Construction and Building Materials 287 (2021) 123021

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Construction and Building Materials

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

Improvement on rheological property of asphalt binder using

synthesized micro-encapsulation phase change material
Tam Minh Phan, Dae-Wook Park ⇑, Tri Ho Minh Le
Dept. of Civil Engineering, Kunsan National University, Gunsan-si 54150, Jeollabuk-do, Republic of Korea

h i g h l i g h t s

Two lPCMs were successfully synthesized via encapsulation method.

CaCO3-lPCM presented good thermal stability with 95% residual weight at 160 °C.

SiO2-lPCM acquired prime encapsulation ratio (RE = 52.9%).

lPCMs released latent heat that increased asphalt binder temperature of 1.5 °C.

Both lPCMs enhanced thermal cracking resistance by reducing binder stiffness.

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

Article history: Temperature is a governing parameter that affects the rheological property of asphalt binder. Upon cool-
Received 20 January 2021 ing, bitumen becomes stiffer and prone to thermal cracking. To reduce the negative impact of tempera-
Received in revised form 26 February 2021 ture, utilizing the thermal energy storage of phase change material is a promising solution. This study
Accepted 8 March 2021
provides an approach to synthesize micro-encapsulation phase change material (lPCM) and its applica-
Available online 25 March 2021
tion to enhance the binder’s rheological property and mitigate black ice. Two lPCMs were prepared with
n-Tetradecane as a core, while Calcium carbonate (CaCO3) and Silicate (SiO2) as a shell. SEM test exhibited
Keywords:
that lPCM had a spherical shape with a diameter ranging from 1 to 7 lm. Meanwhile, thermogravimetric
Asphalt binder
Synthesized PCMs
analysis proved that the encapsulation method could protect and prevent leakage of n-Tetradecane under
Rheological property high temperature. The residual weight of CaCO3-lPCM was 95% and 84% at 160 °C and 350 °C, respec-
Thermal cracking tively. The differential scanning calorimeter results showed that the encapsulation ratio was approxi-
Black ice mately 52.9% (DH = 99.94 W/g). Moreover, different lPCM modified asphalt binders were examined to
evaluate the rheological property. Results from rotational viscosity test at 135 °C pointed out that adding
lPCM did not affect binder viscosity. DSR test showed that the incorporation of lPCM could reduce bin-
der stiffness at low temperatures. The thermal effect of lPCM was analyzed by low-temperature sweep
test. With simultaneous cooling, lPCM released latent heat, thus increasing the binder’s temperature by
1.5 °C. The low values of G*sind indicated the outperformance of lPCM-binder compared to conventional
binder in terms of thermal cracking resistance.
Ó 2021 Elsevier Ltd. All rights reserved.

1. Introduction impact on the asphalt pavement [3–5]. Temperature change influ-

ences internal pavement stress and strain, its deformation, and
Asphalt mixtures are widely used to pave roads and highways thermal cracking. Nowadays, to improve the performance of
due to their advantages, such as safety, smoothness, and construc- asphalt pavement, and extending its service life is challenging for
tion time. During its service life, asphalt road surfaces are directly researchers. The conventional improvement of pavement can
exposed to environmental conditions [1]. Other than traffic load, exhaust the use of natural resources. Many studies have been
asphalt pavement must withstand seasonal and diurnal variations developed to reduce the burden on natural resources by utilizing
in temperature [2]. Several studies pointed out that environmental by-products [6,7]. Some include using fibers to enhance the perfor-
factors, especially ambient temperature, impose significantly mance [8,9], and others utilize self-healing material to extend ser-
vice life [10,11]. Moreover, the enhancement on the binder’s
rheological property using varied modifiers is a key tool to improve
⇑ Corresponding author.
the overall asphalt mixture performance. Asphalt binder plays an
E-mail address: [email protected] (D.-W. Park).

https://doi.org/10.1016/j.conbuildmat.2021.123021
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

