sustainability

Article
Mechanical Degradation and Thermal Decomposition
of Ethylene-Vinyl Acetate (EVA) Polymer-Modified
Cement Mortar (PCM) Exposed to High-Temperature
Hyung-Jun Kim 1 , Jae-Yeon Park 2 , Heong-Won Suh 2 , Beom-Yeon Cho 3 , Won-Jun Park 4 and
Sung-Chul Bae 2, *
1 Hazard Mitigation Evaluation Technology Center, Korea Conformity Laboratories, Cheongju 28115, Korea;
arc7707@kcl.re.kr
2 Department of Architectural Engineering, Hanyang University, Seoul 04763, Korea;
p9206@naver.com (J.-Y.P.); christ1205@naver.com (H.-W.S.)
3 Korea Institute of Civil Engineering and Building Technology, Gyeonggi-do 10223, Korea;
choby277@kict.re.kr
4 Department of Architectural Engineering, Kangwon National University, Samcheok 25913, Korea;
wjpark@kangwon.ac.kr
* Correspondence: sbae@hanyang.ac.kr; Tel.: +82-2-2220-0302




Received: 14 December 2018; Accepted: 17 January 2019; Published: 18 January 2019


Abstract: A polymer-modified cement mortar (PCM) is widely used as a repair material for reinforced
concrete (RC) structures owing to its excellent strength and durability. However, considering
the maintenance of the RC structures and the use period of the structures, the change in the
physical properties of the PCM should be evaluated when exposed to various high-temperature
environments, such as fires. In this study, the degradation of the mechanical properties (compressive
strength and modulus of elasticity), thermal decomposition of the PCM in various high-temperature
environments, and the change in the pore structure of the PCM after exposure to high temperatures
were quantitatively investigated. A mechanical property evaluation of PCM was performed under
three heating conditions: (i) heating in a compression tester, (ii) heating the specimen in an oven
to a predetermined temperature and then moving it to a compression tester preheated to the
same temperature, and (iii) cooling to room temperature after heating. In the experiment, a PCM
specimen was prepared by changing the polymer–cement ratio (polymer content) of ethylene-vinyl
acetate (EVA), the most commonly used polymer, to perform a high-temperature sectional test
from 200 to 800 ◦ C. In addition, to investigate the change in the PCM mechanical properties in the
high-temperature region, in terms of the pyrolysis of EVA, the porosity change and mass change were
examined using thermal analysis and mercury intrusion porosimetry. Before heating, the compressive
strength of the PCM increased with the EVA content up to 10 % of the polymer–cement ratio. Under
the cooling conditions after heating up to 200 ◦ C, the mechanical performance of the PCM was
restored, whereas the degradation of the mechanical properties of the PCM without cooling was
more pronounced. Furthermore, the mass loss, heat flow, and the total porosity of the PCM increased
as the EVA content increased, which is correlated with the degradation of the mechanical properties
of the PCM.

Keywords: polymer-modified cement mortar; ethylene-vinyl acetate; mechanical properties; repair

materials; heating

Sustainability 2019, 11, 500; doi:10.3390/su11020500 www.mdpi.com/journal/sustainability

Sustainability 2019, 11, 500 2 of 18

1. Introduction
Polymer-modified cement mortar (PCM) is superior to ordinary cement mortar in terms of
strength, durability, chemical resistance, and workability and is widely used for repairing and
strengthening reinforced concrete (RC) structures [1–4]. In earlier studies, PCM has shown different
physical and mechanical properties than those of ordinary inorganic cement mortar and concrete
because PCM is a mixture of polymeric organic material and cement mortar [5–7]. Considering the
maintenance of RC buildings and the use period of the structures, the change in the physical properties
of the PCM when exposed to high-temperature environments, such as fires, should be evaluated [8,9].
However, currently, studies on the mechanical properties of PCM exposed to high-temperature
environments and experiments on PCM before and after exposure to high temperatures are
insufficient [10–12]. It is due to the difficulties to obtain sufficient experimental data on the PCM
mechanical properties at high temperatures, as the evaluation (compression test) in a high-temperature
environment (or during a fire) requires a long preparation time, expensive measuring equipment,
heating, and temperature control for each high-temperature region [10–13]. Moreover, there is a risk
that the test equipment may be damaged if spalling occurs during heating in a state where the test
object is completely shut off. Therefore, an easier method to evaluate the mechanical characteristics of
the PCM in a high-temperature environment is required.
Conversely, concrete, which is an inorganic material, is known to undergo mechanical property
changes depending on the heating temperature range. Its compressive strength is reduced at 100 ◦ C
and recovers to near room temperature strength at 200 ◦ C. The strength decreases at a temperature
range of 450–550 ◦ C, at which calcium hydroxide, which is the main hydration product of cement
clinkers C3 S (tricalcium silicate) and C2 S (dicalcium silicate), decomposes in the section exceeding
300 ◦ C [14–16]. The reason for the decrease in the compressive strength at 100 ◦ C is the expansion of
the aggregate and the contraction and stress in the cement hydrate owing to water evaporation inside
the concrete. The change in the compressive strength at 100–300 ◦ C is attributed to complicated causes,
such as the difference in the thermal expansion and the deformation of different constituents of the
concrete and the acceleration of the hydration of the untreated cement clinker particles owing to the
moisture evaporating at a high-temperature in the concrete [14,17].
For PCM-applied concrete, the relationship between the compressive strength and temperature
under heating and cooling-after-heating, for concrete with the same materials and composition,
is summarized as follows [13]. The compressive strength for regular concrete decreases when heating
to 100 ◦ C and increases again between 200 and 300 ◦ C. Thereafter, as the temperature increases, the
compressive strength gradually decreases and then sharply decreases at 400 ◦ C or higher. However,
because the effect of the thermal decomposition of the polymer and the origin of the high-temperature
characteristics of ordinary concrete must be considered for PCM, a more complex analysis of the effects
of pyrolysis of the polymer (mass and porosity) is required, along with an empirical assessment of the
expected fire resistance and yield strength degradation of the PCM used in concrete structure repair.
Moreover, although PCM is widely used as a repair material for reinforced concrete structures, when
PCM is burned, that is, when it is exposed to a high temperature owing to a fire in buildings that are
repaired using PCM, spallation and ignition from the thermal decomposition of the polymer occur and
the strength of the structure is expected to decrease [11–13,18]. Therefore, to understand the change
in the mechanical properties of the PCM in high-temperature environments, in terms of the reuse
of the PCM-applied structures after a fire, the mechanical properties of PCM should be understood
in addition to the evaluated mechanical properties of the PCM under high-temperature conditions
similar to the actual fire environment [19].
Therefore, in this study, the mechanical performance (compressive strength and elastic modulus)
of the PCM at high temperatures, thermal decomposition, and the variation in the pore structure of
the PCM after exposure to high temperatures were experimentally evaluated. PCM test specimens,
in which the ethylene-vinyl acetate (EVA) content was varied in the polymer–cement ratio (EVA
polymer incorporation amount), were prepared using two heating processes to carry out per-section
 Sustainability 2019, 11, 500 3 of 18

