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Materials 12 03863
Materials 12 03863
Article
Influence of Effective Water-to-Cement Ratios on
Internal Damage and Salt Scaling of Concrete with
Superabsorbent Polymer
Minsoo Kim 1 , Sung-Hoon Kang 1 , Sung-Gul Hong 1, * and Juhyuk Moon 2, *
1 Department of Architecture & Architectural Engineering, Seoul National University, 1 Gwanak-ro,
Gwanak-gu, Seoul 08826, Korea; ms607@hanmail.net (M.K.); medesis@snu.ac.kr (S.-H.K.)
2 Department of Civil & Environmental Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu,
Seoul 08826, Korea
* Correspondence: sglhong@snu.ac.kr (S.-G.H.); juhyukmoon@snu.ac.kr (J.M.); Tel.: +82-2-880-8360 (S.-G.H);
+82-2-880-1524 (J.M.)
Received: 12 September 2019; Accepted: 20 November 2019; Published: 22 November 2019
1. Introduction
Superabsorbent polymers (SAPs) are powdery products that absorb water of masses several tens
or hundreds of times their own mass. Studies have reported on SAP-induced changes in cement
composite properties after Jensen et al. proposed SAP as a water-entraining admixture for internal
curing in high-performance concrete [1,2]. It has been reported that SAPs can reduce the permeability
of water through cracks when cracks occur in cement composites [3–6]. It also has been reported that
SAPs heal cracks by supplying moisture to cement composites [7–10].
Studies on the effect of SAPs on the freeze–thaw resistance of concrete have also been reported.
SAPs that absorb water in fresh concrete release the water when the humidity inside the concrete
decreases due to the hydration of concrete and the evaporation of water. The water release reduces the
volume of the SAP and creates an air void inside the concrete. This air void is expected to improve the
freeze–thaw resistance of concrete. Similarly, the pore structure of concrete mixed with various types of
SAPs and the freeze–thaw resistance of concrete containing SAPs have been studied [11]. Freeze–thaw
resistance tests for concrete have been conducted by setting the SAP dosage and SAP particle size
as variables [12]. Recently, the effect of two types of SAPs on the freeze–thaw resistance of concrete
in various regions of the world has been reported via the results of an inter-laboratory study [13].
In those studies, reference mixtures with different water-to-cement ratios were compared with respect
to the freeze–thaw resistance. However, the effect of mixtures incorporating SAPs with different
effective water-to-cement ratios (i.e., total-water-to-cement ratio minus water-stored-by-SAP-to-cement
ratio) has not been fully elucidated. In this study, mixtures incorporating SAP with different effective
water-to-cement ratios and SAP content have been studied with respect to pore size distribution,
capillary water absorption, expansion of mixtures under freezing, and freeze–thaw resistance.
Along with the issue of effective water-to-cement ratios, there have been contradictory results
regarding the freeze–thaw resistance of concrete with SAPs. Many experimental studies have found that
SAP improves the freeze–thaw resistance of concrete [11–15]; however, opposite cases have also been
reported [13,14,16]. A possible explanation for these conflicting results could be the complex absorption
behavior of SAPs in hardened concrete when the concrete is exposed to water. This absorption and
further desorption behavior will change the effective water-to-cement ratio, which is treated as the
most important parameter in the mix design of concrete.
When hardened concrete is exposed to water, capillary pores (pores with a diameter of less than
10 µm) are known to be filled with water via capillary pressure. However, air in the air voids (pores
with a diameter larger than 10 µm) is trapped during capillary absorption [17]. In the case of air in the
air voids formed by SAPs, it will be trapped as well. The water in the capillary pores around an air void
will continuously evaporate until the water in the capillary pores and the water vapor in the air void
reach a thermodynamic equilibrium. A dry SAP in the air void will be exposed to this environment.
Furthermore, the absorption behavior of SAPs in hardened concrete may vary depending on the type
and size of the SAPs.