essential role in an asphalt pavement system [1]. During low tem- dynamic shear rheometer test (DSR), and low-temperature sweep
peratures, asphalt binder can become stiff reaching a brittle condi- test. The whole process can be referenced in Fig. 1.
tion resulting to thermal cracking. Thus, repeating the freeze and
thaw process is one of the primary pavement distresses. In the 2. Design and preparation of micro-encapsulation phase change
winter season, snow and ice can reduce the friction between the material
tire and road surface. This is especially dangerous during black
ice formation. The black ice phenomenon is hazardous on driving 2.1. Optimum phase change material design
and affects the temperature cracking of asphalt pavement. Several
methods have been developed to mitigate the adverse effects of The one-dimensional (1D) heat transfer has been widely used to
low temperature such as road salt, using a gas-fired or electric boi- predict pavement surface temperature. This is because the pave-
ler, and incorporating phase change material [11–13]. ment thickness is smaller than other dimensions of the road [4].
Phase change material (PCM) is a latent heat fusion material The governing equation of heat transfer is written in Eq. (1).
that releases/absorbs latent heat during the melting/crystallization Where, q = density (kg/m3); cq = specific heat capacity; T = temper-
process [14]. At the melting temperature (solid–liquid transition), ature (°C) t = time (s); z = thickness (m).
PCM absorbs thermal energy. Then, the stored thermal energy will
@T @ @T
be released when the surrounding temperature is lower. PCM has qcp ¼ ðk Þ ð1Þ
been receiving attention in various applications. Several studies @t @z @z
have been incorporating PCM in asphalt mixture to moderate pave- Asphalt concrete’s thermophysical properties are related to
ment temperature. For instance, the appropriate dosage of PCM aggregate types, air voids, and mineral particles [5,23]. Besides,
could regulate extreme temperature and reduce rutting of asphalt pavement temperature also depends on the effect of external fac-
pavement [15,16]. Besides, PCM was also used to delay or prevent tors as shown in Fig. 2. For example, the pavement surface is
pavement freezing at a low temperature. The research done by affected by solar radiation, air temperature, wind speed, and con-
Manning et al. proved that containing of PCM-6 (6 °C phase vection between the surface and surrounding air [17]. Equation
change) could mitigate the impact of frozen process freezing (2) shows the total boundary heat flux (Q) at the surface tempera-
[12]. Karka et al. showed that PCM has a vital ability on thermal ture involved in the heat exchange with the surrounding. The
regulation of asphalt mixture [13]. It is well known that the phase absorbed heat flux (qr) is highly dependent on the thermal absorp-
change temperature is a critical factor that tightly associates with tivity of asphalt pavement and incident solar radiation [4,24]. The
the warming or cooling temperature of asphalt mixture. The effect longwave length heat flux (ql) is related to the sky’s fraction cov-
of phase change material on thermal properties of asphalt pave- ered by the clouds [25]. While Hermansson’s research presented
ment has been calculated by the Finite Element Model (FEM) [17]. the convection heat flux (qc) between asphalt pavement and the
Nevertheless, direct incorporating PCM into asphalt mixture is surrounding air [3]. Moreover, the asphalt pavement emits infrared
restricted due to leakage and weak thermal stability [14]. The leak- thermal radiation to the surrounding as a function of temperature.
age caused a reduction in adhesion between aggregate and asphalt Report indicates that the emissivity of asphalt pavement usually
binder, resulting in lower asphalt mixture’s performance. There- ranges from 0.80 to 0.93 [4].
fore, different ways have been developed to mitigate the leakage
Q ¼ qr þ ql  qc  qe ð2Þ
problem and enhance thermal stability. Wang et al. provided a
novel microencapsulated PCM with CaCO3-shell and paraffin-core Several studies have considered the effect of incorporating PCM
[18]. Fang et al. recommended the micro-encapsulation process in asphalt concrete to improve the volumetric heat capacity (qcqeff)
using silicate (SiO2) as a shell and n-Tetradecane as a core [19]. as shown in Eq. (3) [17,26]. Where, / = PCM volume (%); n = the
Both encapsulated PCMs presented a high storage latent heat and volume fraction of PCM (%); qAC = asphalt concrete density (kg/
good thermal stability. Nowadays, many studies have been devel- m3); qPCM = PCM density (kg/m3); cqs, cql = specific heat capacity
oped to enhance the rheological property of asphalt binders at of PCM (J/kgK); cqAC = specific heat capacity of asphalt concrete
low temperatures, such as utilizing bio-oil [20], using SBS (J/kgK).
(styrene–butadienestyrene) modified asphalt binder [21], and
qcpeff ¼ /qPCM ðncpl þ ð1  nÞcps Þ þ ð1  /ÞqAC cpAC ð3Þ
incorporation of PCM in asphalt binder [22]. Due to the releasing
latent heat, PCM was utilized to improve the rheological property Besides, the thermal conductivity of PCM-modified asphalt con-
of asphalt binder at low temperature. crete is related to the matrix’s thermal conductivity. This value can
In this research, to improve the rheological property of asphalt be expressed by PCM’s volume fraction, and thermal conductivity
binder and mitigate black ice phenomenon at low temperature, a of asphalt concrete and PCM. Karol and Tomasz recommended that
one-dimensional (1D) numerical model of PCM modified asphalt the effective thermal conductivity can be calculated by the Max-
pavement was developed to calculate the optimal phase change well model [26]. The expression can be referenced from Eq. (4).
material (such as PCM’s content, phase change temperature, latent Where, keff = effective thermal conductivity (W/mK); / = PCM’s
heat fusion). Based on the FEM results, two micro-encapsulation volume (%); kAC, kPCM = thermal conductivity (W/mK) of AC and
phase change materials were synthesized using the encapsulation PCM, respectively.
method. Two shell-materials were developed, including Calcium
keff 3/
carbonate (CaCO3) and silicate (SiO2). Serval laboratory tests was ¼ 1 þ k þ2k ð4Þ
then conducted to examine the properties of lPCMs. A scanning
kAC ð PCM AC
Þ/
kPCM kAC
electron microscope (SEM) was employed to observe the morphol-
Based on the Maxwell model, the thermal conductivity of PCM
ogy, diameter, and surface of lPCM. While a thermogravimetric
was calculated only if PCM content was lower than 25% of total
analysis was adopted to specify the thermal stability. Differential
mixture volume. The kPCM was depended on the liquid and solid
scanning calorimeter (DSC) determined the phase change proper-
fractions, as shown in Eq. (5). Where, n = volume fraction (%); kl,
ties such as phase-change temperatures and latent heat fusion.
ks = thermal conductivity (W/mK) at liquid and solid phase,
Subsequently, base asphalt binder (PG 64–22) was modified with
respectively.
the two new lPCMs to investigate the effect on rheological prop-
erty. This investigation included rotational viscosity test (RV), kPCM ¼ nkl þ ð1  nÞks ð5Þ

