8003.99 347
SG50-Na 15 933.82 1200.6 1334.01 8003.99 400
572 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

carried out. Mortar cube (50  50  50 mm3) and prism (40  40  160 mm3) sam- Table 4
ples were made following ASTM C109 [21] and ASTM C348 [22], respectively. The Concentration of ingredients of seawater.
samples were demolded after 24 h and placed in water for curing until the desired
test time was reached. In the case of prism specimens, two layers of reinforcement NaCl MgCl26H2O Na2SO4 CaCl2 KCl
(2 mm diameter wires) were provided, and each layer contained two wires. The 24.5 11.1 4.1 1.2 0.7
mortar was placed in three layers, and the depth of each layer varied from 130 to
135 mm. The reinforcement wires were placed after the first and second layers.
Vibration compaction in a vibrating table was carried out during casting for all
the samples. After 28 days of curing, the prism specimens were removed from observation, relative dynamic modulus of elasticity, ultrasonic pulse velocity, and
water and cracks (width under 0.3 mm) were introduced via a three-point bending water permeability tests. At each age of testing, the specimens were removed from
machine. The procedure for obtaining crack width under 0.3 mm is discussed in Ref. seawater and allowed to dry for 12 h. Relative dynamic modulus of elasticity mea-
[23]. Fig. 3 depicts the details of the reinforcement wires and provide a procedure surements were conducted according to ASTM C215 [25]. The details of this test can
for introducing cracks. Crack widths were measured using a microscope as shown be found somewhere else [23]. To calculate the relative dynamic modulus of elas-
in Fig. 4. After the introduction of cracks, the mortar specimens were placed in a ticity, the following equation is used [18,20]:
seawater environment. The seawater was made following KS F 2599-2 [24]. The


concentration of the ingredients used to make seawater is shown in Table 4. nc 2
Pc ¼  100 ð1Þ
n0 2
2.4. Methods
where Pc represents the relative dynamic modulus of elasticity with respect to time
Compressive strength tests on the mortar cubes were conducted after 3, 7, and (%), n0 represents the 1st horizontal vibration before the crack introduction, and nc
28 days following ASTM C109 [21]. Three replicates were used for each mix. The represents the horizontal vibration frequency after the crack introduction depending
self-healing performance of the mortar specimens was investigated via microscopic on the elapsed time.

Fig. 3. Reinforcement wire details and crack introduction procedure.

Fig. 4. Measurement of crack widths by microscope.

 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582 573

An ultrasonic pulse velocity test was conducted following ASTM C 597 [26]. The
pulse velocity was measured in indirect mode (i.e., using transducers on the same
surface of the samples), with the crack being at the center as shown in Fig. 5. The
procedure for measuring the crack depth is discussed elsewhere [27,28] and is pre-
sented schematically in Fig. 6.
The crack depths were calculated using the following equation [27,28]:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
L Di  DðtÞ
D¼ T 2C  T 20
T0
where, D is crack depth, L is the distance of the transducers from the crack (note that
transducers must be placed equidistant from the crack), Tc is propagation time
around the crack, T0 is propagation time along the surface of the same specimen
without any cracks (note that the surface path length for Tc and T0 must be equal).
The values obtained using Eq. (2) at a specific time were used to calculate crack
closing ratio (bðtÞ) using the following equation [20]:
ð2Þ bðtÞ ¼ 1  ð3Þ
Di

Fig. 5. Procedure for crack depth measurement on (a) a mortar sample without a crack and (b) a mortar sample with a crack.

Fig. 6. Water permeability test setup (a) side view and (b) top view.
574 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

Here, Di is a crack depth before self-healing, D(t) is crack depth at a specific
time.
b(t) = 1 means that no internal crack-closing occurred, while b(t) = 0 means that
complete internal crack-closing was achieved.
Water permeability tests were conducted according to the RILEM test Method
II.4 [29]. A modified test setup was used, and the tubes were manufactured using
acrylic. The details are shown in Fig. 6. All the sides were sealed with epoxy to pre-
vent the leakage of water except through the crack. The tube was filled with water,
and the surface was covered to avoid the loss of water due to evaporation.
The water permeability coefficient was calculated using the following equa-
tion [23]:
 
