Construction and Building Materials 203 (2019) 621–632

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Construction and Building Materials

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

Evaluation of the potential use of form-stable phase change materials to

improve the freeze-thaw resistance of concrete
Wenting Li a, Chaowei Ling a, Zhengwu Jiang a,⇑, Qian-qian Yu b
a
Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, Shanghai 200092, PR China
b
Department of Structural Engineering, Tongji University, Shanghai 200092, PR China

h i g h l i g h t s

Cement paste is recommended as a good alternative surface coating material of LWA-PCM for a better compatibility.

Exothermic/endothermic events validate that PCM can delay or prevent ice formation.

When the replacement of LWA is up to 50% vol., the heat released by PCM is sufficiently high to inhibit ice formation.

Time offset between solidification of PCM and pore solution is relevant to effective utilization of PCM in improving freeze-thaw resistance of concrete.

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

Article history: This paper investigates the preparation and assessment of mortar-phase change materials (PCM) systems
Received 5 June 2018 to gain a full understanding of using the heat stored in PCMs to delay or prevent ice formation in concrete.
Received in revised form 20 December 2018 Desirable PCMs and light weight aggregates (LWA), which act as carriers of the PCMs, were first selected
Accepted 17 January 2019
based on their thermal and physical properties. LWAs containing PCMs were prepared and assessed for
different combinations of materials. Cyclic freeze-thaw mass loss, latent heat attenuation, and FTIR tests
were conducted to characterize the stabilities of the LWA-PCMs. The thermal performances of the mor-
Keywords:
tars containing LWA-PCMs were investigated using a longitudinal guarded comparative calorimeter
Concrete
Freeze-thaw
(LGCC) that was operated under quasi-steady state conditions during the cooling/heating process. The
Phase change materials results confirmed that PCMs can be steadily absorbed in LWAs without chemical reactions or great losses
Lightweight aggregates in latent heat when the LWA-PCMs were coated in a certain way. Cement paste was recommended to
Exothermic coat the surface of the LWA-PCMs for better compatibility with the system than that of traditional coating
Endothermic materials. The ability of the PCM to delay or prevent ice formation in mortar was verified from the
exothermic/endothermic events associated with the phase transformations of the pore solution and
PCM. In the present study, when up to 50% vol. of the LWA was replaced as carriers of PCM, the heat
released by the PCM was sufficiently high to inhibit ice formation.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction occupant comfort [9,10]; and (3) concrete pavement applications

In recent years, phase change materials (PCMs) have become
more widely used as a promising way to improve the thermal
response of concrete infrastructures due to their ability to absorb
and release a considerable amount of latent heat during the
solid-liquid transformation process [1,2]. The application of PCMs
in concrete construction is conventionally focused on three
aspects: (1) temperature control in concrete to avoid the formation
of thermal cracks [3–8]; (2) thermal energy storage in buildings to
decrease energy loss from air conditioning systems and increase
⇑ Corresponding author.
E-mail address: jzhw@tongji.edu.cn (Z. Jiang).
to melt ice and snow on road layers [11,12] and to improve the
freeze-thaw resistance of pavements [13–19].
Concrete is comparatively vulnerable to damage in cyclic
freeze-thaw conditions as a consequence of stress associated with
ice formation of the solution in capillary pores [20,21]. It has been
suggested that when PCMs with suitable melting points are incor-
porated into concrete, PCMs can release a large amount of latent
heat during phase transformation to prevent or delay the freezing
of pore solutions and accordingly reduce the number of freeze-
thaw cycles experienced by the pavements [11,16,17]. This reduc-
tion in the number of freeze-thaw cycles is beneficial to extending
the service life of pavements [18,22].