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Fig. 1. Research flowchart.

Fig. 2. Pavement temperature profile.

Report suggests that the PCM’s volume fraction has a tight cor- and volume fraction of PCM at the ith layer were ki, zi, qi, and ni
relation with the temperature [17]. The expression of volume frac- (with i = 1, 2, 3, . . ., n), respectively. The recursive numerical model
tion is written in Eq. (6). Where, n(T) = volume fraction at the was employed to analyze the transient temperature response of
temperature T (%); T = temperature (°C); Tl, Ts = liquid and solid the PCM-modified asphalt concrete as shown in Eq. (8). Where,
temperature (°C), respectively. Tp+1
i and Tpi = temperature at the time p + 1 and p (°C), respectively;
8 Dt = time step (s); Dz = depth increment (m) np+1 i and npi = PCM’s
>
< 0; T < T s ; Solid phase fraction volume at the time p + 1 and p (%), respectively.
nðTÞ ¼ TT s
T l T s
; T s < T < T l ; Mushy phase ð6Þ p p
>
: T pþ1  T pi T p  T pi T  T iþ1
1; T > T l ; Liquid phase qcpeff ð i
ÞDz ¼ ki ð i1 Þ  ki ð i Þ
Dt Dz Dz
pþ1 p
When PCM-modified asphalt concrete’s temperature n  ni
 /qPCM Lð i Þ Dz ð8Þ
approaches the phase change temperature, PCM can absorb or Dt
release thermal energy heat (L). Hence, the transient heat conduc-
The unknown PCM’s fraction volume (nt+1) at the time tp+1 was
tion of PCM-modified asphalt concrete is expressed in Eq. (7).
determined by an iterative method. As shown in Eq. (9), the inter-
@T @ @T @n mediate temperature (Tm+1 i ) was calculated based on the tempera-
qcpeff ¼ ðkeff Þ  /qPCM L þ Q ð7Þ ture of the previous time (tp). The Tm+1 is then used to update the
@t @z @z @t i
unknown nt+1. The iterative process was repeated until
The MATLAB R2020a was employed to program and solve the  
 mþ1 
T  T p  < 105 [28].
numerical equations [27]. Fig. 2 depicts a schematic diagram of
the asphalt pavement. Thermal conductivity, thickness, density,
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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