Sustainability
experiments2018, 11,between
x FOR PEER and 800 ◦ C: (i) heating in the compression tester and (ii) heating
REVIEW
200 3 of the
18 specimen

in the oven to the specified temperature and then moving it to a preheated compression tester. The
tester. The specimens were compared to a specimen that was cooled to room temperature after
specimens were compared to a specimen that was cooled to room temperature after heating. Through
heating. Through this study, the relationships between the compressive strength, modulus of
this study, the relationships between the compressive strength, modulus of elasticity, mass changes
elasticity, mass changes owing to the thermal decompositions, and pore structure of the PCM at
owing
various to the thermal
temperature rangesdecompositions, andconditions
for different heating pore structure of the PCM at investigated.
were experimentally various temperature ranges
for different heating conditions were experimentally investigated.
2. Experiment Overview
2. Experiment Overview
2.1. Materials and Compositions
2.1. Materials and Compositions
The types and properties of the polymers used in the experiments are listed in Table 1. EVA was
used as The types and
the polymer, as properties
standardized of in
thethepolymers
Japanese used in the
Industrial experiments
Standards are6203
(JIS) A listed in Table 1. EVA
(polymer
was usedand
dispersions as re-dispersible
the polymer, polymer
as standardized
powders for in the Japanese
cement Industrial
modifiers). Standards
The mixing ratios (JIS)
of theAPCM
6203 (polymer
specimens are listed
dispersions in Table 2 [11,12].
and re-dispersible The water–cement
polymer powders forratio of the
cement PCM specimens
modifiers). was 50%,
The mixing andof the PCM
ratios
thespecimens
polymer–cement ratios
are listed in were
Table0,2 5, 10, and
[11,12]. 20%.
The In terms of cement,
water–cement ratio of Type
the PCMI ordinary
specimensPortland
was 50%, and
cement specified in JIS R 5210 was used in addition to fine aggregate (fineness modulus
the polymer–cement ratios were 0, 5, 10, and 20%. In terms of cement, Type I ordinary Portland 2.97, density
2.63cement
g/cm3, and water in
specified absorption
JIS R 52101.81%)
was specified in JIS A 5308
used in addition [20,21].
to fine The chemical
aggregate composition
(fineness modulus of 2.97, density
the cement was 3 determined via X-ray fluorescence spectroscopy (XRF, ZSX Primus Ⅱ, Rigaku,
2.63 g/cm , and water absorption 1.81%) specified in JIS A 5308 [20,21]. The chemical composition of
Tokyo, Japan) as presented in Table 3. Meanwhile, 1% of a blowing agent was added in order to
the cement was determined via X-ray fluorescence spectroscopy (XRF, ZSX Primus II, Rigaku, Tokyo,
disperse the polymer powders in the PCM. The cement-fine aggregate ratio (weight ratio) was 1:3,
Japan) as presented in Table 3. Meanwhile, 1% of a blowing agent was added in order to disperse
and three specimens at each level were fabricated and tested. In this study, the amount of the polymer
wasthe polymeraspowders
expressed weight per inunit
the PCM.
volume. The
Forcement-fine
example, 10 aggregate
kg/m3 of the ratio
unit(weight
polymerratio)
weight was 1:3, and three
in the
specimens at each level were fabricated
PCM composition corresponded to a 2% polymer–cement ratio.and tested. In this study, the amount of the polymer was
expressed as weight per unit volume. For example, 10 kg/m3 of the unit polymer weight in the PCM
composition correspondedTable
to a 1.
2% polymer–cement
Properties ratio.
of the polymer (EVA).

Residual Mass
Table 1. Properties of the polymer (EVA).
Volatile Apparent
Type and Structure of Ratio of Acid Value
Portion Density
the Polymer
Type and Structure of Volatile(%)
Portion Particle* (mg KOH/mg)
Residual Mass Ratio Acid Value (g/ml)
Apparent Density
the Polymer (%) (%)
of Particle * (%) (mg KOH/mg) (g/mL)
Ethylene-vinyl acetate
Ethylene-vinyl acetate
(EVA)
(EVA)

Less
Lessthan
than2.0
2.0 Less than 2.0than 2.0 Less thanLess
Less 2.0 than 2.0 0.50 ± 0.100.50 ± 0.10

*Residual* Residual
mass ratio afterratio
mass passing
after through a 300 μm
passing through sieve.
a 300 µm sieve.

Table 2. Mix proportions of the PCM specimens.

Table 2. Mix proportionsWater–Cement
of the PCM specimens.
Type of Polymer–Cement Ratio (P/C) Water–Binder Ratio
Specimens Ratio
Polymer (%) Polymer–Cement Water–Cement (W/B) Water–Binder
Type of Polymer Specimens (W/C)
None E0 0
Ratio (P/C) (%)
0.5
Ratio (W/C) Ratio (W/B)
NoneE5 E0 5 0 0.53 0.5
0.5
EVA E10 10 0.56
E5 5 0.53 0.5
E20 20 0.63
EVA E10 10 0.56
E20 20 0.63
Table 3. Chemical compositions of ordinary Portland cement, as measured by XRF.

Composition SiO23. Chemical

Table Al2O3 compositions
Fe2O3 CaO MgO Portland
of ordinary K2O cement,
SO3 TiO
as LOI by XRF.
measured
2 Total
(wt%) 18.42 2.84 2.16 68.18 2.35 1.13 3.01 0.15 1.76 100
Composition SiO2 Al2 O3 Fe2 O3 CaO MgO K2 O SO3 TiO2 LOI Total
(wt%) 18.42 2.84 2.16 68.18 2.35 1.13 3.01 0.15 1.76 100
2.2. Heating Conditions and Test Method
Sustainability 2019, 11, 500 4 of 18