https://doi.org/10.1016/j.conbuildmat.2019.01.098
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
622 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
It is crucial to find suitable PCMs that exhibit desirable proper-
ties at low temperature, in which the melting point and latent heat
of the PCM are essential [23,24]. Previous studies have verified and
concluded that PCMs used for ice melting and freezing prevention
in concrete should have a transition temperature slightly above
0 °C and a high latent heat of fusion (>150 J/g) [13,16–18,25].
Moreover, the methods used to properly incorporate PCMs into
host matrices are also relevant to achieving the expected perfor-
mance. There are several methods available for PCM incorporation
in concrete: (1) traditional methods, such as direct incorporation
and encapsulation of PCMs in embedded pipes or tubes
[11,16,26]; (2) microencapsulated PCMs [27–29]; and (3) form-
stable PCMs [30–32], which are typically composed of supporting
materials and PCMs. Form-stable PCMs have received increasing
attention in recent years because the supporting material can
improve the mechanical properties of the composite system [33].
Porous lightweight aggregates (LWAs) are a type of supporting
material that is often used in concrete. Nevertheless, using an
LWA as a supporting material may cause an absorbed PCM to leak
from the LWA during service. If the PCMs leak, they may interact
with the matrix and thus compromise its mechanical properties
[34,35]. Therefore, it is necessary to seal or coat impregnated
LWA-PCMs. In previous studies, organic coating materials have
often been used to coat LWA-PCMs [15,36,37]. However, these
coatings may lead to a weak interface between the coating layer
and cement matrix because of chemical incompatibility, which
consequently weakens the mechanical properties of the matrix.
Thus, more efficient coating methods are necessary. Moreover,
the properties of LWA-PCMs must be better understood, such as
the encasement effectivities and stabilities of LWA-PCMs, which
were barely considered in previous studies.
The efficient use of PCMs in concrete requires a series of tasks,
including choosing desirable materials, determining an efficient
method to incorporate PCMs in concrete elements, assembling
the materials together without extensive intervention to the con-
crete base, and assessing the thermal properties of the final com-
posites. Previous studies have usually focused on some specific
aspects of this issue, whereas our work intends to present a more
in-depth understanding of the abovementioned processes. In
detail, the chemical and physical features of three PCMs and four
LWAs were investigated to determine suitable materials for
LWA-PCMs. In addition to conventional waterproofing materials,
cement paste was used as an alternative coating for the LWA-
PCM because it is more compatible with the system. FTIR and
DSC tests were carried out to characterize and evaluate the encase-
ment effectivities and stabilities of the coated LWA-PCMs. The
effects of various PCM contents on the delay or prevention of ice
formation in mortars were assessed from the exothermic/
endothermic events associated with the phase transformation of
the pore solutions and PCMs during freeze-thaw cycling in longitu-
dinal guarded comparative calorimeter (LGCC) tests.
2. Materials and methods
2.1. Materials
2.1.1. Phase change materials
Three types of commercially available PCMs were considered in
the present study: a vegetable-based methyl laurate and two types
of petroleum-based paraffins (OP2E and OP3E). The properties of
the PCMs, as provided by the manufacturers, are listed in Table 1.
The phase transition temperatures of the PCMs vary from 0 to 5 °C
to improve the freeze-thaw resistance of cement-based materials
[15].
Table 1
Preliminary properties of the PCMs.
PCMs Density at 15 °C Melting area Enthalpy(kJ/kg)
(g/cm3) (°C) (±7.5%)
Methyl laurate 0.87 5.2 –
OP2E 0.77 1–3 205
OP3E 0.77 3–5 250
2.1.2. Lightweight aggregates
Four lightweight aggregates (with diameters less than 5 mm)
were selected to encapsulate the PCMs: two types of expanded clay
(NT-A and NT-B), expanded perlite (P) and broken expanded shale