T mþ1  T pi T p  T pi T p  T piþ1 Tetradecane was first dissolved with an emulsifier solution of

qcpeff ð i
ÞDz ¼ ki ð i1 Þ  ki ð i Þ Tween 80 and Span 80. At the same time, a PVA solution was pre-
Dt Dz Dz
n mþ1
 ni p pared by mixing deionized water and PVA in a 500 ml flask. Two
 /qPCM Lð i ÞDz; m ¼ 1; 2; 3; ::: ð9Þ solutions (core-solution and PVA-solution) were then mixed. After-
Dt
ward, the TEOS and acetic acid solution were dripped into solution
Overall, the interaction between the pavement surface and its at 35 °C with a speed of 300 RPM for 3 h. Finally, the resulting
surrounding is written in Eq. (10). products were filtered and washed by ethanol three times before
p p drying in the oven at 35 °C for 24 h.
T pþ1  T pi T p  T pi T  T iþ1
qcpeff ð i
ÞDz ¼ ki ð i1 Þ  ki ð i Þ
Dt Dz Dz
npþ1  npi 3. Test methods
 /qPCM Lð i ÞDz þ Q ð10Þ
Dt
3.1. Properties of micro-encapsulation phase change materials
This study aims to evaluate the effect of lPCM on rheological
properties of asphalt binder; therefore, the PCM content is deter-
3.1.1. Scanning electron microscope (SEM test)
mined by the weight of asphalt binder through equation (11).
The scanning electron microscope (HITACHI SU3800) was
Where, pPCM = PCM content (%), / = optimum PCM volume (%),
employed to observe the morphology, size, and particle shape of
qPCM = PCM density (kg/m3), pb = binder content in asphalt mixture
micro-encapsulation phase change material (Fig. 6a).
(%), and qb = binder density (kg/m3).

/  qPCM
pPCM ¼ ð11Þ 3.1.2. Thermogravimetric analysis (TGA test)
pb  qb
Thermogravimetric analysis is adopted to determine a mate-
The temperature of PCM-modified asphalt concrete was ana- rial’s thermal stability and fraction by monitoring the weight
lyzed to predict PCM’s optimum contents in asphalt mixture. In change [31]. In the current research, the thermal stability of differ-
this research, boundary conditions (air temperature, wind speed, ent PCMs was analyzed by TA Instruments SDT Q600 (Fig. 6b). The
and solar radiation) were obtained from South Korea’s climate size of a single PCM sample ranged from 1 to 5 mg. Each sample
data, as shown in Fig. 3a [29]. The thickness of PCM-AC, base was heated from room temperature (25 °C) to 350 °C with a heat-
course, and subgrade was 10 cm, 15.2 cm, and 20 cm, respectively. ing ramp of 20 °C /min under a nitrogen atmosphere. Concurrently,
Based on previous studies, the materials’ thermophysical proper- the weight of the sample was recorded during the whole analysis
ties are presented in Table 1 and Table 2 [4,17,24,30]. The results period.
from Fig. 3b shows that the PCM addition of 1.5% by wt. of asphalt
mixture (7.5% by wt. asphalt binder) helps pavement temperature
3.1.3. Differential scanning calorimetry (DSC test)
gain 1.5 °C higher than that of without PCM. Therefore, 2.5% and
Differential scanning calorimetry (DSC) measures samples’
7.5% by weight of the binder were chosen as the main contents
energy transfer undergoing a physical or chemical change [32].
to examine PCM’s effect on the rheological property of asphalt
The TA DSC250 was assigned to investigate the thermal transition
binder.
of synthesized PCM (Fig. 6c). A prepared sample of 10–15 mg is
shown in Fig. 6d. For each sample, the DSC test consisted of a heat-
2.2. Preparation of micro-encapsulation phase change material ing and cooling process. Firstly, the sample cooled down from
room temperature to 40 °C and was maintained for 5 mins. The
2.2.1. Raw materials sample was then heated to 40 °C and kept for 5 mins before cooling
In this study, n-Tetradecane (C14H30) was used as a core. The n- again to 40 °C. The test was conducted with a heating/cooling
Tetradecane had a molecular weight of 198.39 g/mol, latent heat rate of 10 °C /min. The PCM’s heat flow (W/g) was recorded during
capacity of 154.7 J/g, and melting point of 10 °C. Two surfactants the process. The encapsulation ratio (RE) was estimated to deter-
were used in this experiment. First, Tween 80 (C64H124O26) had mine the effect of the encapsulation method on energy storage of
molecular weight of 1310 g/mol. Second, Span 80 (C24H44O6) had lPCM. The RE (%) was defined as the enthalpy (DH) ratio of lPCM
a molecular weight of 428.6 g/mol. Shell material used in this by n-Tetradecane, as shown in Eq. (12).
study included calcium chloride (CaCl2) and sodium carbonate
(Na2CO3), Tetra-ethyl silicate (TEOS), Poly Vinyl Alcohol (PVA), DHlPCM
Ethanol, and Acetic acid. RE ¼  100 ð12Þ
DHTetradencan