Common types of SAPs include cross-linked acylamide/acrylic acid copolymers, cross-linked
sodium polyacrylate, polymethacrylic acid, and polyethylene oxide. Among these, cross-linked
acylamide/acrylic acid copolymer is easy to manufacture and has a relatively high absorption rate
in the cement pore solution environment whereas cross-linked sodium polyacrylate is mostly used
for personal hygiene products. In our study, a cross-linked sodium polyacrylate (SAP_SP) which is
generally the most inexpensive was selected to clarify its effect on concrete materials under freeze–thaw
cycles. Because SAP_SP generally absorbs water in fresh mixtures, additional water should be added if
considering the SAP’s absorbency. However, it was found that the used SAP_SP prematurely released
the stored water. Thus, the effective water-to-cement ratios were increased with higher SAP_SP
contents. Therefore, it has to be pointed out that experimental results obtained from the used SAP_SP
may not be directly comparable to the available experimental data based on other types of SAPs with
different absorption and desorption characteristics.
As an outline of the test program, the SAP_SP absorbencies in pore solution and fresh mortar
were measured through a tea bag test and mortar flow test, respectively. The amount of capillary water
absorption and pore size distribution were measured in mortar samples with effective water-to-cement
ratio and SAP_SP dosage as variables. Moreover, the deformation of mortar samples during freeze–thaw
cycles was recorded. As a main discussion point, the measured internal damage and salt scaling of
concrete samples are considered.
Materials 2019, 12, 3863 3 of 14
2. Experimental Procedure
In preparing the mortar samples, a mortar mixer with a paddle that revolves in a planetary motion
was used. Cement was mixed with silica sand for 5 min and then mixed with dry SAP_SP powders for
2 min. Subsequently, water and polycarboxylate ether (PCE)-type superplasticizer (FLOWMIX P-STD,
Dongnam, Pyeongtaek, Korea) were added into the mixtures and then mixed for 5 min. In preparing
the concrete samples, mortar and gravels were weighed and then mixed for 10 min. The samples were
sealed with a polyester film after casting, demolded after 24 h, and stored in a climate chamber (20 ◦ C
and relative humidity (RH) 60%) until tests were performed. The American Society for Testing and
Materials (ASTM) C231 test was performed to measure the air content of the fresh concrete. The test
results are shown in Table 2.
14 140
8 80
6 60
4 40
2 20
0 0
0 50 100 150 200 250 300
Strain gauge
15 mm Acryl
container
Thermo
3 mm T couple
Aluminum
foil
20 mm Aluminum
35 mm Specimen foil
Epoxy resin
Spacer
(a) (b)
Figure 2. (a) Capillary suction test setup for mortar (section). (b) Strain measurement test setup for
Figureduring
mortar 2. (a) Capillary suction
freeze–thaw cyclestest setup for mortar (section). (b) Strain measurement test setup for
(elevation).
mortar during freeze–thaw cycles (elevation).
Concrete samples used in the freeze–thaw resistance test were prepared according to CEN/TS
3. Results
12390-9, but the process that involves curing the samples in tap water was excluded to avoid the
SAP_SPs from absorbing tap water at the early curing stage. The samples (150 mm × 150 mm × 50 mm)
3.1. Absorption
were Rate of SAPs
obtained through in Concrete
wet sawing from 150 mm cubes on the 21st day and then stored in a climate
chamber ◦
(20 3aC and RHthe
60%). Four samples
Figure shows absorbency of thewere prepared
SAP_SPs from forthe
each
teaseries. Before
bag test. Thethe 28th day,
highest rubber
absorbency
cloths wereg/g
was 21.3 glued
at 10onto
min,allwhich
surfaces except decreased
gradually one surfacewith
(thetime.
test surface)
However, of the samples
it was foundandthata SAP_SP
silicon
string was placed
prematurely on the
released theedge of water.
stored the testThe
surface. Pure water
absorbency from thewasflow
poured ontomuch
test was the test surface
lower thantothat
a
depth of 3 mm at 28 days from the start of the experiment. This condition lasted for 3 days at 20 ◦ C.
obtained from the tea bag test. This can be explained by the actual impact of the absorbency of
At 31 days,
SAP_SP in3mortar
mass %samples
NaCl solution was pouredchanges
on the rheological onto thewhich
test surface
can betodifferent
a depthfrom
of 3 mm before the
the absorbance
relative dynamicof
characteristics modulus
SAP_SPofparticles
the samples was measured.
themselves. Except absorbency
The highest for the test surface,
of the all surfacesinoffresh
SAP_SPs the
samples were insulated with 20 mm thick polystyrene
mortar was 3.1 g/g, which was observed at 10 min (Figure 3b).cellular plastic. The samples were placed in an
environmental chamber and then subjected to freeze–thaw cycles. After 7, 14, 28, 42, and 56 cycles,
the mass of fragments scaled from the test surface and the relative dynamic modulus of the samples
were measured.