(YT). The size distribution of LWAs was first assessed by the sieving
method [38], and the results are reported in Table 2. NT-A and P
have continuously graded diameters in the range of 2–5 mm and
3–5 mm, respectively.
2.1.3. Coating materials
To prevent the leakage of PCMs from LWAs, two kinds of coating
materials were used: (a) a capillary/crystalline waterproofing
material (CC) and (b) Portland cement (PC). Both of these coating
materials can serve the temperature range of tests.
2.1.4. Other mixture materials
Ordinary Portland cement (Type II 52.5) was used in this work.
The chemical composition, as provided by the manufacturer, is
given in Table 3. River sand with a fineness modulus of 3.45 and
tap water were also used.
2.2. Test procedures
2.2.1. Thermal properties of the PCMs
The thermal properties of the PCMs were measured by differen-
tial scanning calorimetry (DSC). Temperature and heat flow during
the complete phase transformation process were recorded. Each
sample was tested in a high-volume pan under a N2 atmosphere,
and the sample mass was maintained at approximately 3–7 mg.
A hermetic lid was used to seal the pan to prevent leakage of the
PCM. The initial temperature was set to 30 °C and maintained
isothermally for 5 min. Cooling was then initiated at a rate of
5 °C/min, and the temperature was decreased to 30 °C and main-
tained isothermally for 5 min. The temperature was then increased
back to 30 °C at a rate of 5 °C/min. TA Universal Analysis software
was used to process the data and phase change diagrams.
2.2.2. LWA testing
2.2.2.1. MIP tests. The pore structures of four LWAs were assessed
by mercury intrusion porosimetry (MIP). Prior to the test, 0.4–
0.5 g of the samples were oven dried for 2 d. Porosities and pore
size distributions were obtained by MIP in a pressure range
between 3 and 414 MPa.
2.2.2.2. Water absorption. Before the water absorption test, the four
LWAs were dried in an oven at 105 °C until their mass changes
were less than 0.1% over 2 d. For the tests under ambient condi-
tions, the oven-dried LWAs were weighed and immersed in water
in a beaker for 24 h under atmospheric pressure. The masses of the
LWAs under saturated surface dry conditions (SSD) were then
measured. The SSD conditions were achieved as follows: a cloth
was used to remove the water on the surface of the LWAs, and then
the samples were placed on a mesh at room temperature for
120 min [12,17]. For water absorption under evacuated conditions,
the oven-dried samples were first weighed, then placed inside a
desiccator and evacuated to a residual pressure of 0.1 MPa for
 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
Table 2
Mass retention (%) of the four lightweight aggregates.
Mesh size (mm) 4.75 2.36
NT-A 1.6 71.4
NT-B 2.1 54.4
P 12.8 96.4
YT 9.2 62.3
Table 3
Chemical composition of the cement by mass percentage (%).
Na2O MgO Al2O3 SiO2 P2 O5
0.03 0.68 4.51 20.0 0.15
1 h. After evacuation and while still under vacuum, the valve was
opened to introduce water into the desiccators until the samples
were submerged. The samples were left in the desiccators, and
the pressure was held for 2 h. The amount of water absorption
was calculated as follows:
mt  m0
Absorptionamount ¼  100%
m0
where m0 is the initial mass of the LWAs and mt is the mass of the
LWAs after water absorption.
2.2.3. Preparation of the coated LWA-PCMs
2.2.3.1. Impregnation of the LWAs with the PCMs. The absorption
capacities of the LWAs with respect to the PCMs were measured
under normal and evacuated conditions. The procedure was the
same as the test of water absorption. The LWAs impregnated by
PCMs were denoted as LWA-PCMs in this study.
2.2.3.2. Encasement of the LWA-PCMs. Since each PCM used in the
experiment is in a liquid state at room temperature, every LWA-
PCM should be coated to prevent the potential leakage of the
PCM. To do this, the LWA-PCMs in SSD conditions were placed into
a refrigerator for at least 3 h to allow the liquid PCM to solidify.
Then, the LWA-PCMs were subsequently encased with two differ-
ent coating materials, the CC and PC, with the following proce-
dures. The coated LWA-PCMs were denoted as LWA/PCM/CC and
LWA/PCM/PC, respectively.
For preparation of an LWA/PCM/CC, CC was mixed with the