2.2.2. Preparation of lPCMs

The CaCO3 micro-encapsulation process is depicted in Fig. 4. 3.2. Rheological property of lPCM modified asphalt binder
The core–shell ratio was 1:1. Firstly, the core material (n-
Tetradecane) and the surfactants (Tween 80 and Span 80) were dis- 3.2.1. Rotational viscosity test (RV test)
solved in deionized water in a 500 ml flask. The dissolved process The RV test determines the viscosity of asphalt binders in the
took for 20 min with stirring speed of 300 RPM (rotation per min). high temperature of production and construction. The smaller vis-
Secondly, in preparation of shell material, the calcium chloride cosity value at the high temperature (e.g., 135 °C) indicates the bet-
(CaCl2) was dissolved in deionized water (50 ml), then dropped ter workability of asphalt mixture in the mixing and compaction
into the core solution, and continuously mixed for four hours at process [33]. According to Superpave binder specification, the vis-
300 RPM. The sodium carbonate solution (Na2CO3 + deionized cosity shall not exceed 3 Pa.s [1]. In this study, the Brooked vis-
water) was initiated into the mixture by dripping into the flask. cometer was employed to measure the viscosity of lPCM
After dripping, a centrifuge was employed to purify the resultant modified asphalt binder. The base binder (PG 64–22) was modified
microcapsules. The process was conducted at a temperature of with the highest lPCM content (7.5% by weight of binder). The
35 °C. Finally, micro-encapsulation PCM was dried at 60 °C for 12 h. rotational test was conducted with a constant rotational speed of
The SiO2 micro-encapsulation process is shown in Fig. 5. In this 20 RPM at 135 °C. For each replicate, the viscosity was measured
process, the core–shell ratio was the same with 1:1. The n- at 1-min intervals for a total of 3 min [34].
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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Fig. 3. (a) Climate data, (b) surface temperature of PCM-modified asphalt pavement.

Table 1
Thermophysical properties of materials.

Thickness (cm) Density (kg/m3) Thermal conductivity (W/mK) Heat capacity (J/kgK)
AC 10.2 2288 1.2 950
Base course 15.2 1950 1.0 1000
Subgrade 20.0 1760 1.0 1100

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Table 2
Thermophysical properties of lPCM.

Latent heat fusion (J/g) Density (kg/m3) Thermal conductivity (W/mK) Heat capacity (J/kgK)
Tl = 3 °C 50 768 Liquid phase: 0.15 Liquid phase: 2330
Ts = 8 °C Solid phase: 0.37 Solid phase: 1930

Fig. 4. The micro-encapsulation process of CaCO3-lPCM.

Fig. 5. The micro-encapsulation process of SiO2-lPCM.

3.2.2. Dynamic shear rheometer (DSR test) p  a  c  ebþclogðf aT Þ

uf ¼  2
ð14Þ
½1 þ k  ebþclogðf aT Þ ð kÞ
The dynamic shear rheometer (DSR) test was executed to mea- 1þ1
sure rheological properties such as complex modulus (G*) and
phase angle (u) parameters. Two lPCM contents were considered,
C 1  ðT  T r Þ
including 2.5% and 7.5% by weight of binder. The DSR was exam- logaT ¼  ð15Þ
ined in several temperatures, including 0 °C, 10 °C, 20 °C, 30 °C, C 2 þ ðT  T r Þ
40 °C, 50 °C, 60 °C, and 70 °C. For each temperature, the frequency In this study, the reference temperature of 20 °C was chosen to
ranged from 0.1 to 20 Hz. At low temperature (0 °C–30 °C), the generate the master curve of both dynamic modulus and phase
25 mm diameter plate, 1 mm gap, and constant strain amplitude angle. The MATLABÒ optimization toolbox was employed to deter-
of 0.05% were used (Fig. 7). Otherwise, the 8 mm diameter plate, mined several unknown model parameters (i.e., d, a, k, b, c, C1, and
2 mm gap and constant strain amplitude of 0.1% was used at high C2) with the minimum sum of error [27,39]. The sum of error (SE)
temperature (40 °C–70 °C) [35]. can be referenced in equation (16). Where, SE = sum of error;
At reference temperature (Tr), the complex modulus and phase N = number of measured data; G*m, i, um, i = measured dynamic
angle master curve were generated using time-temperatures modulus, measured phase angle at point ith, respectively; G*p, i,
superposition principle [36]. The dynamic modulus master curve up, i = predicted modulus, predicted phase angle at point ith,
and phase angle master curve were expressed in equation (13) respectively.
and (14), respectively [37]. The shift factor (aT) was employed to
shift complex modulus or phase angle at a certain temperature SE ¼ ErrorG þ Error u
 2  2 
(T) to a master curve for a reference temperature. As shown in P
N ð16Þ
SE ¼ Gm;i  Gp;i þ um;i  up;i
equation (15), the shift factor was calculated based on Williams- i¼1
Landel-Ferry (WLF) relation [38]. Where, Gf*, uf = dynamic modu-
lus and phase angle at frequency, respectively; f = loading fre-
quency (Hz); d, a, k, b, c = fitting parameters; aT = time– 3.2.3. Low-temperature sweep test
temperature shift factor; T = test temperature (°C); Tr = reference The low-temperature sweep test was employed to measure the
temperature (°C); C1, C2 = fitting parameters. thermal effect of lPCM on the rheological response of the modified
  a asphalt binders. The specimens had a size of 8 mm in diameter
 