3. Results
25.0 3.5
3
Absorbency (g/g)
Absorbency (g/g)
20.0
2.5
15.0 2
10.0 1.5
1
5.0
0.5
0.0 0
0 30 60 90 120 150 180 0 5 10 15 20
(a) (b)
Figure3.3.Absorbencies
Figure Absorbenciesofofthe
theSAP_SPs
SAP_SPsinin
solution according
solution to absorption
according time
to absorption as measured
time by (a)
as measured bytea
(a)
bag test and (b) flow test.
tea bag test and (b) flow test.
3.2. Pore Size Distribution
3.2. Pore Size Distribution
The bulk and skeletal densities and porosity of mortar samples as measured by an MIP test are
The bulk and skeletal densities and porosity of mortar samples as measured by an MIP test are
shown in Table 3. The bulk density of the mortars containing the SAP_SPs were slightly smaller than
shown in Table 3. The bulk density of the mortars containing the SAP_SPs were slightly smaller than
that of the reference mortar (Ref.). The capillary pore structure of mortars containing large amounts of
that of the reference mortar (Ref.). The capillary pore structure of mortars containing large amounts
SAPs (for which the range of w/c(stored by SAPs) was 0.04–0.3) has been studied by Snoeck et al. [23,24].
of SAPs (for which the range of w/c(stored by SAPs) was 0.04–0.3) has been studied by Snoeck et al. [23,24].
Their research showed that the capillary porosity of a reference mortar and mortars with SAPs are
Their research showed that the capillary porosity of a reference mortar and mortars with SAPs are
nearly the same, with the same w/c(effective) being observed, although the water stored by SAPs was
nearly the same, with the same w/c(effective) being observed, although the water stored by SAPs was
observed to cause further hydration of the cement, resulting in a small reduction in porosity. In the
observed to cause further hydration of the cement, resulting in a small reduction in porosity. In the
MIP test of the present study, porosity tended to increase with increasing w/c(effective) . Given the
MIP test of the present study, porosity tended to increase with increasing w/c(effective). Given the
considerably low w/c(stored by SAPs) values observed in this study, the hydration caused by the SAP_SPs
considerably low w/c(stored by SAPs) values observed in this study, the hydration caused by the SAP_SPs
was found to be negligible. The skeletal density showed no meaningful difference between samples.
was found to be negligible. The skeletal density showed no meaningful difference between samples.
Figure 4 shows the pore size distribution of the mortar samples. The pore volume per unit mass of the
Figure 4 shows the pore size distribution of the mortar samples. The pore volume per unit mass of
Ref. sample is larger than that of the samples containing the SAP_SPs at a pore radius of 40–90 nm.
the Ref. sample is larger than that of the samples containing the SAP_SPs at a pore radius of 40–90
On the contrary, when the pore radius is 90–400 nm or larger than 30 µm, the pore volume per unit
nm. On2019,
Materials the 12,
contrary, when
x FOR PEER the pore radius is 90–400 nm or larger than 30 μm, the pore volume
REVIEW 7 ofper
15
mass of the samples containing the SAP_SPs can be seen to be larger than that of the Ref.
unit mass of the samples containing the SAP_SPs can be seen to be larger than that of the Ref.
0.014 0.12
Incremental intrusion (mL/g)
0 0
1 100 10000 1000000 1 100 10000 1000000
Pore radius (nm) Pore radius (nm)
(a) (b)
Figure 4. Pore size distribution of the mortar samples. (a) Incremental intrusion and (b) cumulative
Figure 4. Pore size distribution of the mortar samples. (a) Incremental intrusion and (b) cumulative
intrusion according to pore radius.
intrusion according to pore radius.