2.2. Heating Conditions and Test Method

The PCM specimens for the mechanical test were manufactured with a dimension of
ϕ 100 × 200 mm. After mixing the raw materials, the air content and the slump flow of the fresh PCM
were measured. The specimens were wet-cured for 2 days (20 ◦ C, 90% RH) and then underwater-cured
at 20 ◦ C for 28 days. After curing in water, aerial curing was carried out for 63 days under an
environment of 20 ◦ C and 60% RH. The specimens were dried in a drying furnace at 60 ◦ C for one
week before the heating test and then cooled to room temperature in a desiccator. Through these
steps, the water absorption of the specimen was adjusted to within the range of 1.5 to 2.0% [22,23].
The curing procedure described above was accessed in accordance with JIS A 1171 (test methods for
polymer-modified mortar).
Conversely, the appropriate heating rate should be determined to prevent spalling or an explosion
owing to the thermal stress caused by the temperature difference between the center and surface
of the specimen. In one of the preliminary experiments (the water content of the test body was
approximately 3.0%), when the heating rate was 150 ◦ C/h, the specimen spalled 3 h after heating;
however, the specimen did not spall when the heating rate was 100 ◦ C/h. Based on the results of
the preliminary test, the water content of the test specimen was maintained below 2.0%, considering
the two high-temperature environments and the heating program, as shown in Figure 1, was set at a
heating rate of 100 ◦ C/h [11–13]. To monitor the temperature at the center and surface of the specimen,
a thermocouple was pre-embedded in the specimen, as shown in Figure 2a.
In the conventional compression test under heating, as shown in Figure 2b, a compression test
was conducted after heating with the heater installed; however, there were issues with this test, such
as a restriction of the number of experiments and equipment damage [13]. In this study, a specimen
that reached a predetermined temperature during heating in the oven (Figure 2c) was transferred to a
compression tester (Figure 2d) preheated to the same temperature and compressed. As a comparison,
the sample heated until the internal temperature of the sample reached a predetermined temperature,
as shown in Figure 1, and then the sample cooled in air was tested on the compressive machine.
In this study, (i) heating in a compression tester, (ii) heating the specimen in an oven to a
predetermined temperature and then moving it to a compression tester preheated to the same
temperature, and (iii) cooling to room temperature after heating were referred to as (i) in situ-heating,
(ii) oven-heating, and (iii) cooling, respectively. Meanwhile, in the compression test during in situ- and
oven-heating, the heating temperature was maintained for 0.5 to 2.5 h until the internal temperature of
the test specimen reached the set temperature.
Pyrolysis of the PCM occurs in a high-temperature environment to generate gas, and most of the
generated gas is released to the exterior of the test body; however, some of it is trapped in the pore
structure inside the test body. The total amount of porosity and pore distribution were measured using
mercury intrusion porosimetry (MIP, AutoPore IV, Micromeritics, Norcross, GA, USA). Moreover,
the mass change and heat flow of EVA and PCM was measured by thermogravimetry (TG, heating
rate: 20 ◦ C/min, STA7200, Hitachi, Japan) and differential scanning calorimetry (DSC, heating rate:
20 ◦ C/min, DSC7020, Hitachi, Tokyo, Japan). For the tests, the PCM specimen with dimension of
100 × 100 × 400 mm was prepared. The specimen was cured using the same protocol of the specimen
for the mechanical test. After the curing, the specimen was sliced (100 × 100 × 10 mm) and dried in a
drying furnace at 60 ◦ C to control the water absorption of the specimen within the range of 1.5 to 2.0%.
Sustainability 2019, 11, 500 5 of 18
Sustainability
Sustainability2018,
2018,11,
11,xxFOR
FORPEER
PEERREVIEW
REVIEW 55 of
of 18
18

Figure
Figure 1.
Figure 1. Heating
1. Heating program
Heating program for
program for the
for the PCM
the PCM specimens
PCM specimens (in
specimens (in situ-heating,
(in oven-heating,
situ-heating, oven-heating,
situ-heating, and
oven-heating,and cooling).
andcooling).
cooling).

Figure
Figure2. 2.Setup
Setupfor
Setup for the
the compression
compressiontest:
compression test:(a)
(a) specimen
specimendimension
specimen dimensionand
dimension andthe
thelocation
the locationof
location ofthe
thethermocouple
the thermocouple
thermocouple
installation
installation (unit:
(unit: mm),
mm), (b)
(b) compressive
compressive strength
strength test
test machine
machine (in (in situ-heating)
situ-heating) (previously
(previously
installation (unit: mm), (b) compressive strength test machine (in situ-heating) (previously used used
in in
[13]),
used in
[13]),
(c) (c)
heatingheating
oven oven (oven-heating),
(oven-heating), and and
(d) (d) compressive
compressive strength
strength test test
machinemachine (oven-heating).
(oven-heating).
[13]), (c) heating oven (oven-heating), and (d) compressive strength test machine (oven-heating).

3. Experimental
3. Experimental Results and
and Analysis
3. Experimental Results
Results and Analysis
Analysis
3.1. Mechanical Properties of the PCM at Room Temperature (before Heating)
3.1.
3.1. Mechanical
Mechanical Properties
Properties ofof the
the PCM
PCM atat Room
Room Temperature
Temperature (before
(before Heating)
Heating)
Figure 3 shows the compressive strength and modulus of elasticity of the PCM specimens with
Figure
Figure 33 shows
shows thethe compressive
compressive strength
strength and
and modulus
modulus of of elasticity
elasticity of
of the
the PCM
PCM specimens
specimens with
with
different mixing ratios of EVA at room temperature (unheated). The compressive strength of the PCM
different mixing ratios of EVA at room temperature (unheated). The compressive
different mixing ratios of EVA at room temperature (unheated). The compressive strength of the PCMstrength of the PCM
increased with the EVA content up to 10% of the polymer–cement ratio; however, the compressive
increased
increased with
with the
the EVA
EVA content
content up up to
to 10%
10% of
of the
the polymer–cement
polymer–cement ratio;ratio; however,
however, thethe compressive
compressive
strength slightly decreased when the ratio was increased to 20%. Similar to the compressive strength,
strength
strength slightly
slightly decreased
decreasedwhen when the
the ratio
ratio was
was increased
increased to
to 20%.
20%. Similar
Similar to
to the
the compressive
compressive strength,
strength,
the
the modulus of elasticity of the PCM mixed with EVA increased for the 10% polymer–cement ratio
modulus of elasticity of the PCM mixed with EVA increased for the 10% polymer–cement ratio
and
and decreased
decreased forfor 20%
20% incorporation.
incorporation.
Sustainability 2019, 11, 500 6 of 18

the modulus2018,
Sustainability of elasticity of theREVIEW
11, x FOR PEER PCM mixed with EVA increased for the 10% polymer–cement ratio6 and
of 18
decreased for 20% incorporation.
Sustainability 2018, 11, x FOR PEER REVIEW 6 of 18

Figure 3. Mechanical properties of the PCM (unheated specimen): (a) compressive strength and (b)
elastic 3.
Figure modulus.
Mechanical
Mechanical properties
properties of
of the
the PCM
PCM (unheated
(unheated specimen):
specimen): (a)
(a) compressive
compressive strength
strength and
and (b)
(b)
elastic modulus.
3.2. Preliminary Review of the Heating Methods (In Situ-Heating vs. Oven-Heating)
3.2. Preliminary
3.2. Preliminary Review
Review of of the
the Heating
Heating Methods
Methods (In(In Situ-Heating
Situ-Heating vs. Oven-Heating)
vs. Oven-Heating)
Unlike the existing in situ-heating methods, the oven-heating method requires the movement of
Unlike
Unlike
a large the existing
the
number existing in
in situ-heating
frommethods,
situ-heating
of test specimens methods, the
theoven-heating
the preheating oven to themethod
oven-heating methodrequires testthe
requires
compressive themovement andofthe
movement
apparatus ofa
large number
atemperature
large number of test
ofofthetestspecimens
specimens
test from
specimenfrom the
maythe preheating
droppreheating oven
when theoven to the compressive
to the is
specimen compressive test
moved intotest apparatus
theapparatus and the
andfrom
test machine the
temperature
temperature of
of the
the test
test specimen
specimen may
may drop
drop when
when the
the specimen
specimen is
is moved
moved
the preheating oven. Figure 4 shows the temperature drop from the moment the specimen heated to into
into the
the test
test machine
machine from
from
the
the preheating
800preheating
°C was removedoven. Figure
oven. Figure
from the 44 shows
shows the temperature
the
preheating temperature
oven; this wasdrop
drop from the
from
measured thewith
moment
moment the specimen
the specimen
a thermocouple heated
heated
buried to
to
in the
800 ◦ C was removed from the preheating oven; this was measured with a thermocouple buried in the
800 °C was removed
specimen, as shownfrom the preheating
in Figure 2a. In thisoven; this wasthe
experiment, measured with astrength
compressive thermocouple buried
test was in the
carried out
specimen,
specimen,
within 4 min as shown
as shown in Figure
in Figure
of removing 2a. In
2a. In
the test this experiment,
this experiment,
specimen the compressive
the compressive
from the oven, strength
strength test
and the temperature test
dropwas
was carried
wascarried out
out
confirmed
within
within
to be 3044 min
min ofless,
of
°C or removing
removing the
exceptthe test
fortest specimen
thespecimen fromportion
from
surface layer the oven,
the oven, and
(A and the temperature
the
in Figure temperature
4) and bottom drop(Ewas
drop was confirmed
confirmed
in Figure 4) of
to ◦ C or less, except for the surface layer portion (A in Figure 4) and bottom (E in Figure 4) of the
bespecimen
30
to be
the 30 °C or less,
within except for the surface layer portion (A in Figure 4) and bottom (E in Figure 4) of
the range.
specimen within the range.
the specimen within the range.