aL h1
k¼ ln ð4Þ
At h2
Here, k represents the water permeability coefficient (cm/s), a represents the
cross-sectional area of the pipette (cm2), L represents the specimen thickness
(cm), A represents the cross-sectional area of the specimen (cm2), T represents
the time (s), h1 represents the initial water head (cm), and h2 represents the final
water head (cm).
The internal crack closing ratio (b(t)) using the water permeability coefficient
was calculated using the following equation [28]:
ki  kðtÞ
bðtÞ ¼ 1  ð5Þ
ki
Here, ki is a water permeability coefficient before self-healing, and k(t) is a
water permeability coefficient at a specific time.
The healing products inside the filled cracks were analyzed via SEM and EDS
analysis. The products were also examined via microhardness tests. Fig. 7 presents
the procedure for obtaining specimens for SEM-EDS and microhardness tests. A
scanning electron microscope (accelerating voltage: 0.2–30 kV, probe current:
10E12 to 10E5A, SEI resolution: 3.5 nm), EDS spectrometer (detector type:
SDD Apollo XL, resolution: 134.49, take-off angle: 35°, accelerating voltage:

Fig. 7. Sample preparation procedure for SEM and microhardness test.

Fig. 8. Compressive strength of the mortar samples.

 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582 575

Table 5 compressive strength results. Standard deviation of the compres-

Standard deviation values of compressive strength test results. sive strength values was calculated as summarized in Table 5. As
Mortar mix Standard deviation shown, the mortar mix SG30 presented an increase of 9% and
3 days 7 days 28 days 47% in compressive strength at 3 days in comparison with SG40
and SG50, respectively. After 28 days, the increase in the compres-
SG30 2.41 1.70 1.65
SG30-Ca10 1.82 2.26 0.85
sive strength of SG30 was 16% and 19% as compared to SG40 and
SG30-Ca13 0.73 1.39 1.22 SG50, respectively. The increase in the GGBFS content reduced
SG30-Ca15 2.46 0.91 2.00 the compressive strength. The decrease in the compressive
SG30-Na10 2.73 1.27 1.25 strength is due to the dilution effect [32] and a relatively slower
SG30-Na13 1.87 1.59 1.09
rate of the pozzolanic reaction of GGBFS [33–35]. The mortar sam-
SG30-Na15 0.53 0.88 1.00
SG40 0.66 1.18 0.39 ples SG30 containing 10, 13 and 15% of the granulated activator (Ca
SG40-Ca10 1.01 0.97 1.36 (OH)2) presented compressive strengths of 33.55, 25.98 and
SG40-Ca13 1.23 2.45 1.20 17.19 MPa after 3 days, respectively. After 28 days, these samples
SG40-Ca15 2.00 1.51 1.34
presented compressive strengths of 61.58, 61.78 and 37.44 MPa,
SG40-Na10 1.13 1.90 1.13
SG40-Na13 0.38 0.78 0.66
respectively. Likewise, the mortar samples containing SG30 with
SG40-Na15 1.34 1.63 0.37 10, 13 and 15% of the granulated activator (Na2SO4) illustrated
SG50 0.87 0.98 1.51 compressive strength results similar to those with granulated acti-
SG50-Ca10 3.10 1.99 0.65 vator (Ca(OH)2). The compressive strength decreased with an
SG50-Ca13 0.79 1.39 0.23
increase in the usage of the granulated alkali-activator. Similar
SG50-Ca15 1.78 1.46 0.86
SG50-Na10 1.15 1.13 1.59 behavior was observed for SG40 and SG50 mortar mixes. The com-
SG50-Na13 1.64 1.39 1.68 pressive strength values of SG30 specimens with granulated acti-
SG50-Na15 0.57 0.70 1.57 vators showed an increase in the range of 6%–28% as compared
with the SG40 specimens containing granulated activators at dif-
ferent ages. Additionally, the compressive strength of SG50 speci-
20 kV), and Vickers microhardness tester (Model No. THV-1MD, China) were used in mens with the granulated activators at various ages showed a
this study. The procedures for sample preparation for SEM analysis and microhard-
decrease in the range of 20%–28% in comparison with SG30 con-
ness tests are discussed elsewhere [30,31].
taining granulated activators. The decrease in the compressive
strength with the increase in granule content may be due to the
3. Results and discussion weak bonding of the coated granules with the cement matrix.