Incremental intrusio
Cumulative intrusio
SAP_SP_0.3 0.08 SAP_SP_0.3
0.008
0.06
0.006
0.04
0.004
Materials 2019, 12, 3863 0.02 7 of 14
0.002
0 0
1 100 10000 1000000 1 samples100
Table 3. Bulk density, skeletal density, and porosity of mortar as measured 10000 1000000
by a mercury
Pore radius (nm)
intrusion porosimetry (MIP) test. Pore radius (nm)
(a) (b)
Sample Ref. SAP_SP_0.1 SAP_SP_0.2 SAP_SP_0.3
Bulk Density (g/mL) 2.05 2.04 2.01 2.04
Figure 4. Pore size distribution of the mortar samples. (a) Incremental intrusion and (b) cumulative
Skeletal Density (g/mL) 2.55 2.57 2.54 2.59
intrusion according
Porosity (vol. %) to pore radius.19.4 20.5 20.8 21.0
12
Water / dry mortar (mass %)
10
6
Ref.
4
SAP_SP_0.1
2 SAP_SP_0.2
SAP_SP_0.3
0
0 2 4 6 8
Time (day)
Figure 5. Capillary water absorption of mortar samples according to time immersed in water.
Figure 5. Capillary water absorption of mortar samples according to time immersed in water.
3.4. Strain on Mortar During Freeze–Thaw Cycles
3.4. Strain on Mortar During Freeze–Thaw Cycles
The strain of three samples was measured for each series during the freeze–thaw cycles. Figure 6
shows Thethestrain
sampleof three
with samples wasstrain
the largest measured for each
for each seriesseries during the
as a function of freeze–thaw cycles. Figure
water temperature in the
6 shows
acryl the sample
container. withfirst
In the the cycle,
largestallstrain for can
strains eachbe series
seenastoa decrease
function with
of water temperature
a similar slope inin the
the
acryl container.
freezing phase. In thethe first cycle,
second all strains
cycle, can beinseen
differences to decrease
strain with a similar
can be observed slope on
depending in the
thefreezing
sample.
phase.
The In the
strain second cycle,
of SAP_SP_0.3 differences
increases in strain
in the freezingcanphase,
be observed
whereasdepending
that of theon the samples
other sample. The strain
decreases.
of the
In SAP_SP_0.3
third cycle,increases in the
the strain of freezing
SAP_SP_0.3 phase, whereas
increases that of the other
significantly in thesamples
freezingdecreases. In the
phase, whereas
third
the cycle,of
strains theSAP_SP_0.2
strain of SAP_SP_0.3 increasesonly
and Ref. increase significantly
slightly. in the freezing
Finally, phase,
the peak whereas
points of thethe strains
strain for
of SAP_SP_0.2 and Ref. increase only slightly. Finally, the peak points of the
SAP_SP_0.3, SAP_SP_0.2, Ref, SAP_SP_0.14, and SAP_SP_0.1 in the freezing phase of the fourth cycle strain for SAP_SP_0.3,
are 1047 × 10−6
SAP_SP_0.2, Ref,
, 637 × 10−6 , 479 and
SAP_SP_0.14, −6 , 369 × 10−6
× 10SAP_SP_0.1 in, the
andfreezing −6 , respectively.
129 × 10phase of the fourth cycle
Table are 1047
4 shows the×
average peak points of the strains of the three samples for each series during the freezing phase of the
fourth cycle. The results show that SAP_SP_0.3 and SAP_SP_0.2, which have higher w/c(effective) than
the other samples, expand more as the freeze–thaw cycle repeats.
samples, expand more as the freeze–thaw cycle repeats.
Table 4. Average peak points of the strains on three specimens for each series during the freezing
phase of the fourth cycle.