Figure4.4.Temperature
Figure Temperaturedrop
dropupon
uponmoving
movingthetheoven-heated
oven-heatedtest
testspecimen
specimenfrom
fromthe
thepreheating
preheatingoven
oven
tothe
to thecompression
Figure compression
4. tester
Temperature drop
tester (dimension unitof
upon moving
(dimension unit ofthe
thethe specimen:mm).
oven-heated
specimen: mm).
test A–E:Location
Location
specimen
A–E: ofthermocouples
from the
of thermocouples
preheating ovenin
in
the
to
the specimen.
the compression tester (dimension unit of the specimen: mm). A–E: Location of thermocouples in
specimen.
the specimen.
In addition, for a comparison with the test method of the compressive strength during heating
In addition, for
in the preheating a comparison
oven proposed in with
thisthe test method
study, of the
the validity ofcompressive strength
the test method during heating
was examined using
inthe
thesame
preheating
level ofoven proposed as
test materials in those
this study,
in thethe
in validity of theIntest
situ-heating. themethod was examined
comparative using
experiment, the
the same levelstrength
compressive of test materials
and elasticasmodulus
those inwere
the in situ-heating.
measured at 20, In
200,the comparative
400, and 600 °C experiment, the
for the specimen
compressive
with 10% EVA strength and elastic
(E10, water modulus
content were
2.0%) and measured
without EVA at(E0),
20, 200,
at a400, and rate
heating 600 °C for the
of 100 specimen
°C/h. The test
with 10% EVA (E10, water content 2.0%) and without EVA (E0), at a heating rate of 100 °C/h. The test
Sustainability 2019, 11, 500 7 of 18

In addition, for a comparison with the test method of the compressive strength during heating
in the preheating oven proposed in this study, the validity of the test method was examined using
the same level
Sustainability of xtest
2018, 11, FORmaterials
PEER REVIEWas those in the in situ-heating. In the comparative experiment, 7 ofthe
18
compressive strength and elastic modulus were measured at 20, 200, 400, and 600 ◦ C for the specimen
with 10%
results areEVAshown(E10, inwater
Figure content
5. For 2.0%) and without
the mortar withoutEVA EVA,(E0),
theatcompressive
a heating rate of 100 ◦and
strength C/h.modulus
The test
results
of are shown
elasticity graduallyin Figure 5. Forcompared
decreased the mortar without
with the roomEVA,temperature
the compressive strength and
measurements. Formodulus
E10, the
of elasticity
strength gradually
decreased by decreased
approximatelycompared with the
50% when roomup
heating temperature
to 200 °C. measurements. For E10,and
However, the strength the
strength decreased by partially
approximately 50% when heating ◦
elastic modulus were restored when heating upupto to
400200°C.C. However, the
Furthermore, strength
they and
decreased
elasticheating
when modulus upwere partially
to 600 restored
°C. Thus, when heating
regardless up to 400 ◦ C. of
of the incorporation Furthermore,
EVA, both the theyheating
decreased when
methods
heating
(in situ- up 600 ◦ C. Thus,showed
andtooven-heating) regardless of the incorporation
a similar of EVA, both
relationship. Therefore, the the heating methods
correlation between the(in situ-
test
and oven-heating)
method showed a similar
using the preheating relationship.
oven proposed Therefore,
in this the correlation and
study (oven-heating) between the test method
the existing hot test
using the(in
method preheating oven was
situ-heating) proposed in this study
established. Based(oven-heating)
on the results, and wetheconcluded
existing hot testthe
that method
drop (inin
situ-heating) was established. Based on the results, we concluded that
temperature (up to 30 °C) when the sample was moved from the oven to the compression test the drop in temperature (up to
◦
30 C) when the sample
apparatus did not have was moved from
a significant the
effect onoven
the to
testthe compression
results. test apparatus
The results did not have
of the evaluation of thea
significant effect
mechanical on the test
performance ofresults.
the PCM Thespecimens
results of the
withevaluation of theincorporation
various EVA mechanical performance
ratios, using of the
PCM specimens
oven-heating with various
method proposed EVA incorporation
in this ratios, using
study, are described the oven-heating
in more detail (Sectionmethod
3.3). proposed in
this study, are described in more detail (Section 3.3).

Figure 5. Comparison
Comparison of
of (a)
(a) the
the compressive
compressive strength
strength and
and (b)
(b) elastic
elastic modulus
modulus (in
(in situ-heating
situ-heating vs.
vs.
oven-heating).

3.3. Physical
3.3. Physical Properties
Properties of
of the
the PCM
PCM
Table 44 lists
Table lists the
the air
air content
content and
and slump flow value
slump flow value for
for each
each combination
combination of of fresh
fresh PCM.
PCM. As As the
the
polymer–cement ratio
polymer–cement ratio increased,
increased, the
the amount
amount ofof air
air and
and slump
slump flow
flow increased.
increased. The
The increase
increase in
in EVA
EVA
content in PCM induced the increased water to cement mass ratio (W/C) of the
content in PCM induced the increased water to cement mass ratio (W/C) of the PCM, resulting in PCM, resulting in
higher air content and larger slump flow because EVA is intrinsically inert and acts as fine
higher air content and larger slump flow because EVA is intrinsically inert and acts as fine aggregates aggregates
in the
in the cement
cement mortar.
mortar. The
The increase
increase in
in the
the number
number of of air
air voids
voids or
or pores
pores in
in different
different scales
scales owing
owing toto the
the
incorporation of the polymer are discussed in detail with the MIP results (Section
incorporation of the polymer are discussed in detail with the MIP results (section 4.). 4).