3.1. Compressive strength test results 3.2. Microscopic analysis of the crack surface

Compressive strength tests were conducted on the mortar spec- Figs. 9–11 display microscopic images on the crack surface for
imens after 3, 7 and 28 days. Fig. 8 shows the average values of the samples containing 30, 40, and 50% of GGBFS and those with 15%

Fig. 9. Microscopic images on the crack surface of the specimens (30% of GGBFS) (a) without granules, (b) 15% Na2SO4, and (c) 15% Ca(OH)2.
576 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

granulated activators, respectively. Only images of the samples It is obvious from the images that the cracks in SG30, SG40 and
with 15% granules are presented to make the discussion of the SG50 specimens were not filled even after 40 days. SG30 speci-
results concise and easy to follow. mens showed a minimal amount of filling products in the cracks.

Fig. 10. Microscopic images on the crack surface of the specimens (40% of GGBFS): (a) without granules, (b) 15% Na2SO4, and (c) 15% Ca(OH)2.

Fig. 11. Microscopic images on the crack surface of the specimens (50% of GGBFS): (a) without granules, (b) 15% Na2SO4, and (c) 15% Ca(OH)2.
 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582 577

This may be because carbonation occurred when specimens were
placed for drying in air. It has been reported that carbonation
occurs as the cementitious samples are exposed to air [36]. Simi-
larly, the cracks in SG30, SG40 and SG50 specimens with granu-
lated activators (Na2SO4) did not show any obvious change after
40 days except for SG40-Na15, which displayed a partial filling of
the crack. On the other hand, the crack in SG30-Ca15 filled partially
after 7 days and completely after 40 days. Likewise, SG40-Ca15
showed a complete filling of the crack at 33 days. In particular,
the crack in the SG50-Ca15 sample filled faster in comparison with
samples containing 30% and 40% of GGBFS. This means the
increased content of GGBFS displayed enhanced self-healing per-
formance with Ca(OH)2 granules. This is due to the availability of
a higher amount of amorphous silica resulting in an increased

Fig. 12. Relative dynamic modulus of elasticity of the specimens.

Fig. 13. Crack closing ratio measured by ultrasonic pulse velocity test.
578 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

pozzolanic reaction. The granulated Ca(OH)2 granules reacted with
silica of GGBFS and formed additional hydration products, which
filled the cracks. On the other hand, the samples with Na2SO4 gran-
ules presented minimal self-healing performance in comparison
with those containing Ca(OH)2 granules.
respectively. The recovery rate of specimens with the granulated
activator (Ca(OH)2) reached 99.9%, whereas the recovery rate of
specimens with the granulated activator (Na2SO4) reached 80%. It

3.3. Relative dynamic modulus of elasticity results

The dynamic modulus of elasticity of the mortar specimens was

measured before the introduction of cracks as well as after immer-
sion in seawater as shown in Fig. 12. From the results, it is evident
that the relative dynamic modulus of elasticity (RDME) of all spec-
imens decreased after the introduction of cracks. Decreases of
61.4%, 72.2% and 61.3% in RDME were observed for SG30, SG40
and SG50 specimens, respectively. It should be noted that we are
discussing the increase in values with respect to the values after
the cracks were introduced. These values increased by 74.3%,
79.3% and 74% after 14 days, and 80%, 82% and 84.1%, after 60 days,
respectively. The reductions in RDME values for SG30-Na10, 13 and
15 specimens were 71.6%, 64.1% and 72.4%, respectively, after
cracks were introduced. RDME values increased by up to 83.1%,
79% and 81.5% after 14 days and 85.7%, 86.1% and 90.1% after
60 days for the same specimens, respectively. Similar results were
observed for specimens containing Na2SO4 granules and 40% and
50% GGBFS. A maximum recovery rate of 80% was indicated for
these samples. On the other hand, SG30-Ca10, 13 and 15 speci-
mens presented a decrease of 65.6%, 73.1% and 69.5% in RDME val-
ues after cracks were introduced, respectively. The increases in
these values after 14 and 60 days were 90.2%, 89.7% and 86.6%,
and 98.3%, 98.6% and 99.3%, respectively. In addition, a decrease
of 75.2%, 66.5% and 59.1% in RDME values was observed for
SG40-Ca10, 13 and 15 specimens after cracks were introduced,
respectively. After 14 and 60 days, increases of 85.6%, 81.3% and
78.6%, and 97%, 99% and 99.5% in RDME values were observed,
respectively. In the case of SG50-Ca10, 13 and 15 specimens,
decreases of 73.2%, 72.3% and 72.2% were observed after crack
introduction, respectively. These values increased to 84%, 85.6%
and 91.4% after 14 days and 95%, 98.6% and 100% after 60 days, Fig. 15. Microhardness test results for specimen SG50-Ca15.