Materials 2019, 12, 3863 8 of 14
Sample Ref. SAP_SP_0.1 SAP_SP_0.2 SAP_SP_0.3
Strain × 106 193.7 87.4 312.3 466.7
1200 1200
Cooling Cooling
1000 1000
Warming Warming
800 End 800
Strain × 10 6
Strain × 10 6
600 600
400 400 End
200 Start 200 Start
0 0
-200 -200
Ref. SAP_SP_0.1
-400 -400
-30 -20 -10 0 10 20 30 -30 -20 -10 0 10 20 30
Temperature (°C) Temperature (°C)
(a) (b)
1200 1200
Cooling Cooling
1000 1000
Warming Warming
800 800
Strain × 10 6
Strain × 10 6
600 End 600 End
400 400
200 Start 200 Start
0 0
-200 -200
SAP_SP_0.2 SAP_SP_0.3
-400 -400
-30 -20 -10 0 10 20 30 -30 -20 -10 0 10 20 30
Temperature (°C) Temperature (°C)
(c) (d)
Figure 6. Strain on mortar samples (a) Ref. (b) SAP_SP_0.1 (c) SAP_SP_0.2 (d) SAP_SP_0.3 during the
Figure 6. Strain on mortar samples (a) Ref. (b) SAP_SP_0.1 (c) SAP_SP_0.2 (d) SAP_SP_0.3 during the
four freeze–thaw cycles.
four freeze–thaw cycles.
Table 4. Average peak points of the strains on three specimens for each series during the freezing phase
3.5. Freeze–Thaw
of the fourth Resistance
cycle. of Concrete
TheSample
relative dynamic Ref.modulus of theSAP_SP_0.1
concrete samples according
SAP_SP_0.2to the number of freeze–thaw
SAP_SP_0.3
cycles is shown in Figure 7. In CEN/TS 12390-9, the sample is defined as damaged when the relative
Strain × 106 193.7 87.4 312.3 466.7
dynamic modulus of the sample is less than 80%. Ref. can be seen to always show the largest relative
dynamic modulus, but after 56 cycles, the value becomes 46%, indicating that the sample experiences
3.5. Freeze–Thaw Resistance of Concrete
critical damage. In the early cycles there was a temporal increase of the dynamic modulus of a few
samples. Stiffnessdynamic
The relative enhancement of concrete
modulus by absorbing
of the concrete samplesfreezing watertomay
according the cause
numbertheofincrease prior
freeze–thaw
to the isintended
cycles shown infreezing-induced
Figure 7. In CEN/TSdamage on the
12390-9, samples.
sampleFor SAP_SP_0.3,
is defined whichwhen
as damaged has the highest
the relative
w/c
dynamic , the relative
(effective)modulus dynamic
of the sample modulus after
is less than 80%.28 Ref.
cycles
canisbe
theseen
smallest, at 22%,
to always showand
theno stablerelative
largest signal
was obtained after 42 and 56 cycles.
dynamic modulus, but after 56 cycles, the value becomes 46%, indicating that the sample experiences
critical damage. In the early cycles there was a temporal increase of the dynamic modulus of a few
samples. Stiffness enhancement of concrete by absorbing freezing water may cause the increase prior to
the intended freezing-induced damage on samples. For SAP_SP_0.3, which has the highest w/c(effective) ,
the relative dynamic modulus after 28 cycles is the smallest, at 22%, and no stable signal was obtained
after 42 and 56 cycles.
Materials 2019, 12, x FOR PEER REVIEW 9 of 15
120
160
Ref. SAP_SP_0.1 SAP_SP_0.2 SAP_SP_0.3
RUPTT (%) RUPTT (%)
100
140
80
120
60
100
40
80
20
60
0
40
0 7 14 28 42 56
20
Number of freeze−thaw cycles
0
0 7 14 28 42 56
Figure 7. Relative dynamic modulus (RUPTT) of samples according to the number of freeze−thaw
cycles. Number of freeze−thaw cycles
Figure 7. Relative dynamic modulus (RUPTT ) of samples according to the number of freeze−thaw cycles.
Although SAP_SP_0.2 shows a larger relative dynamic modulus than SAP_SP_0.1 after 42 and
Figure 7. Relative dynamic modulus (RUPTT) of samples according to the number of freeze−thaw
56 cycles, the overall
Although resultsshows
SAP_SP_0.2 showathat therelative
larger higher dynamic
the SAP_SP content,
modulus theSAP_SP_0.1
than higher the w/c
after(effective)
42 and , and
56
cycles.
the faster
cycles, thethe relative
overall dynamic
results modulus
show that decreases
the higher as the cycle
the SAP_SP content,repeats.