logGf  ¼ d þ ð13Þ with 2 mm in thickness. This test was conducted with a constant
1 þ ebþclogðf aT Þ
strain amplitude of 0.1% and frequency of 1 Hz. The temperature
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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Fig. 6. (a) SEM test, (b) TGA test, and (c, d) DSC test.

was dropped from 20 °C to 10 °C with a cooling ramp of 0.44 °C / [40]. The small partial sizes and de-agglomeration may help lPCM
min [13]. easily distribute in an asphalt mixture. Meanwhile, SiO2-lPCM
showed a smaller diameter than CaCO3-lPCM, which was approx-
imately 0.9–1.5 lm (Fig. 9d). The surface of SiO2-lPCM was gener-
4. Results – discussion ally smoother than that of CaCO3-lPCM.

4.1. Micro-encapsulation PCM properties 4.1.2. Thermogravimetric analysis

Fig. 10 depicts the thermal stability of lPCMs and core material
4.1.1. Scanning electron microscope (n-Tetradecane). This test was measured thermal stability of
The micro-encapsulation process can be explained through lPCMs under the high mixing temperature (e.g., 160 °C). Overall,
Fig. 8. Firstly, n-Tetradecane was dissolved with two surfactants. the encapsulation method improved thermal stability of lPCMs.
After the mixing process, the core was covered by a layer of surfac- The remaining weight of the SiO2 sample decreased to 71% at the
tants, which formed a micelle. By adding calcium chloride (CaCl2) temperature of 160 °C. Meanwhiles, the CaCO3-lPCM acquired
into the n-Tetradecane-emulsion system, the Ca2+ was captured better thermal stability than that of SiO2-lPCM. The residual
on a micelle surface. Then, adding sodium carbonate (Na2CO3) into weight of the CaCO3 sample was reduced by 5% only at 160 °C,
the emulsion creates CaCO3-shell. As a result, the CaCO3-lPCM was and slightly decreased to 84% at 350 °C. The outperformed residual
synthesized with a core of n-Tetradecane and a shell of CaCO3. This weight confirmed that the CaCO3-shell could reduce leakage of the
process was idealized based on the research of Wang et al. [18]. core material. Therefore, the CaCO3 shell is considered as an effec-
Fig. 9 illustrates the morphology of the two lPCMs. Overall, tive method for improving the thermal stability of lPCM in an
both lPCMs archived the perfect spherical micro-encapsulation asphalt mixture. As shown in Fig. 10, the n-Tetradecane exhibited
structure as shown in Fig. 9b and Fig. 9e. The CaCO3-lPCM’s diam- a weight loss of 70% at 160 °C. However, using encapsulation meth-
eter ranged from 5 to 7 lm. The surface of CaCO3-lPCM was gen- ods help n-Tetradecane substantially reduce its weight loss, which
erally quite rough as depicted in Fig. 9c. This is because of the was 5% and 30%, corresponding to CaCO3 and SiO2 shell, respec-
crystalline polymorphs of CaCO3. At 35 °C reaction temperature, tively. Thus, it can be concluded that both encapsulation methods
most of CaCO3 morphological structures were calcite and vaterite showed good protection on n-Tetradecane core.

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Fig. 7. (a, b) DSR test, (c) dynamic modulus, and (d) phase angle master curve generalized by WLF model.

Fig. 8. CaCO3-lPCM synthesis process.

Fig. 9. Microstructure of (a, b, c) CaCO3-lPCM and (d, e, f) SiO2-lPCM.