Table 4.
Table Measurement results
4. Measurement results for
for the
the air
air content
content and
and slum
slum flow
flow of
of the
the PCM
PCM in
in fresh
fresh conditions.
conditions.
Specimen Polymer–Cement Ratio (P/C)
Polymer–Cement Ratio(%)
(P/C) Air Content (Average, %)
Air Content Slum Flow
Slum (mm)
Flow
Specimen
E0 0 (%) (average,
4.9 %) (mm)
161 ± 10
E5
E0 5 0 6.2 4.9 199 ±8
161±10
E10
E5 10 5 7.6 6.2 208 ±9
199±8
E20
E10 20 10 8.7 7.6 215 ±7
208±9
E20 20 8.7 215±7

The changes in the mass of the PCM specimens before and after heating are listed in Table 5. The
mass loss ratios compared to the unheated specimen are also shown in Figure 6. The EVA-
incorporated PCM specimens (E5, E10, and E15) exhibited a larger decrease in the mass loss ratio
upon heating than those of E0. The higher the substitution ratio of EVA and the heating temperature
were, the larger the decrease in the mass loss ratios became. Thus, E20 showed the highest mass loss
ratio (approximately 13%) when heated to 800 °C, compared to the unheated specimen.
Sustainability 2019, 11, 500 8 of 18

The changes in the mass of the PCM specimens before and after heating are listed in Table 5.
The mass loss ratios compared to the unheated specimen are also shown in Figure 6. The EVA-
incorporated PCM specimens (E5, E10, and E15) exhibited a larger decrease in the mass loss ratio upon
heating than those of E0. The higher the substitution ratio of EVA and the heating temperature were,
the larger the decrease in the mass loss ratios became. Thus, E20 showed the highest mass loss ratio
(approximately 13%) when heated to 800 ◦ C, compared to the unheated specimen.

Table 5. Changes in the mass of the specimen before and after heating.

Type of Polymer-Cement Heating Mass (g)

PCM Ratio (P/C) (%) Condition 20 ◦C 200 ◦C 400 ◦ C 600 ◦ C 800 ◦ C
Before
417.0 412.7 414.3 415.5 410.4
E0 0 heating
After
417.0 398.1 393.1 388.2 377.1
heating
Sustainability 2018, 11, x FOR PEER REVIEW 8 of 18
Before
416.9 413.3 421.2 408.9 409.7
E5 5 heating
Table 5. Changes in the mass of the specimen before and after heating.
After
416.9 394.8 396.3 379.9 373.3
heating
Polymer-Cement Ratio (P/C) Heating Mass (g)
Type of PCM
(%) Before Condition 20 °C 200 °C 400 °C 600 °C 800 °C
412.5 heating414.1417.0
Before 412.0
412.7 410.2 415.5
414.3 409.9
410.4
E10
E0 10 0 heating
After After heating 417.0 398.1 393.1 388.2 377.1
412.5 heating394.9416.9
Before 383.3
413.3 377.6 408.9
421.2 368.3
409.7
E5 5 heating
After heating 416.9 394.8 396.3 379.9 373.3
Before Before
E10 10 408.8 heating405.2412.5 414.1
402.4 412.0
408.0 410.2 409.9
399.5
E20 20 heating After heating 412.5 394.9 383.3 377.6 368.3
After Before
E20 20 408.8 heating384.5408.8 405.2
371.2 402.4
370.9 408.0 399.5
353.0
heating After heating 408.8 384.5 371.2 370.9 353.0

Figure 6. Mass loss of the PCM specimens owing to heating.

3.4. Mechanical Properties

3.4. Mechanical Properties of
of the
the PCM
PCM Specimens
Specimens Under
Under Different
Different Heating
Heating Conditions
Conditions
Contents of the Cooling Specimen
3.4.1. Contents of the Cooling Specimen
Table 6 shows the compressive strength and modulus of elasticity change for the PCM specimens,
Table 6 shows the compressive strength and modulus of elasticity change for the PCM
depending on the heating temperature and conditions for cooling to room temperature after heating.
specimens, depending on the heating temperature and conditions for cooling to room temperature
Because the specimen had different initial values before heating, the ratios of residual compressive
after heating. Because the specimen had different initial values before heating, the ratios of residual
strength and elastic modulus were calculated as shown in Figure 7. The compressive strength gradually
compressive strength and elastic modulus were calculated as shown in Figure 7. The compressive
decreased by increasing heating temperatures. In the case of heating up to 600 ◦ C and 800 ◦ C, PCM
strength gradually decreased by increasing heating temperatures. In the case of heating up to 600 °C
exhibited similar compressive strength regardless of EVA contents. The elastic modulus also decreased
and 800 °C, PCM exhibited similar compressive strength regardless of EVA contents. The elastic
modulus also decreased with the increase of EVA contents and heating temperature. In contrast to
the compressive strength result, there is no significant degradation of elastic modulus when heated
up to 200 °C.
Sustainability 2019, 11, 500 9 of 18

with the increase of EVA contents and heating temperature. In contrast to the compressive strength
result, there is no significant degradation of elastic modulus when heated up to 200 ◦ C.

Table 6. Compressive strength of the PCM specimens cooled after heating (100 × 200 mm) (in graph).

Compressive Strength (MPa) Elastic Modulus (GPa)

Temp. (◦ C)
E0 E5 E10 E20 E0 E5 E10 E20
20 64.0 57.4 57.0 52.6 21.2 19.3 18.7 16.0
200 58.5 52.1 46.1 34.4 17.7 16.1 15.6 12.8
400 45.8 44.7 39.9 31.1 13.9 12.0 12.4 7.5
600 28.3 28.8 28.6 23.8 3.1 6.6 5.1 6.0
Sustainability800 16.6
2018, 11, x FOR 18.0
PEER REVIEW 17.1 12.8 1.7 3.5 3.4 3.1 9 of 18

(a) (b)
1.0
E0 1.0
E0

Residual compressive strength ratio

Residual compressive strength ratio

E5 E5
E10 E10
0.8 E20 0.8 E20

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

Figure 7. (a) The residual compressive strength

Figure 7. strength ratio
ratio and
and (b)
(b) the
the residual
residual elastic
elastic modulus
modulus ratio
ratio of
of the
the
PCM ◦
PCM specimens
specimens cooled
cooled after
after heating
heating at
at different
differenttemperatures
temperatures(200,
(200,400,
400,600,
600,and
and800 C).
800 °C).