the higher the w/c(effective) , and the
The cumulative
fasterAlthough mass
SAP_SP_0.2
the relative of fragments
shows a larger
dynamic modulus scaled
decreasesrelative from
as the dynamicthe surface
modulus
cycle repeats. of the
thansamples according
SAP_SP_0.1 after 42 to and
the
number
56 cycles,of freeze–thaw
the overallmass
The cumulative cycles
results is shown
show that scaled
of fragments in Figure
the higher
fromthe 8. The
theSAP_SP m s,n/A value was calculated according to
surface of content, the higher
the samples the w/c
according to the , and
number
(effective)
CEN/TS
the
of faster12390-9, wherein
the relative
freeze–thaw cyclesdynamicthe cumulative
is shown modulus massTheofmas
in Figuredecreases
8. fragments
s,n /A
the cycle
value was scaled
repeats.
was from
calculated a unit area
according toof the
CEN/TS test
surface.
12390-9, The results
The wherein
cumulative show that
the cumulative the higher
mass of fragments the
mass of scaled w/c
fragments(effective), the larger the mass of fragments scaled from
fromwas thescaled
surface of the
from samples
a unit area ofaccording to the
the test surface.
the sample.
number
The results In SAP_SP_0.3,
of freeze–thaw
show that the the is
cycles
highermass
theof
shown fragments
w/c in Figure , scaled
the8. The from
larger m the
s,n
the
/A sample
value
mass was
of after 56 cycles
calculated
fragments canfrom
according
scaled be seen to
the
(effective)
to have
CEN/TS In
sample. significantly
12390-9,
SAP_SP_0.3,increased
wherein thethe compared
cumulative
mass to
of fragments the other
massscaled samples.
of fragmentsfrom the was scaledafter
sample from56acycles
unit area
can of
be the
seentestto
surface.
have The results
significantly show that
increased the higher
compared to the w/c
other , the larger the mass of fragments scaled from
samples.
(effective)
the sample. In SAP_SP_0.3, the mass of fragments scaled from the sample after 56 cycles can be seen
6000
to have significantly increased compared to the other samples.
Ref. SAP_SP_0.1 SAP_SP_0.2 SAP_SP_0.3
5000
6000
2) /A (g/m 2)
4000
2000
3000
1000
2000
0
0 7 14 28 42 56
1000
Number of freeze−thaw cycles
0
Figure 8. Cumulative mass of fragments scaled from unit area of sample surface (ms,n /A) according to
0 7 14 28 42 56
Figure
the 8. Cumulative
number mass cycles.
of freeze–thaw of fragments scaled from unit area of sample surface (ms,n/A) according to
the number of freeze–thaw cycles. Number of freeze−thaw cycles
4. Discussion
Figure
4.1. Air 8. Cumulative
Voids mass of fragments scaled from unit area of sample surface (ms,n/A) according to
Formed by SAPs
the number of freeze–thaw cycles.
To discuss the characteristics of air voids formed by the SAP_SPs, the quantitative properties of
the air voids in a unit volume of mortar were calculated. First, to estimate the mass of dry SAP_SPs in
a unit volume of the mortar as shown in Table 5, the mass ratio of dry SAP_SPs in the fresh mortar in
Materials 2019, 12, 3863 10 of 14
Table 1 was divided by the density of hardened mortar in Table 3. In this calculation, the bulk density
of the hardened mortar was assumed to be equal to the density of fresh mortar. The volume of air
voids formed by the SAP_SPs in a unit volume of mortar was estimated as in Table 5 by the volume of
water stored by the SAP_SPs (absorbency = 3.1 g/g) in fresh mortar from the flow test.
Table 5. Mass of dry SAP_SPs and volume of air voids formed by the SAP_SPs in a unit volume
of mortar.