LWA-PCM and stirred at room temperature until the outer surface
of the LWA-PCM was covered with the coating material. Then, the
CC was filtered from the mixture and kept at room temperature for
3 d.
When PC was used as the coating material, the LWA-PCM was
first mixed with PC in a tray, and the tray was agitated to force
the LWA-PCM to roll continuously. Water was sprayed onto the
surface of the LWA-PCM during the agitation process. The hydra-
tion of the cement on the surface of the LWA-PCM initiates after
it contacts water. Water spraying was stopped before the LWA-
PCM samples stuck together. It should be noted that the cement
layers on the surfaces of the LWA-PCMs were still very fragile at
this moment because some cement had not yet been exposed to
water (i.e., the cement was not yet hydrated). Thus, additional cur-
ing is necessary to develop the strength of the coating layer due to
the rehydration of the cement. The coated LWA-PCM samples were
kept at room temperature for 1 d and were then immersed in water
for 3 d to allow the cement layers to further hydrate. The coated
LWA-PCMs were dried at 50 °C for 2 h to remove the excess
moisture.
623
1.18 0.60 0.30 0.15
98.3 99.7 100.0 100.0
74.6 92.4 96.3 97.9
99.5 100.0 100.0 100.0
83.8 90.2 93.7 95.2
SO3 K2O CaO TiO2 MnO Fe2O3 ZnO
2.99 0.72 64.3 0.22 0.10 3.11 0.06
2.2.4. Testing the coated LWA-PCMs
A series of tests were performed to characterize the properties
of the coated LWA-PCMs, which are described hereafter.
2.2.4.1. The encasement effectivities of the LWA-PCMs. The mass
losses of the coated and uncoated LWA-PCMs after 20 freeze-
ð1Þ thaw cycles were taken as a criterion to assess the leakage of the
PCMs; the freeze-thaw cycles simulate the service conditions of
mortars. Each freeze-thaw cycle consists of the samples being kept
at 20 °C for 3 h followed by 50 °C for 2 h. The masses of the spec-
imens were recorded after each cycle.
2.2.4.2. The stabilities of the LWA-PCMs. The stabilities of the coated
LWA-PCMs during the freeze-thaw cycles can be assessed from
two perspectives: (a) the enthalpy attenuations of the PCMs over
time by DSC and (b) the physical and/or chemical interactions
between the PCMs and the surrounding constituents by FTIR.
The ground LWAs and the hydrated cement paste were sepa-
rately mixed with the PCMs at a ratio of 1:1 by mass for the DSC
tests at 1 d, 7 d and 70 d after mixing. In parallel, Ca(OH)2 (analyt-
ical grade) was also mixed with the PCMs for comparative testing
because Ca(OH)2 is the primary hydrated product of cement. The
change in enthalpy was recorded to illustrate the compatibility
between the PCMs and LWAs/hydrated cement paste. The experi-
mental conditions were kept the same as those described in
Section 2.2.1.
To further determine the reactivities of the PCMs with the LWAs
or hydrated cement paste, FTIR tests were performed using an
infrared spectrometer [33,39,40]. The spectral wavenumbers var-
ied from 400 to 4000 cm1, and the KBr pellet technique was used
to prepare the specimens. The samples were taken from the mix-
ture used in the aforementioned DSC tests after aging the mixture
for 28 d. In addition, the ground LWAs, hydrated cement paste, and
PCMs were also tested for comparison. Any new peaks in the spec-
tra illustrate new products caused by the chemical reactions
between the PCMs and the LWAs or hydrated cement paste. All
specimens were oven dried at 50 °C for 2 d before testing to
weaken the influence of water.
2.2.5. Mechanical properties of the phase change mortars
The coated LWA-PCMs were used to prepare mortars with a
water-to-cement ratio (w/c) of 0.42 and an aggregate volume frac-
tion of 55% for mechanical testing. The mixture proportion of the
NT-A containing OP3E is given in Table 4. as an example. The
remaining mortars were all kept at the same proportion but with
different LWAs and coating layers. Mixing was performed in accor-
dance with the testing method used to determine the strength of
cements: GB/T 17671-1999 [41]. The mixture was cast into prisms
with dimensions of 40 mm  40 mm  160 mm. The specimens
were demolded after a 24 h cure cycle at room temperature, moved
624 W. Li et al. / Construction and Building Materials 203 (2019) 621–632