Fig. 14. Crack closing ratio measured by water permeability test.

 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582 579

is anticipated that ettringite and CaCO3 were formed in the speci- 0.16, 0.11 and 0.12 and 0.19, 0.12 and 0.09 after 60 days,
mens with Na2SO4. The former is due to the reaction of sulfate ions respectively.
[17], and the latter is due to carbonation [36].

3.5. Water permeability test results

3.4. Ultrasonic pulse velocity test results
Crack closing ratio b(t) was calculated based on water perme-
Ultrasonic pulse velocity tests were used to investigate the
ability tests using Eqs. (4) and (5) as shown in Fig. 14. The results
crack filling of the specimens. This test provides information about
of the water permeability test were similar to those of the ultra-
the internal crack closure. Crack closing ratio (b(t)) was calculated
sonic pulse velocity test. SG30, SG40 and SG50 specimens pre-
following Eqs. (2) and (3) and is displayed in Fig. 13. The crack clos-
sented b(t) values of 0.82, 0.85 and 0.83 after 14 days, and 0.77,
ing ratio (b(t)) = 1 indicates no internal crack closing, while (b(t))
0.89 and 0.67 after 50 days, respectively. On the other hand, b(t)
= 0 indicates complete filling of the crack. From the figures, it is
values for SG30-Na10, 13 and 15 specimens were 0.82, 0.69 and
obvious that the specimens without activator granules presented
0.83 after 14 days and 0.68, 0.67 and 0.67 after 50 days respec-
an insignificant variation in the b(t) values with respect to time.
tively. Similar results were observed for the corresponding speci-
For example, SG30, SG40 and SG50 specimens presented b(t) val-
mens with 40% and 50% GGBFS. Contrary to this, SG30-Ca10, 13
ues of 0.93, 0.92 and 0.99 after 7 days, 0.92, 0.82 and 0.83 after
and 15 specimens presented b(t) values of 0.32, 0.55 and 0.55 after
14 days, and 0.76, 0.67 and 0.71 after 60 days, respectively. In con-
14 days and 0.19, 0.14 and 0.10 after 50 days, respectively. b(t) val-
trast to this, b(t) values for SG30-Na10, 13 and 15 specimens were
ues for SG40 and 50-Ca10, 13 and 15 specimens were observed in
observed at 0.88, 0.92 and 0.94 after 7 days, 0.74, 0.84 and 0.72
the range of 0.32 to 0.55 after 14 days, 0.18 to 0.32 after 28 days,
after 14 days, and 0.60, 0.62 and 0.62 after 60 days, respectively.
and 0.01 to 0.14 after 50 days.
Likewise, after 60 days, the specimens SG40-Na10, 13 and 15 pre-
sented b(t) values of 0.61, 0.61 and 0.64, respectively. b(t) values
for SG50-Na10, 13 and 15 specimens were 0.65, 0.63 and 0.61 after 3.6. Microhardness test results
60 days, respectively. This means that specimens with Na2SO4
granules showed a minimal crack closing rate. However, the spec- The filled crack zone was examined via microhardness testing
imens with Ca(OH)2 granules presented a significant amount of as shown in Fig. 15. As shown, the microhardness value on the
crack closing. For example, SG30-Ca10, 13 and 15 specimens pre- paste surface (left side of the crack) was 210.5 Hv. Contrary to this,
sented b(t) values of 0.93, 0.94 and 0.95 after 7 days and 0.52, the values of microhardness on the self-healed surface (from left to
0.70 and 0.65 after 14 days, respectively. b(t) values for these sam- right) were 142.1, 137.8, 101.8 and 103.45, respectively. Likewise,
ples after 60 days were 0.16, 0.11 and 0.17, respectively. Similar the microhardness value on the paste surface at the right side of
behavior was observed for the respective samples containing 40% the crack was 150.5 Hv. Microhardness tests provide information
and 50% GGBFS. The specimens containing 40% and 50% GGBFS about the compactness of the microstructure of the cement com-
with 10, 13, and 15% Ca(OH)2 granules showed b(t) values of posites [31]. The microhardness values of the paste zone and the