Figure
Figure 8a8a depicts
depictsthe
thecompressive
compressivestrength
strengthofofthethe PCM
PCM specimens
specimens (E0,(E0,
E5, E5,
E10,E10,
and and
E20) E20) at
at each
each
heatingheating temperature
temperature (oven-heating).
(oven-heating). The residual
The residual compressive
compressive strength
strength ratio
ratio of theofheated
the heated
PCM
PCM
specimen compared to the unheated specimen is shown in Figure 7b. The degradation of the
specimen compared to the unheated specimen is shown in Figure 7b. The degradation of the
mechanical
mechanicalproperties
propertiesofofthe
thePCMPCMspecimens
specimensinina ahigh-temperature
high-temperature environment
environment waswasconsidered
considered to be
to
caused by the evaporation of the binding water, the thermal decomposition
be caused by the evaporation of the binding water, the thermal decomposition of the polymer, and of the polymer, and the
thermal decomposition
the thermal decomposition of the hardened
of the hardened cement
cement paste.
paste.The
Thethermal
thermalproperties
propertiesofofthethebonded
bonded water water
and
and cement
cement mortar
mortar and
and the
the deterioration
deterioration of of the
the mechanical
mechanical properties
properties of of the
the mortar
mortar (or(or concrete)
concrete) are are
listed in Table 7, based on the previous studies
listed in Table 7, based on the previous studies [14–17]. [14–17].
In this study, regardless of the heating conditions up to 200 °C, with an increase in the
polymer–cement ratio, theTable compressive strength
7. Thermal decreased
properties sharplycement.
of the hardened (Figure 8a) because the polymer
melting point is from 70 to 120 ◦ C which is very different trend compared to the results of cooling
Temperature Section Internal Reaction Reaction Overview
(see Figure 7). In the heating 200 to 400 ◦ C, the compressive strength slightly recovered upon
rangeofofphysically
Evaporation
cooling,~30–120 °C
E10. Because ofadsorbed
the residual Water evaporation in large pores
water strength ratio (Figure 8b), the strength decreased in proportion to
◦
the increase in the polymer–cement ratio, up to 400 C; however, Stepwise
when dehydration
heated to C3A3◦CSH
of 600 C and
32 800◦ C, the
residual strength ratio was approximately 0.4 and 0.3,Crespectively,3ACSH12 is dehydrated and forms (C4A3S) or CaO
regardless of the polymer–cement
Release of chemically Dehydration of aluminate-based hydrates: C3AH6
ratio. The decomposition
~30–300 °C of EVA dominated the deteriorationDehydrates of the mechanical
at ~270–330 °Cproperties of the
adsorbed water;
PCM when~120–600 °C up to 200 °C. However, the effectCompletely
heated of the decomposition
dehydrates at 550 °C and forms C12Ais
of C-S-H, which the
7 or CaOmain
Gel tissue breakdown
hydration product of cement clinker, was dominant above 600
160 °C: ◦
CaSOC.4・2H2O (Gypsum)→CaSO4 + H2O
~450–550 °C: Ca(OH)2→CaO + 2H2O
573 °C Quartz phase change Phase change α→β-SiO2
~600–700 °C C-S-H decomposition β-C2S formation
Calcium Carbonate (CaCO3) Decomposition of limestone aggregate
~580–920 °C
decomposition CaCO3 → CaO + CO2
~1100–1200 °C Concrete melting Cement paste: melts around 1200 °C

In this study, regardless of the heating conditions up to 200 ℃, with an increase in the polymer–
cement ratio, the compressive strength decreased sharply (Figure 8a) because the polymer melting
point is from 70 to 120 °C which is very different trend compared to the results of cooling (see Figure
Sustainability 2019, 11, 500 10 of 18

Table 7. Thermal properties of the hardened cement.

Temperature Section Internal Reaction Reaction Overview

◦C Evaporation of physically
~30–120 Water evaporation in large pores
adsorbed water
Stepwise dehydration of C3 A3 CSH32
C3 ACSH12 is dehydrated and forms (C4 A3 S) or CaO
Release of chemically Dehydration of aluminate-based hydrates: C3 AH6
~30–300 ◦ C
adsorbed water; Dehydrates at ~270–330 ◦ C
~120–600 ◦ C
Gel tissue breakdown Completely dehydrates at 550 ◦ C and forms C12 A7 or CaO
160 ◦ C: CaSO4 · 2H2 O (Gypsum)→CaSO4 + H2 O
~450–550 ◦ C: Ca(OH)2 →CaO + 2H2 O
573 ◦ C Quartz phase change Phase change α→β-SiO2
~600–700 ◦C C-S-H decomposition β-C2 S formation
Calcium Carbonate Decomposition of limestone aggregate
~580–920 ◦ C
(CaCO3 ) decomposition CaCO3 → CaO + CO2
~1100–1200 ◦ C Concrete melting Cement paste: melts around 1200 ◦ C
Sustainability 2018, 11, x FOR PEER REVIEW 10 of 18

Figure 8. (a) Compressive strength of the PCM specimens heated at different temperatures
Figure 8. (a) Compressive
(oven-heating, 200, 400, 600,strength ◦ C)the
and 800 of andPCM specimens
(b) the residual heated at different
compressive temperatures
strength (oven-
ratio compared to
the unheated
heating, 200, specimen.
400, 600, and 800 °C) and (b) the residual compressive strength ratio compared to the
unheated specimen.
Figure 9a shows the relationship between the moduli of elasticity of the PCM specimens at
different
Figureheating temperatures,
9a shows and Figure
the relationship 9b shows
between the ratio
the moduli of of the modulus
elasticity of the of
PCMelasticity at each
specimens at
heating temperature relative to the PCM at room temperature (unheated). The elastic
different heating temperatures, and Figure 9b shows the ratio of the modulus of elasticity at each modulus of the
PCM decreased
heating temperaturewith relative
an increase in PCM
to the the polymer–cement
at room temperature ratio.(unheated).
In the case of
TheE10 and E20,
elastic the elastic
modulus of the
modulus up to a heating temperature of 200 ◦ C showed a sharp decrease as the polymer-cement ratio
PCM decreased with an increase in the polymer–cement ratio. In the case of E10 and E20, the elastic
increased,
modulus up as to
found in thetemperature
a heating compressiveofstrength results. aInsharp
200 °C showed addition, E10 as
decrease and
theE20 exhibited a similar
polymer-cement ratio
elastic modulus.
increased, as found in the compressive strength results. In addition, E10 and E20 exhibited a similar
Figure
elastic 10 shows the stress–strain curve of the EVA-incorporated PCM at different heating
modulus.
temperatures (cooling). Before heating, more of the amount of EVA added a larger strain at the fracture
of PCM was found. For all the PCMs, the strain at the fracture heated to 200 ◦ C decreased, and when
heated to 200 ◦ C, the specimen became more brittle owing to the evaporation of free water. However,
as the heating temperature increased, the strain value at the fracture point increased, indicating a more
ductile characteristic. In E20, the ultimate strength and the strain at the time of fracture at 200 ◦ C
drastically decreased compared to E20 before heating; however, no significant difference was observed
in the stress-strain curve compared to other PCM (E0, E5, and E10) at temperatures above 800 ◦ C.
different heating temperatures, and Figure 9b shows the ratio of the modulus of elasticity at each
heating temperature relative to the PCM at room temperature (unheated). The elastic modulus of the
PCM decreased with an increase in the polymer–cement ratio. In the case of E10 and E20, the elastic
modulus up to a heating temperature of 200 °C showed a sharp decrease as the polymer-cement ratio
increased, 2019,
Sustainability as found
11, 500in the compressive strength results. In addition, E10 and E20 exhibited a similar
11 of 18
elastic modulus.

Sustainability
Figure 2018,
9. (a)11, x FORmodulus
Elastic PEER REVIEW 11 of 18
of the PCM specimens heated at different temperatures (oven-heating,
Figure 9. (a) Elastic modulus of the PCM specimens heated at different temperatures (oven-heating,
200, ◦ C) and (b) the residual elastic modulus ratio of the PCM specimens compared
200, 400,
400, 600,
600, and
and 800
800 °C) modulus ratio specimens compared
difference
to
was observed in the stress-strain curve compared to other PCM (E0, E5, and E10) at
to the
the unheated
unheated specimen.
specimen.
temperatures above 800 °C.
Figure 10 shows the stress–strain curve of the EVA-incorporated PCM at different heating
temperatures (cooling). Before heating, more of the amount of EVA added a larger strain at the
fracture of PCM was found. For all the PCMs, the strain at the fracture heated to 200 °C decreased,
and when heated to 200 °C, the specimen became more brittle owing to the evaporation of free water.
However, as the heating temperature increased, the strain value at the fracture point increased,
indicating a more ductile characteristic. In E20, the ultimate strength and the strain at the time of
fracture at 200 °C drastically decreased compared to E20 before heating; however, no significant

Figure 10. Stress–strain

Figure curve
Stress–strain of the
curve PCMs
of the ((a) E0,
PCMs ((a) (b)
E0,E5,
(b)(c)E10, and (d)and
E5, (c)E10, E20)(d)
heated
E20) atheated
different
at
temperatures.
different temperatures.