Table 4
Mixture proportion of NT-A/OP3E mortar coated with CC (kg/m3).

No Cement Water Sand LWA (sand replacement ratio)

0 596.6 250.6 1485 0.0(0%)
1 1336.5 71.5(10%)
2 1188 143.0(20%)
3 1039.5 214.5(30%)
4 742.5 357.5(50%)
5 445.5 500.5(70%)
6 0 715.0(100%)

to a curing room that was maintained at 20 ± 2 °C and RH 95%, The heat flow consumed or released by the mortar can be calcu-
and then aged for 28 d. The compressive and flexural strengths lated by Eq. (4) provided the values of the heat flow per unit area
were then tested following GB/T 17671-1999 [41]. through the lower meter bar and upper meter bar are known [42]:

DQ mortar ¼ ðqB  qT Þ  A ð4Þ

2.2.6. Thermal responses of the phase change mortars
To determine whether the LWA-PCM assembled with the
selected materials can delay or prevent ice formation in cement
mortars, the thermal responses of the mortars in one-
dimensional quasi-steady conditions were investigated using a
longitudinal guarded comparative calorimeter (LGCC), as shown
in Fig. 1. A detailed description of the test setup can be found in
the literature [42,43]. The specimens were vacuum-saturated
before testing. In general, a sample stack was placed on a cold plate
that is capable of decreasing the temperature to 30 °C in a con-
trolled fashion. The sample stack consisted of a mortar specimen
with dimensions of 25 mm  25 mm  30 mm that was prepared
following the procedure listed in section 2.2.5 using the mixture
proportion shown in Table 5 and a pair of meter bars, which were
composed of a zirconia ceramic whose thermal conductivity is
3.0 W/(mK). The specimen was set between two meter bars, and
thermally conductive pads were used to ensure good contact
between the specimen and the meter bars and between the cold
plate and the meter bars. Temperatures were recorded using T-
type thermocouples at seven different locations, as illustrated in
Fig. 1c. Insulation material (extruded polystyrene with a thermal
conductivity less than 0.03 W/(mK)) was used to tightly surround
the sample stack to minimize heat loss.
The temperature profile used in this study is shown in Fig. 2.
Each cooling and heating cycle was performed between 25 and
30 °C with a cooling rate of 2 °C/h and a heating rate of 4 °C/h.
The heat flow per unit area through the lower meter bar qB and
the upper meter bar qT can be calculated by Eqs. (2) and (3) [42]:
T2  T3
qB ¼ kPC 
dPC
T6  T7
qT ¼ kPC 
dPC
where kPC is the thermal conductivity of the meter bar (W/(mK)), T i
is the temperature at position i of the sample stack in Fig. 1c (°C),
and dPC is the thickness of the meter bars (m).
2
where A is the cross-sectional area of the specimen (m ).
3. Results and discussion
3.1. DSC test results of the PCMs
The thermal responses of the PCMs during cooling and heating
by LT-DSC are shown in Fig. 3a and b, respectively. The critical data
including Tonset (the onset temperature of the phase transformation
in each PCM), Tmax-peak (the temperature at the peak of heat flow),
Tcompletion (the temperature when each PCM completes the phase
transformation), and DH (the latent heat of each PCM), are summa-
rized in Table 6.
It is clear that the melting point of methyl laurate is higher than
those of OP2E and OP3E, but its enthalpy of fusion is much lower.
Taking this into account, methyl laurate is no longer considered in
the following study. The melting points of OP2E and OP3E are very
similar; however, OP3E can produce more heat during the phase
change. Therefore, OP3E was the primary PCM used in the subse-
quent experiments in this study.
3.2. LWA testing results
3.2.1. Pore size distributions
Fig. 4a shows the pore size distribution in terms of logarithmic
differential intrusion volume (V) with respect to pore size diameter
(D) in four LWAs by MIP. It can be seen that P has a greater number
of large pores (between 5000 and 50,000 nm in diameter) than are
ð2Þ observed in the other three LWAs. The average pore diameters of
the other three LWAs are similar, which are mainly in the range
of 60–140 nm. Moreover, the pore distribution of NT-A is wider
ð3Þ than that of NT-B or YT: there are some pores larger than
5000 nm in NT-A, whereas neither NT-B nor YT have any pores in
this range. Fig. 4b shows that the cumulative volume of larger
pores in P was much higher than that in the other three LWAs.
The critical parameters of the pore structures are listed in Table 7.