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

4.1.3. Differential scanning calorimetry

The phase change properties of two lPCMs are shown in Fig. 11.
The phase change temperature ranged from 0 to 6 °C, which can
prevent/delay the pavement’s freezing of black ice [12]. When
the environment temperature approaches 0 °C (black ice occur-
rence), lPCM releases latent heat energy to warm the surrounding
environment (asphalt mixture). The utilization of this latent heat
can be used to delay the black ice formation and improve thermal
cracking resistance of asphalt binder at low temperatures. The
energy storage of lPCM was mainly related to the core material
that releases/absorbs thermal energy. Therefore, the encapsulation
(RE) ratio indicated the storage effect of the encapsulation method.
The higher RE corresponds to better thermal energy storage. The
latent heat fusion of SiO2-lPCM was higher than that of CaCO3-
lPCM. The SiO2 sample’s enthalpy was approximately 99.94 J/g
(RE = 52.9%), while CaCO3 presented an enthalpy of 71.83 J/g
(RE = 37.9%). This can be explained by the thermal stability of
CaCO3-shell compared that of SiO2-shell (as mentioned in 4.1.2),
which may reduce the release latent heat of core material. More-
Fig. 10. Thermogravimetric analysis result.
over, the difference of melting and freezing point between n-
Tetradecane and lPCMs indicated that the shell material slightly
delayed the phase change process.

Fig. 12. (a) Dynamic modulus and (b) phase angle master curves of lPCM modified
Fig. 11. DSC curves of CaCO3 and SiO2 lPCM: (a) cooling curve, (b) heating curve. asphalt binders.

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

Table 3
Parameters of master curves model.

Mix types d a k b c C1 C2 SE
PG 64–22 11.59 7.40 0.18 0.99 0.42 36.67 191.26 1.12
CaCO3-lPCM-2.5% 14.15 20.19 4.61 1.75 0.39 17.44 146.55 1.26
CaCO3-lPCM-7.5% 13.79 19.13 3.86 1.41 0.43 13.58 115.06 1.15
SiO2-lPCM-2.5% 7.53 13.89 1.36 1.75 0.39 17.14 123.15 1.13
SiO2-lPCM-7.5% 6.00 12.51 0.71 1.11 0.29 15.46 134.04 1.21

4.2. Rheological properties SiO2-lPCM-7.5% presented the lowest dynamic modulus value at
high frequencies (low temperatures). This can be explained that
4.2.1. Rotational viscosity the latent heat released by the addition of lPCM which help warm-
Among the different contents, the highest lPCM dosage (7.5% ing the surrounded binder and thereby, mitigating the increase in
by wt.) was chosen to analyze rotational viscosity behavior. The binder stiffness. In other words, lPCM could improve the thermal
rotational viscosity of 7.5% lPCM modified asphalt binder was cracking resistance of asphalt binder. When temperature increases,
approximately 0.5 Pa.s at the temperature of 135 °C. Based on the CaCO3-lPCM-7.5% gained the highest dynamic modulus,
the Superpave specification of asphalt binder, the RV has met the improving rutting resistance. At this stage, the effect of latent heat
criterion of 3 Pa.s [1]. It could be found that the addition of lPCM was negligible; thereby, lPCMs played a role as mineral particles.
did not affect viscosity of asphalt binder at the high range temper- Fig. 12b illustrates phase angle master curves of lPCM modified
ature. In other words, the addition of lPCM did not affect the pro- asphalt binders. The phase angle is an indicator which demon-
duction and compaction of asphalt mixture. strates the ratio of viscosity and elasticity. The lPCM modified
asphalt binders obtained a lower phase angle than the base binder
4.2.2. Dynamic shear rheometer at the high frequencies or low temperatures. The lower phase angle
The dynamic modulus master curves are illustrated in Fig. 12a. indicated less viscous behavior. Therefore, the asphalt binder can
In this study, the reference temperature was 20 °C. For each lPCM, deter the occurrence of low temperature cracking.
two different contents were examined (e.g., 2.5% and 7.5%). The Fig. 13 shows dynamic modulus and phase angle at different
predicted parameters are shown in Table 3. Overall, asphalt binder frequencies (e.g., 0.1 Hz, 1.0 Hz, 10 Hz, and 20 Hz). Overall, the
containing lPCM obtained a lower dynamic modulus at low tem- dynamic modulus decreased while the phase angle increased when
peratures or high frequencies compared to the control one. The the temperature was elevated. At the low temperature (0–10 °C),

Fig. 13. Dynamic modulus and phase angle at different frequencies.