3.5. Comparison of the PCM Mechanical Properties During Heating (In Situ- and Oven-Heating) and After
Cooling
To confirm the mechanical properties of the PCM in a fire, a compression test under heating was
conducted, and the compressive strength and elastic modulus were measured. In this study, a simpler
heating method (oven-heating) was suggested and compared to the normal heating method (in situ-
heating). In situ-heating of the PCM at high temperatures resembling a fire is more complicated than
the compressive strength test for cooling after heating. For normal concrete, the strength (general
Sustainability 2019, 11, 500 12 of 18

3.5. Comparison of the PCM Mechanical Properties during Heating (In Situ- and Oven-Heating) and
after Cooling
To confirm the mechanical properties of the PCM in a fire, a compression test under heating
was conducted, and the compressive strength and elastic modulus were measured. In this study,
a simpler heating method (oven-heating) was suggested and compared to the normal heating method
(in situ-heating). In situ-heating of the PCM at high temperatures resembling a fire is more complicated
than the compressive strength test for cooling after heating. For normal concrete, the strength (general
strength and high strength) and residual ratio of the strength have been considered using different
heating methods. However, for PCM, the residual ratio relationship of the specimen conditions
(heating and cooling after heating) has not been considered.
Figure 11a,b shows the comparison of residual compressive strength and elastic modulus of
the PCM, respectively, heated at different temperatures, depending on the mixing ratio of the EVA
polymer and heating methods (oven-heating, and cooling). In the figure, the calculated values of
the residual compressive strength and the elastic modulus of ordinary concrete without the polymer
using a Eurocode [19] (in situ-heating) and Japanese code (JIS A 1171, cooling) are also shown. In the
experimental results of the PCM using a cooling method, assuming that the PCM was cooled after a
fire, the compressive strength ratio decreased gradually with the amount of incorporated polymer for
all temperature ranges, which is similar to concrete followed by Euro and Japanese codes. However,
the compressive strength ratio of the PCM in the oven-heating test showed sudden decreasing trends
with the increase in the incorporation of the polymer, up to a temperature of 200 ◦ C. The sudden
change in compressive strength was assumed to be due to EVA decomposition in PCM which will be
further discussed in the thermal analysis (see Section 4). The cooling process (from 200 ◦ C to ambient
temperature (20 ◦ C)) was assumed to recover the cement paste matrix of the PCM. The residual
modulus of elasticity also exhibited very similar trends to the results of compressive strength. It should
be noted that the residual compressive strength ratio of the PCM converged to a similar value when
heated up to 600 ◦ C. In contrast, the residual elastic modulus ratio of PCM showed very similar values
when heated up to 400 ◦ C, which implies that the decomposition of the EVA affected the modulus of
elasticity at lower temperatures.
Compared with the pyrolysis of the concrete properties shown as the Eurocode (in situ-heating) in
Figure 11 [24], the mechanical properties of the PCM degraded with an increase in the polymer
incorporation, although it varied slightly in the range of 200–400 ◦ C. This was because of the
evaporation of bound water in the mortar and the increase in the number of internal voids owing to
polymer decomposition. At 600 ◦ C and higher, the PCM strength remained constant, regardless of
the amount of polymer and the heating method. At this temperature range, the decrease in strength
was caused by the thermal decomposition of the cement paste material rather than the thermal
decomposition of the polymer.
Sustainability 2019, 11, 500 13 of 18
Sustainability 2018, 11, x FOR PEER REVIEW 13 of 18

11. Changes
Figure 11. Changesin
in(a)
(a)the
theresidual compressive
residual compressivestrength ratio
strength andand
ratio (b) residual elastic
(b) residual modulus
elastic ratio
modulus
of theofPCM,
ratio depending
the PCM, on theonheating
depending method
the heating (in situ-heating,
method oven-heating,
(in situ-heating, and cooling).
oven-heating, and cooling).

4. Thermogravimetric Results and Pore Structure of PCM Exposed to a High-Temperature

4. Thermogravimetric Results and Pore Structure of PCM Exposed to a High-Temperature
The mechanical properties of the PCM at high temperatures were experimentally confirmed
The mechanical properties of the PCM at high temperatures were experimentally confirmed by
by measuring the compressive strength and elastic modulus for each type and amount of polymer.
measuring the compressive strength and elastic modulus for each type and amount of polymer. The
The mechanical properties of the PCM specimens were different depending on the heating conditions
mechanical properties of the PCM specimens were different depending on the heating conditions (in
(in situ-heating, oven-heating, and cooling). Furthermore, to investigate the PCM mechanical
situ-heating, oven-heating, and cooling). Furthermore, to investigate the PCM mechanical properties
properties in the high-temperature region, in terms of the thermal decomposition of the polymer
in the high-temperature region, in terms of the thermal decomposition of the polymer rather than the
rather than the cement paste, the changes in mass, heat flow, and porosity were measured using TG,
cement paste, the changes in mass, heat flow, and porosity were measured using TG, DSC, and MIP,
DSC, and MIP, respectively. Figure 12a depicts the mass change and heat flow of EVA. In the result of
respectively. Figure 12a depicts the mass change and heat flow of EVA. In the result of TG, there was
TG, there was a drastic mass reduction due to the decomposition of EVA (endothermic reaction) in the
a drastic mass reduction due to the decomposition of EVA (endothermic reaction) in the temperature
Sustainability 2018, 11, x FOR PEER REVIEW 14 of 18
Sustainability 2019, 11, 500 14 of 18

range from 280 °C to 400 °C. From 400 °C, exothermic heat flow was detected in EVA due to the
combustion process.
temperature range fromApproximately
280 ◦ C to 400 at 500
◦ C. °C, 400
From all EVA was decomposed
◦ C, exothermic heat flow(100%
was mass reduction).
detected in EVA due
to theFigure 12b shows
combustion the Approximately
process. change in the mass (TG)
at 500 ◦ C,with the was
all EVA amount of incorporated
decomposed polymer
(100% mass for the
reduction).
EVA-incorporated
Figure 12b shows the change in the mass (TG) with the amount of incorporated polymer forEVA
PCM. The mass change in the PCM confirmed that the higher the the
substitution ratio, the
EVA-incorporated PCM.greater the mass
The mass reduction
change owing
in the PCM to a temperature
confirmed at 400 °C
that the higher thewhich was mostly
EVA substitution
causedthe
ratio, bygreater
the thermal decomposition
the mass of EVA
reduction owing toand the dehydration
a temperature at 400of◦ Ccement
whichhydrates
was mostlyas listed
caused in
Table 4. The decomposition of calcium hydroxide in the PCM was also observed
by the thermal decomposition of EVA and the dehydration of cement hydrates as listed in Table 4. between 400 and
500 decomposition
The °C. The mass loss above 600
of calcium °C was in
hydroxide caused
the PCM by the
wasdecomposition
also observedof carbonates
between and 500
400 and C–S–H
◦ C.
[25,26].
The mass loss above 600 ◦ C was caused by the decomposition of carbonates and C–S–H [25,26].