Fig. 16. SEM micrographs and EDS analysis results (SG50-Ca15 specimen).
580 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582

self-healed zone are comparable. This means the cracks were con-
siderably filled with the healing products.
3.7. SEM and EDS analysis results
The healing products formed in the filled cracks were analyzed
via SEM and EDS analysis. The specimen SG50-Ca15 was selected
for SEM analysis because it presented higher crack filling effi-
ciency. Fig. 16 displays the SEM micrograph and results of EDS
analysis carried out on the healing products and the zone around
the crack, respectively. The magnified (10000) SEM micrographs
are also presented in the figures, clearly showing the healing prod-
ucts formed in the cracks. The SEM and EDS results in Fig. 16
clearly indicate that the healing products contained higher concen-
trations of calcium, magnesium, silicon and aluminum. It is antic-
ipated that C-S-H, ettringite, gypsum, brucite, calcium chloride,
and calcium carbonate are formed in the cracks. The calcium
hydroxide (CH) reacted with aluminum, magnesium, chlorine,
and sulfate ions, resulting in the formation of ettringite, gypsum,
brucite and calcium chloride [2,37,38]. The higher concentration
of silicon on the crack surface in comparison with the region
around the crack indicates the pozzolanic reaction of Ca(OH)2

Fig. 17. EDS mapping results (SG50-Ca15 specimen).