Fig. 1. LGCC test setup: (a) insulation; (b) sample during testing; (c) locations of temperature to be measured.
 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
Table 5
Mixture proportions of the mortars for the LGCC tests.
Specimen Cement
NT-A/W/CC
NT-A/OP3E/CC 596.6
NT-A/OP3E/CC
Fig. 2. Temperature profile generated by the cold plate.
The average pore diameter of P is 2340 nm, which is 2 orders of
magnitude larger than that of NT-A, NT-B, and YT. The average pore
diameter of NT-A is larger than that of NT-B and YT, and YT has the
smallest average pore diameter. The pore structure of an LWA has a
strong influence on its absorptivity. First, an LWA should have a
sufficient number of pores in which to fill liquid. Second, the pore
size distribution of an LWA should be in an appropriate range.
Overly large pores can carry more liquid, but the capillary force
in these pores is too weak to hold the liquid, which may lead to
the leakage of the liquid. Compared to large pores, small pores
encapsulate less liquid. More properties associated with the capac-
ities of LWAs to encapsulate PCMs are further assessed in the fol-
lowing experiments.
Fig. 3. DSC curves of the PCMs: (a) exotherm curves; (b) endotherm curves.
625
Water Sand Coated LWA (sand replacement ratio)
742.5 357.5(50%)
250.6 1039.5 214.5(30%)
742.5 357.5(50%)
3.2.2. Water absorption of the LWAs
The water absorption amounts of the LWAs under normal pres-
sure and under vacuum are presented in Fig. 5. P has the highest
absorptivity, which reaches as high as 250% under normal pressure
due to its high proportion of large pores. The water absorption
amounts of the other three LWAs are much lower than that of P.
The absorptivity of NT-A is higher than that of NT-B and YT because
of its wider pore size distribution. These results are consistent with
the MIP test results, as shown in Fig. 4a, where NT-A has multiple
peaks in the range of 5000–50,000 nm.
It is interesting to note that the water absorption amount of NT-
B is less than that of NT-A, although NT-B has a higher porosity.
This implies that not all the pores were filled with water even
under evacuated conditions. There is a minimum pore diameter
that water can penetrate under vacuum. This minimum value
can be found based on the cumulative pore volume curves, the liq-
uid absorptivity of the LWA and the density of the liquid [10]. The
water absorptivity of NT-A at normal pressure is 25.5%, which
means that the volume of liquid absorbed by 1 g of NT-A is
0.25/1 = 0.25 ml. Therefore, the minimum pore diameter of NT-A
is approximately 113 nm, according to Fig. 4b. The other values
listed in Table 8 were obtained by following the same method.
It is important to note that the minimum pore diameter of NT-A
(113 nm) is smaller than its average pore diameter (135.1 nm). In
contrast, the minimum pore diameter of NT-B (101 nm) is larger
than its average pore diameter (88.7 nm), as shown in Fig. 4a. This
means that nearly half of the pores in NT-B were too fine to be pen-
etrated by water, which explains why NT-B has a larger porosity
but lower water absorptivity in comparison to those of NT-A.
Based on this analysis, YT is eliminated in this study because of
its low porosity and absorptivity. NT-A, NT-B and P were further
assessed as carriers of PCMs in the subsequent experiments.
626 W. Li et al. / Construction and Building Materials 203 (2019) 621–632

Table 6
Thermal properties of the PCMs obtained by DSC.