20
(a) 0
(b) 0
Exothermal
EVA (TG) 15

-20
10 -5

Heat Flow (mW)

-40 5
TG (%)

TG (%)
-10
-60 0

-5
-80 EVA (DSC) E0 (TG)
-15
Endothermal E5 (TG)
-10 E10 (TG)
-100 E20 (TG)
-15 -20
0 200 400 600 0 200 400 600 800 1000

Temperature (°C) Temperature (°C)

Figure
Figure 12. (a)Mass
12. (a) Masschange
change(TG)
(TG) and
and heat
heat flow
flow (DSC)
(DSC) for for
the the
EVAEVA
andand (b) PCM
(b) PCM based
based onEVA
on the the
EVA content.
content.

Figure
Figure 13
13 shows
shows the
the change
change in
in the
the accumulated
accumulated porosity
porosity (Figure
(Figure 13a–d)
13a–d) and
and the
the distribution
distribution of
of
the pores (Figure 13e–h) in the PCM mixed with EVA heated at different temperatures.
the pores (Figure 13e–h) in the PCM mixed with EVA heated at different temperatures.
With an increase in the heating temperature, the pore size larger than 100 µm increased, and the
increase was significant when heating to 600 ◦ C. Except for E20, the porosity increased from 0.1 to
10 µm with an increase in the heating temperature.
Figure 14 shows the changes in the total porosity of the PCM depending on the EVA replacement
rate with the heating temperature. Under the same heating temperature, the total porosity of the
PCM increased as the EVA content increased. The total porosity of the PCM increased sharply at all
levels when heating to 600 ◦ C. This was because of the complete decomposition of calcium hydroxide
in the cement paste and the initiation of the dissolution of carbonates and C–S–H. The porosity and
pore diameter increased as the heating temperature increased, even at the same mixing ratio of EVA.
Note that 600 ◦ C was the critical temperature for the degradation of the elastic modulus. Therefore,
the increase in the total pore and the pore structural changes had strong correlations with the elastic
modulus of PCM.
In conclusion, the pore diameter and pore size of the PCM increased at each temperature range
with an increase in the polymer incorporation ratio, and the total porosity increased from 19.1 to
30.8 vol.% for the EVA-free PCM and from 20.0, 21.0, and 23.6 vol.% to 35.1, 38.3, and 37.4 vol.% for
the EVA-incorporated PCM when heating at 800 ◦ C.
Sustainability 2019, 11, 500 15 of 18
Sustainability 2018, 11, x FOR PEER REVIEW 15 of 18

Figure 13. Changes

Changes inin the
the porosity
porosity distribution
distribution and
and total
total accumulation
accumulation porosity
porosity for
for the
the EVA
EVA
incorporation
incorporation amount
amountand andtemperature
temperaturerange.
range.(a), (b),shows
(a–d) (c), and (d)accumulated
the shows the accumulated porosity
porosity of E0, of
E5, E10,
E0,
andE5, E10,
E20, and E20, respectively.
respectively. (e–h) shows (e), (f), (g), and
the porosity (h) showsofthe
distribution E0,porosity
E5, E10,distribution of E0, E5, E10,
and E20, respectively.
and E20, respectively.
increase in the total pore and the pore structural changes had strong correlations with the elastic
modulus of PCM.
In conclusion, the pore diameter and pore size of the PCM increased at each temperature range
with an increase in the polymer incorporation ratio, and the total porosity increased from 19.1 to 30.8
vol.% for the EVA-free PCM and from 20.0, 21.0, and 23.6 vol.% to 35.1, 38.3, and 37.4 vol.% for
Sustainability 2019, 11, 500
the
16 of 18
EVA-incorporated PCM when heating at 800 °C.

Figure
Figure 14. Comparison of
14. Comparison of the
the total
total accumulated
accumulated porosity
porosity with
with the
the heating
heating temperature
temperature and
and EVA
EVA
replacement ratios.
replacement ratios.

5. Conclusions
5. Conclusions
In this study, the degradation in the mechanical properties of EVA-incorporated PCM, depending
In this study, the degradation in the mechanical properties of EVA-incorporated PCM,
on the mixing ratio and heating temperature, was evaluated. The compressive strength and
depending on the mixing ratio and heating temperature, was evaluated. The compressive strength
elastic modulus were measured in different heating conditions, and the characteristics of thermal
and elastic modulus were measured in different heating conditions, and the characteristics of thermal
decomposition and the change in the pore structure after heating were measured to analyze the
decomposition and the change in the pore structure after heating were measured to analyze the
correlation. The experimental results of this study are summarized as follows.
correlation. The experimental results of this study are summarized as follows.
1. Regarding the mechanical properties of the PCM, the compressive strength and elastic modulus
1. Regarding the mechanical properties of the PCM, the compressive strength and elastic modulus
decreased when exposed to heating at different temperatures.
decreased when exposed to heating at different temperatures.
2. The compressive strength and elastic modulus of the PCM during heating at high temperatures
2. The compressive strength and elastic modulus of the PCM during heating at high temperatures
significantly decreased when heated to 200 ◦ C and 400 ◦ C, respectively, regardless of the EVA
significantly decreased when heated to 200 °C and 400 °C, respectively, regardless of the EVA
mixing ratio. This was found to be because of the decomposition of EVA.
mixing ratio. This was found to be because of the decomposition of EVA.
3. When the
3. When the PCM
PCM waswas exposed
exposed toto high
high temperatures,
temperatures, itit was
was determined that the
determined that the bonded
bonded water
water
evaporated with an increase in the heating temperature, and simultaneously, the increase in
evaporated with an increase in the heating temperature, and simultaneously, the increase in the
the
mass reduction and increase in the total amount of pores owing to the decomposition
mass reduction and increase in the total amount of pores owing to the decomposition of the of the
polymer and
polymer and cement
cement paste
paste matrix
matrix decreased
decreased the
the mechanical
mechanical performance
performance of
of PCM.
PCM.
4. For the amount of polymer admixture, there was a decrease in the mechanical properties at a
polymer–cement ratio of 20% and a high temperature. When the polymer–cement ratio was 10%
or less, a high residual ratio was observed.
5. The number of large pores and the total pore volume significantly increased with an increase in
the polymer incorporation ratio. We also found that the decrease in the elastic modulus of the
PCM at high temperatures was because of the increase in the number of pores, caused by the
decomposition and the combustion of the polymer combined with the thermal decomposition of
the cement paste.

Author Contributions: Investigation, H.-J.K., J.-Y.P. and B.-Y.C.; resources, H.-J.K.; visualization, J.-Y.P., H.-W.S.
and S.-C.B.; Writing—Original Draft, H.-J.K. and S.-C.B.; Writing—Review and Editing, W.-J.P. and S.-C.B.
Funding: This research was funded by the National Fire Agency, “NEMA-Next Generation-2014-58”.
Acknowledgments: This research was supported by the Field-oriented Support of the Fire Fighting Technology
Research and Development Program funded by the National Fire Agency (“NEMA-Next Generation-2014-58”).
Conflicts of Interest: The authors declare no conflict of interest.
Sustainability 2019, 11, 500 17 of 18

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