 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582
Fig. 18. SEM micrographs at the internal surface of the crack (SG50-Ca15 specimen).
granules with the silica provided by GGBFS. Additionally, calcium
carbonate may be formed due to the carbonation of available Ca
(OH)2 [36]. Fig. 17 portrays the results of EDS mapping carried
out on the crack region. A higher concentration of calcium and
magnesium was observed in the crack zone. To investigate the
healing products inside the crack, the specimen was split into
two parts, and SEM analysis was carried out on the crack surface
as shown in Fig. 18.
This study used granulated Ca(OH)2 and Na2SO4 activators as
self-healing materials in GGBFS blended cement composites
exposed to seawater. Seawater used in this study contained vari-
ous aggressive ions, i.e., magnesium, chloride, and sulfate ions. It
is well established that these ions react with the hydration prod-
ucts of the cement composites. The major reactions involved in this
system are as follows [38,39]:
MgSO4 þ CaðOHÞ2 ! MgðOHÞ2 ðBruciteÞ þ CaSO4 2H2 O ðGypsumÞ
MgSO4 þ ½CaðOHÞ2 þ CaO  Al2 O3  CaSO4
 18H2 O ðCalcium monosulfoaluminate hydrateÞ
! MgðOHÞ2 þ 3CaO  Al2 O3  3CaSO4  32H2 O ðEttringiteÞ
The reaction of magnesium chloride with Ca(OH)2 results in the
formation of brucite and calcium chloride as follows:
MgCl2 þ CaðOHÞ2 ! MgðOHÞ2 ðBruciteÞ
þ CaCl2 ðcalcium chlorideÞ
Calcium carbonate is formed when dissolved carbon dioxide
reacts with Ca(OH)2, which is further transformed to calcium bicar-
bonate as:
581
CO2 þ CaðOHÞ2 ! CaCO3 ðCalcium CarbonateÞ þ H2 O
CaCO2 þ H2 O þ CO2 ! CaðHCO3 Þ2 ðCalcium bicarbonateÞ
Gypsum is formed when CO2 reacts with Ca(OH)2 and calcium
monosulfoaluminate hydrate as follows:
CO2 þ ½CaðOHÞ2 þ CaO  Al2 O3  CaSO4
 18H2 O ðCalcium monosulfoaluminate hydrateÞ
! 3CaO  Al2 O3  CaCO3  xH2 O þ CaSO4  2H2 O ðGypsumÞ
4. Conclusion
This paper utilized Ca(OH)2 and Na2SO4 in the form of coated
granules to investigate their self-healing performance in GGBFS
blended cement composites in seawater. Based on the results, fol-
lowing conclusions can be made:
(1) The specimens without any activator granules did not show
any self-healing performance. Cracks were not filled even
after 60 days. The specimens with Na2SO4 showed a minimal
crack filling efficiency. However, specimens with incorpo-
rated Ca(OH)2 granules showed significant self-healing per-
formance in the form of crack filling. The healing products
were formed even in at very early immersion times in sea-
water. After 60 days, complete closure of the cracks was
observed.
(2) The crack closing efficiencies were verified by relative
dynamic modulus of elasticity, ultrasonic pulse velocity
and water permeability tests. The specimens with the gran-
582 H.G. Kim et al. / Construction and Building Materials 188 (2018) 569–582
ulated activator (Ca(OH)2) showed the filling of the cracks
internally, whereas the specimens without or with the gran-
ulated activator (Na2SO4) were not filled completely. The
internal crack closing of specimens with the granulated acti-
vator (Ca(OH)2) was almost achieved after 39 days.
(3) The major healing products formed in the cracks were C-S-H,
ettringite, gypsum, brucite, calcium chloride, and calcium
carbonate. The calcium hydroxide reacted with aluminum,
magnesium, chlorine, and sulfate ions, resulting in the for-
mation of ettringite, gypsum, brucite and calcium chloride.
The higher concentrations of silicon on the crack surface in
comparison with the region around the crack indicated the
pozzolanic reaction of Ca(OH)2 granules with the silica pro-
vided by GGBFS. Additionally, calcium carbonate may be
formed due to the carbonation of available Ca(OH)2.
It can be concluded that Ca(OH)2 activators in the form of
coated granules can be efficiently used as a self-healing material
in GGBFS blended cement composites exposed to seawater.
Conflict of interest
The authors have no conflict of interest.
References
[1] M. Otieno, H. Beushausen, M. Alexander, Chloride-induced corrosion of steel in
cracked concrete–part I: experimental studies under accelerated and natural
marine environments, Cem. Concr. Res. 79 (2016) 373–385.
[2] M. Maes, D. Snoeck, N. De Belie, Chloride penetration in cracked mortar and the
influence of autogenous crack healing, Constr. Build. Mater. 115 (2016) 114–
124.
[3] H. Huang, Thermodynamics of autogenous self-healing in cementitious
materials, (2014).
[4] D. Jaroenratanapirom, R. Sahamitmongkol, Self-crack closing ability of mortar
with different additives, J. Metals, Mater. Minerals 21 (1) (2011) 9–17.
[5] B. Ghent, Self-Healing Concrete through Incorporation of Encapsulated
Bacteria-or Polymer-Based Healing Agents, (2012).
[6] M. Wu, B. Johannesson, M. Geiker, A review: Self-healing in cementitious
materials and engineered cementitious composite as a self-healing material,
Constr. Build. Mater. 28 (1) (2012) 571–583.
[7] D. Snoeck, N. De Belie, From straw in bricks to modern use of microfibers in