PCMs Toneset/°C Tmax-Peak/°C Tcompletion/°C DH/J/g

OP2E 1.85 3.47 8.57 92.23
OP3E 2.04 5.71 9.69 202.1
Methyl laurate 5.21 6.85 11.36 79.83

Fig. 4. Pore size distribution of LWAs measured by MIP: (a) differential intrusion volume; (b) cumulative pore volume.

Table 7
Pore structures of the four LWAs.

NT-A NT-B YT P
Porosity/% 49.4 58.4 32.9 91.0
Average pore diameter/nm 135.1 88.7 62.5 2340
Mean pore diameter (volume)/nm 214.4 156.9 186.6 12,450

Fig. 6. PCM absorption amounts of LWAs under normal pressure and under
vacuum.

3.3. Encapsulation of PCMs by LWAs

3.3.1. PCM absorption in the LWAs

PCM absorption in the LWAs under normal pressure and under
vacuum was measured in the same way as the water absorption,
and the results are shown in Fig. 6. The overall trends are consis-
tent with those of water absorption, but the absorption amounts
Fig. 5. Water absorption amounts of the LWAs under normal pressure and vacuum. are lower because of the different viscosity, density and surface
tension of the PCMs [15]. Under normal pressure, the PCM absorp-
tion amount is close between NT-A and NT-B, whereas NT-A
absorbed much more than NT-B under vacuum (34.7% vs. 20.8%).
Table 8
Minimum pore diameters of NT-A and NT-B under different conditions. Although the PCM absorption amount of P is quite high under
both conditions, its ability to retain PCM is still unknown. Taking
NT-A NT-B
this into account, the LWA-PCMs were encased to avoid the poten-
Normal pressure 260 nm 232 nm tial leakage of the PCMs; this process will be discussed in section
Vacuum condition 113 nm 101 nm
3.4.1.
 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
By now, it was found that the combined performance of NT-A
was superior to that of NT-B; thus, NT-A and P were mainly used
in the following study.
3.3.2. Encasement of the LWA-PCMs
Figs. 7 and 8 show NT-A and P containing PCM and coated with
different materials, respectively. The cross-section of the LWA-
PCMs coated with PC are illustrated in Fig. 9.
The thicknesses of the outer PC layers of the LWAs were mea-
sured at a minimum of 6 locations. The average values are
0.78 mm and 0.83 mm for NT-A/OP3E and P/OP3E, respectively.
3.4. Test results of the coated LWA-PCMs
3.4.1. The coating effectivities of the LWA-PCMs
Fig. 10 shows the mass losses of the coated LWA-PCMs during
freeze-thaw cycling. The mass losses are substantially reduced
and converge to constant values after 15 cycles for the coated sam-
ples, whereas the mass loss of the reference consistently increased.
Furthermore, the mass loss of P (Fig. 10b) is approximately 1.5
times greater than that of NT-A (Fig. 10a) for the comparative sam-
ples. This is attributed to the high porosity and the high proportion
of large pores of P, which results in a capillary force that is insuffi-
cient to retain the PCM. The mass loss of NT-A/OP3E, coated by
either PC or CC, was less than 2%, which is considered acceptable.
In general, CC has a better coating effectivity than that of PC
according to its lower mass loss. This is attributed to the fact that
the nanoparticles in CC, a capillary/crystalline waterproofing mate-
rial, more easily permeate into LWA and block the pores to prevent
fluid leakage [44].
3.4.2. The stabilities of the coated LWA-PCMs
The stability of a coated LWA-PCM in mortar during its service
life can be assessed by the change in latent heat with time and any
potential interactions between the LWA and PCM.
3.4.2.1. Thermal properties of the PCM over time measured by
DSC. Fig. 11 shows the latent heat retention of OP3E after mixing
with different materials, CH(Ca(OH)2) and C (hydrated cement
paste), for 1 d, 7 d, and 70 d. The reduction in latent heat of the
mixture implies whether the mixture is chemically durable. The
retention rates of OP3E in NT-A and P decrease slightly over time,
and the latent heat still remains at 95% and 94% of the original
value, respectively, after 70 d. These results are acceptable because
over 90% of latent heat is still available at this stage. When the PCM
was exposed to hydrated cement paste or Ca(OH)2, higher reduc-
tions in latent heat were observed: only 83% and 69% of latent heat
remained, respectively. These results can be explained by the inter-
actions between the hydration products (i.e., aluminate phases and
Fig. 7. NT-A containing PCM and coated with different materials.
627
Ca(OH)2) of cement and PCMs, which reduce the enthalpy of fusion
of the PCM [11].
3.4.2.2. FTIR test results of the PCM mixed with LWA or hydrated
cement paste. Fig. 12 shows the FTIR spectra of PCM mixed with
different materials. There are mainly three absorption peaks in
the spectra of PCM. The peaks at 720 cm1 and 1462 cm1 are
caused by the deformation vibrations of ACH2 and ACH3, respec-
tively. The peak between 2848 and 2956 cm1 belongs to the
stretching vibration of CAH. The spectra of NT-A and P are quite
similar because their principal chemical compositions are SiO2
and Al2O3. The observed absorption peaks of NT-A and P are dis-
tributed in the frequency range below 1500 cm1. The peak at
788 cm1 corresponds to the stretching vibration of OAH, and
the peak between 1056 and 1076 cm1 is the asymmetric stretch-
ing vibration of SiAOASi [33]. For the spectrum of hydrated
cement paste (Fig. 12c), the peak at 3643 cm1 is attributed to
the structural water of the cement paste, and the peak at approx-
imately 3401 cm1 is caused by liquid water that is not completely
dry. The peaks at 976 cm1 and 874 cm1 are the absorption peaks
of CASAH and the siloxane polymer, respectively. No new distinct
peaks were observed in the spectra of NT-A/PCM and P/PCM, which
means that all absorption peaks can be found in the spectra of
either the LWA or PCM. This phenomenon indicates that the PCM
can be absorbed and remain in both NT-A and P. However, two
new peaks appeared at 2513 cm1 and 1798 cm1 in the spectrum
of cement paste/PCM, as shown in Fig. 12c, which suggests that
there are new constituents produced due to a chemical reaction
between the paste and PCM.
3.5. The mechanical properties of the phase change mortars
The compressive strength of mortar at 28 d is presented in
Fig. 13. Generally, the strength decreases with increasing content
of LWA-PCM in the mortar because the porous LWA has much
lower strength than natural sand [14,16,17].
When P was coated with either CC or PC, the compressive
strength of the mortar was lower than that of the mortars contain-
ing NT-A. Their strength decreases sharply with increases in the
sand replacement ratio. NT-A coated with PC exhibits the best
mechanical performance of all the tested samples. The coating
layer of CC results in a decrease in the strength at the same content
of sand.
Using cement as a coating material has an advantage because
the cement layer of the coated LWA-PCM and the cement matrix
are chemically compatible, which is beneficial for interfacial bond-
ing between the coated LWA-PCM and cement matrix. This effect
becomes clearer when the content of LWA increases to 50%, at
which the mortar containing the LWA-PCM coated with CC experi-
628 W. Li et al. / Construction and Building Materials 203 (2019) 621–632