The derivation of Equation (1) can be referred to in [17]. Since the radius of the uncompressed air
bubble is determined by the radius of the pore containing the bubble, the volume of water absorbed by
a unit volume of the pore along the pore radius can be estimated. The cumulative volume of water
RA3 + 1.48 × 10−3 RA2 − R3 = 0 (1)
The derivation of Equation (1) can be referred to in [17]. Since the radius of the uncompressed
air bubble is determined
Materials 2019, 12, 3863 by the radius of the pore containing the bubble, the volume of 11water of 14
absorbed by a unit volume of the pore along the pore radius can be estimated. The cumulative volume
of water absorbed by a unit volume of mortar according to the pore radius is shown in Figure 9. The
absorbed
results basedby aon unit
thevolume
raw MIPof data
mortar areaccording to the pore
shown in Figure radius
9a and is shown
the results in Figure
based 9. The
on the MIP results
data after
based on the raw MIP data are shown in Figure 9a and the results based on the
modification are shown in Figure 9b. Data presented in Figure 9b well predicts the absorption amount MIP data after
modification are shown
of capillary water in Figure
considering the9b. Data presented
limitation in Figure
of the MIP 9b wellTherefore,
experiment. predicts the absorption
data in Figureamount
9b was
of capillary water considering the limitation of the MIP
used for the calculation of water volume in mortar in Table 6. experiment. Therefore, data in Figure 9b was
used for the calculation of water volume in mortar in Table 6.
0.2 0.2
Ref. Ref.
Cumulative volume of water
0.08 0.08
0.04 0.04
0 0
1 10 100 1000 10000 1 10 100 1000 10000
Pore radius (nm) Pore radius (nm)
(a) (b)
Figure 9. Cumulative volume of water absorbed by a unit volume of mortar. (a) Raw MIP data and (b)
Figure
MIP data9. after
Cumulative volume
modifications of water
were absorbed
applied by a unit volume of mortar. (a) Raw MIP data and
in the calculations.
(b) MIP data after modifications were applied in the calculations.
Table 6. Calculation procedure for absorbency of SAP_SP during capillary water uptake in mortar.
the SAP_SP but will expand to the relatively large capillary pores or air voids surrounding it. On the
other hand, a simple comparison of measured water uptake and capillary porosity shows that Ref.
absorbed a smaller volume of water than the capillary porosity but that the samples containing SAPs
absorbed a greater volume of water.
brine. These pockets make the ice easier to crack. Medium NaCl (2–5 mass %) solution forms a layer of
ice with moderate strength to damage the concrete [28].
When concrete shrinks as the temperature decreases below the freezing point, critical tensile stress
will not be applied to the ice layer. When the concrete considerably expands, critical tensile stress
will be applied to the ice layer and the concrete will also be damaged. Referring to the strain on the
mortar sample shown in Figure 6, it can be expected that the higher the SAP_SP content (i.e., the higher
the w/c(effective) in our system) the more damage there will be on the concrete surface due to a weaker
matrix. This prediction is consistent with the salt scaling results of the freeze–thaw resistance test as
shown in Figure 8.
5. Conclusions
In this work, a reference mixture and mixtures incorporating SAP with different w/c(effective) and
SAP_SP content have been studied with respect to pore size distribution, capillary water absorption,
expansion of mixtures under freezing, and freeze–thaw resistance. The fact that the internal damage
and salt scaling were found to increase as the SAP_SP content increased can be explained mainly by a
weaker cementitious matrix due to the increased w/c(effective) in the samples. In addition, the capillary
suction test results showed that the higher the SAP_SP content (i.e., the higher the w/c(effective) ), the
greater the amount of water absorbed in a unit volume of mortar. Assuming that SAP_SP absorbed
the increased water uptake, the absorbency of SAP_SP was calculated to be 23 g/g–44 g/g. This value
is considerably larger than the SAP_SP absorbency of 3.1 g/g of fresh mortar. Therefore, it can be
inferred that water-absorbing SAP_SP does not stay in the air voids formed by SAP_SP but expands to
the relatively large surrounding capillary pores or neighbor air voids. In this case, the freeze–thaw
resistance may be adversely affected.
Author Contributions: Conceptualization, investigation, and writing of the first draft, M.K.; resources, data
curation, and visualization, S.-H.K.; methodology and manuscript review and editing, S.-G.H. and J.M.
Funding: This work was supported by the Korea Agency for Infrastructure Technology Advancement (KAIA)
grant funded by the Ministry of Land, Infrastructure and Transport (Grant 19AUDP-B121595-04).
Acknowledgments: The Institute of Engineering Research in Seoul National University provided research facilities
for this work.
Conflicts of Interest: The authors declare no conflict of interest.
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