cementitious composites for improved autogenous healing–a review, Constr.
Build. Mater. 95 (2015) 774–787.
[8] M.B. Haha, G. Le Saout, F. Winnefeld, B. Lothenbach, Influence of activator type
on hydration kinetics, hydrate assemblage and microstructural development
of alkali activated blast-furnace slags, Cem. Concr. Res. 41 (3) (2011) 301–310.
[9] C. Shi, A.F. Jiménez, A. Palomo, New cements for the 21st century: the pursuit
of an alternative to Portland cement, Cem. Concr. Res. 41 (7) (2011) 750–763.
[10] C. Shi, R.L. Day, Some factors affecting early hydration of alkali-slag cements,
Cem. Concr. Res. 26 (3) (1996) 439–447.
[11] D. Ravikumar, N. Neithalath, Effects of activator characteristics on the reaction
product formation in slag binders activated using alkali silicate powder and
NaOH, Cem. Concr. Compos. 34 (7) (2012) 809–818.
[12] K.-H. Yang, A.-R. Cho, J.-K. Song, S.-H. Nam, Hydration products and strength
development of calcium hydroxide-based alkali-activated slag mortars,
Constr. Build. Mater. 29 (2012) 410–419.
[13] W. Ma, P.W. Brown, Hydrothermal reactions of fly ash with Ca (OH)2 and
CaSO42H2O, Cem. Concr. Res. 27 (8) (1997) 1237–1248.
[14] Y. Jeong, J.E. Oh, Y. Jun, J. Park, J.-H. Ha, S.G. Sohn, Influence of four additional
activators on hydrated-lime [Ca (OH)2] activated ground granulated blast-
furnace slag, Cem. Concr. Compos. 65 (2016) 1–10.
[15] C. Shi, D. Roy, P. Krivenko, Alkali-activated Cements and Concretes, CRC Press,
2003.
[16] C. Shi, R.L. Day, Comparison of different methods for enhancing reactivity of
pozzolans, Cem. Concr. Res. 31 (5) (2001) 813–818.
[17] C. Shi, R.L. Day, in: Chemical Activation of Lime-slag Blends, Special
Publication, 1995, pp. 1165–1178.
[18] Y.-S. Lee, J.-S. Ryou, Self healing behavior for crack closing of expansive agent
via granulation/film coating method, Constr. Build. Mater. 71 (2014) 188–193.
[19] ASTM, ASTM C150/C150M - 17, Standard Specification for Portland Cement,
West Conshohocken, PA, 2017.
[20] Y.-S. Lee, Study on Crack-sealing of Cement Composite via Encapsulating the
Granulated Healing Material, Structural engineering, Hanyang University,
South Korea, 2015.
[21] C. ASTM, 109, Standard Test Method for Compressive Strength of Hydraulic
Cement Mortars (Using 2-in. or [50-mm] Cube Specimens) (2007).
[22] C. ASTM, 348: 02, Standard test method for flexural strength of hydraulic-
cement mortars (2002).
[23] Y.-S. Lee, J.-S. Ryou, Crack healing performance of PVA-coated granules made
of cement, CSA, and Na2CO3 in the cement matrix, Materials 9 (7) (2016) 555.
[24] K.S. Association, KS F 2599-2: The accelerated corrosion test of reinforced
concrete (wet-drying cycles method), South Korea (2008).
[25] C. ASTM, 215: 08, Standard Test Method for Fundamental Transverse,
Longitudinal, and Torsional Frequencies of Concrete Specimens (2008).
[26] C. ASTM 597, Standard Test Method for Pulse Velocity Through Concrete,
ASTM International, West Conshohocken, PA, 2009.
[27] S.A. Kumar, M. Santhanam, Detection of concrete damage using ultrasonic
pulse velocity method, National Seminar on Non-Destructive Evaluation,
Hyderabad Hyderabad (2006).
[28] T.R. Naik, V.M. Malhotra, J.S. Popovics, The ultrasonic pulse velocity method,
Handbook on nondestructive testing of concrete (2004) 169–188.
[29] RILEM, Water, Absorption Tube RILEM II.4 France (2006).
[30] N. Hollis, D. Stephen, P. Stu, Petrographic Methods of Examining Hardened
Concrete: A Petrographic Manual, United States Department of Transportation,
Virginia, 2006.
[31] A. Qudoos, H.G. Kim, J.-S. Ryou, Influence of the surface roughness of crushed
natural aggregates on the microhardness of the interfacial transition zone of
concrete with mineral admixtures and polymer latex, Constr. Build. Mater. 168
(2018) 946–957.
[32] P. Lawrence, M. Cyr, E. Ringot, Mineral admixtures in mortars: effect of inert
materials on short-term hydration, Cem. Concr. Res. 33 (12) (2003) 1939–
1947.
[33] P.K. Mehta, in: Pozzolanic and Cementitious Byproducts as Mineral
Admixtures for Concrete-a Critical Review, Special Publication, 1983, pp. 1–46.
[34] V. Papadakis, S. Tsimas, Supplementary cementing materials in concrete: part
I: efficiency and design, Cem. Concr. Res. 32 (10) (2002) 1525–1532.
[35] A. Memon, S. Radin, M.F.M. Zain, J.-F. Trottier, Effects of mineral and chemical
admixtures on high-strength concrete in seawater, Cem. Concr. Res. 32 (3)
(2002) 373–377.
[36] C. Edvardsen, Water permeability and autogenous healing of cracks in
concrete, Mater. J. 96 (4) (1999) 448–454.
[37] S. Jacobsen, E.J. Sellevold, Self healing of high strength concrete after
deterioration by freeze/thaw, Cem. Concr. Res. 26 (1) (1996) 55–62.
[38] D. Palin, V. Wiktor, H. Jonkers, Autogenous healing of marine exposed
concrete: characterization and quantification through visual crack closure,
Cem. Concr. Res. 73 (2015) 17–24.
[39] P.K. Mehta, in: Durability of Concrete in Marine Environment–A Review,
Special Publication, 1980, pp. 1–20.