Fig. 8. P containing PCM and coated with different materials.

Fig. 9. Cross-sections of (a) NT-A/OP3E/PC and (b) P/OP3E/PC.

Fig. 10. Mass losses of the LWA-PCMs after thermal cycling for (a) NT-A and (b) P.

ences a greater decrease in strength compared to mortar contain-
ing the LWA-PCM coated with PC.
3.6. The thermal responses of the mortars containing PCMs
The temperature profiles and the heat flows of the sample
stacks are presented in Figs. 14–16.
Fig. 14 shows the result for the mortar containing NT-A that was
preimmersed in water. The temperature linearly decreased with
time until the bottom of the specimen (T4) reached 5°C, at which
an abrupt increase in temperature can be observed during the
cooling stage. Correspondingly, a substantial exothermic peak
can also be seen from the heat flow curve. This exothermic phase
transformation (freezing peak) is attributed to the freezing of the
pore solution in the mortar. During the heating stage, an endother-
mic peak (melting peak) was observed when T4 increased to 5°C,
which indicated that the frozen pore solution began to melt. The
heat flow of mortar versus temperature, as presented in Fig. 14b,
shows that the onset points (the dashed line in Fig. 14b) of freezing
and thawing of the pore solution were almost the same (5°C),
which implies that no supercooling phenomenon occurred during
the phase transformation.
 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
Fig. 11. Latent heat attenuations of OP3E after mixing with different materials.
When 30% vol. of the LWA was used, as shown in Fig. 15, the
temperature increased at 5°C during cooling and exhibited a
remarkable exothermic peak in the heat flow curve. Unlike the
Fig. 12. FTIR spectra of the (a) NT-A/PCM mixture, (b) P/PCM mixture, and (c) cement paste/PCM mixture.
629
water-immersed specimen, this sample exhibits a comparatively
small exothermic peak between 2 and 5°C in the DQ-t curve; this
peak is associated with the freezing of the PCM, which initiates at
approximately 2 °C according to the measurements by the DSC
experiment. It is worth noting that the temperature does not exhi-
bit a corresponding change with this exothermic behavior because
the freezing of the PCM occurs in a wider range of temperatures
and has a lower heat flow compared to that of the intense freezing
of water in the reference (Fig. 14a). There are two endothermic
peaks during the heating stage. It can be seen from Fig. 15b that
the onset points are 5°C and 2 °C, which correspond to the thaw-
ing of the pore solution and OP3E, respectively. In addition, the
endothermic peak of ice melting is larger than that of OP3E. This
result implies that the heat released by OP3E in the cooling stage
was not sufficiently high to prevent the freezing of the pore solu-
tion in the present condition.
In Fig. 16, no sharp exothermic peak of the pore solution is
observed in the heat flow when T4 reaches 5°C, and the rate of
temperature change does not show a distinct variation during cool-
ing when the volumetric replacement of LWA increases to 50%.
Instead, there are two subtle exothermic peaks associated with
the solidification of the PCM at 2 °C and pore solution at 5°C.
When the volumetric replacement of LWA increased from 30% to
50%, the heat flow and temperature change in T4 were subtler. This
630 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
Fig. 13. Compressive strength of mortar at 28 d.
means that the pore solution did not freeze at this moment
because the heat released by OP3E is sufficiently high to inhibit
the freezing of the pore solution. This result can also be validated
Fig. 14. Thermal response of mortar containing NT-A/W/CC: (a) temperature and heat flow (DQs) of mortar; (b) heat flow vs. temperature.
Fig. 15. Thermal response of mortar containing 30% of NT-A/OP3E/CC (a) temperature and heat flow(DQs) of mortar; (b) heat flow vs. temperature.
by the heating process, where the heat absorbed during the melt-
ing of the ice is still close to that observed in the case of 30% LWA;
however, the endothermic peak due to the OP3E melting becomes
greater than that of the pore solution as a result of the increased
amount of OP3E (Fig. 16b).
It should be noted that the phase transformation point of the
PCM was chosen to be slightly higher than that of water, and thus,
the heat release due to phase transformation of the PCM took place
just a little before that of water as the temperature decreases.
Based on the above results, the exothermic peaks of the PCM and
water partially overlapped in the test. This phenomenon is differ-
ent from the study by Sharifi Naser P [14], where two separate
peaks corresponding to the phase transformations of the PCM
and water during cooling and heating were found because of the
higher transformation point of PCM (6 °C). It is possible that
the temperature of the mortar remains higher than 5°C after
the phase transformation of the PCM is complete, which could
differentiate the peaks of the PCM and water. The solidification
of the PCM is supposed to occur prior to water freezing so that
the heat released by the PCM can be absorbed by the water to delay
its freezing. The time offset between the solidification of the PCM
and water is crucial. Thus, further research is necessary concerning
the selection criteria of PCM to effectively utilize PCMs to improve
the freeze resistance of concrete materials.
 W. Li et al. / Construction and Building Materials 203 (2019) 621–632
Fig. 16. Thermal response of mortar containing 50% of NT-A/OP3E/CC (a) temperature and heat flow(DQs) of mortar; (b) heat flow vs. temperature.
4. Conclusions
This paper investigated the preparation and characterization of
a mortar-PCM system whose materials were selected based on
their thermal and physical properties. A detailed analysis of the
encasement effectivities and stabilities of the LWA-PCMs illus-
trates that coating the surface of an LWA that contains a PCM is
necessary because PCMs can react with the hydration products of
cement paste and consequently result in a reduction in the latent
heat of the PCM over time. To solve this problem, cement paste
is recommended as a good alternative surface coating material
for presoaked LWAs.
The effects of the PCMs on ice formation were assessed by the
thermal responses of the mortars during freeze-thaw cycling. The
LGCC tests validated that the PCM can release heat to delay the
cooling of the mortars and thus delay ice formation. The exother-
mic peak corresponding to the freezing of the pore solution during
cooling remarkably attenuated when the PCM was incorporated
into the mortar containing LWA. When the volumetric replace-
ment of the LWA was increased to 50%, the heat released by the
PCM becomes sufficiently high to inhibit the freezing of the pore
solution.
The time offset between the solidification of the PCM and pore
solution is crucial because the solidification of the PCM is supposed
to occur prior to the ice formation so that the heat released by the
PCM can be absorbed by the pore solution to delay its freezing.
Thus, further research is necessary concerning the selection criteria
of PCMs to effectively utilize PCMs to improve the freeze resistance
of concrete materials.
In addition, some issues deserve further investigation to con-
firm the feasibility of PCM incorporation/encasement in LWAs for
materials design and its outcome under actual service conditions,
which are associated with the latent heat attenuation over longer
periods and the thermal responses of materials experiencing mul-
tiple freeze-thaw cycles.
Conflict of interest
We declare that we do not have any commercial or associative
interest that represents a conflict of interest in connection with the
work submitted.
Acknowledgements
The authors gratefully acknowledge the financial supports pro-
vided by National Natural Science Foundation of China (51878481,
631
51678442, 51878480, 51878496), Natural Science Foundation of
Shanghai (18ZR1441500), National Key Research and Development
Projects (2018YFC0705404), National High-speed Train Union
Fund (U1534207), Fundamental Research Funds for the Central
Universities and Top Interdiscipline Funds of Civil Engineering for
Tongji University.
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