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

asphalt binders presented viscous behavior; however, lPCM mod- lus value than the unmodified binder. This phenomenon may be
ified asphalt binders exhibited a lower dynamic modulus than PG due to the phase transition of lPCMs has undergone at the low
64–22 binder. Especially, the SiO2-lPCM-7.5% modified binder temperature (phase change temperature range of 0–6 °C). Thereby,
acquired the lowest dynamic modulus value. It can be explained the effect of latent heat was negligible at high temperature range.
by the latent heat effect from the lPCM, which reduced the stiff- When the influence of latent heat was insignificant the lPCM acts
ness of the asphalt binder as mentioned before. At the high range as the mineral component, which could contribute to the stiffness
temperature (60–70 °C) and low frequencies (e.g., 0.1 Hz and reinforcement of asphalt binder [22].
1.0 Hz), binders containing lPCM gained a higher dynamic modu-
4.2.3. Low-temperature sweep test
The low-temperature sweep test examined the thermal effect of
lPCM on the rheological property of modified asphalt binders.
Dynamic modulus and phase angle of modified binders were
(a) recorded during the cooling process (from 20 °C to 10 °C). The
results infer that asphalt binders containing lPCM obtained a
lower dynamic modulus than the base one. Generally, the dynamic
modulus values increased when the temperature decreased. More-
over, both lPCMs gained a lower dynamic modulus value than that
of an un-modified asphalt binder. The SiO2 samples presented dis-
continuous curves during phase change temperature, as shown in
Fig. 14a. When the environment temperature dropped to 4 °C,
the dynamic modulus value suddenly decreased by 55 to 40 kPa.
At the same time, lPCM released the latent heat, which increased
the whole sample’s temperature by 1.5 °C. Then, the dynamic mod-
ulus value of lPCM modified asphalt mixture continuously
increased. However, it was found that the temperature of modified
mixture still maintains lower than the base asphalt binder (PG 64–
22). It can be concluded that asphalt binder containing lPCM could
reduce stiffness at the low temperature.
The temperature involved time of PCM modified asphalt bin-
ders is displayed in Fig. 14b. As expected, lPCM modified asphalt
(b) binder gained a higher temperature than the control sample due
to the release of latent heat. However, the temperature difference
of CaCO3-lPCM was insignificant compared to that of SiO2-
lPCM. This may be due to the latent heat capacity, as proved in
the 4.1.3 section. The discontinuous curves were only recorded in
SiO2-lPCM samples. Meanwhiles, the CaCO3-PCM with small
latent heat capacity (approximately 70 J/g) and larger size (5–
7 lm) presented continuous curves, as shown in Fig. 14a.
Moreover, the sample binder temperature increased at the
phase transition of lPCM, the G*sind values were calculated at
variable temperatures such as 6, 4, 2, 0, 2, 4, and 6 °C to verify
the effect of lPCM on low temperature cracking (Fig. 14c). Based
on the study of Brown et al., the lower G*sind value indicated a bet-
ter low temperature cracking resistance [1]. This behavior was
observed for SiO2-lPCM-7.5%, gaining the lowest value among dif-
ferent asphalt binders. Meanwhile, the conventional asphalt binder
showed the highest G*sind value. Overall, the addition of both
types and mixture weight percentage of lPCM could improve the
(c) thermal cracking resistance of asphalt binder at low temperature.

5. Conclusions

In this study, two micro-encapsulation phase change materials

(lPCMs) are synthesized for heat energy storage, including CaCO3-
lPCM and SiO2-lPCM. The improvement on rheological properties
of lPCM modified asphalt binder were confirmed by the dynamic
shear rheometer test and the low-temperature sweep test. The fol-
lowing key findings can be drawn:

Two micro-encapsulation phase change materials were success-

fully synthesized with the core–shell ratio of 1:1. Both lPCMs
archived the perfect spherical micro-encapsulation structure.
The diameter of CaCO3-lPCM and SiO2-lPCM ranged from 5
to 7 lm and 0.9–1.5 lm, respectively.
Fig. 14. (a) Dynamic modulus and (b) time–temperature relationship, and (c)
G*sind.

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T. Minh Phan, Dae-Wook Park and T. Ho Minh Le Construction and Building Materials 287 (2021) 123021

The SiO2-lPCM acquired a higher latent heat of 99.94 J/g machine learning approaches, Constr. Build. Mater. 247 (2020), https://doi.org/
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asphalt concrete, Int. J. Therm. Sci. 133 (2018) 140–150, https://doi.org/
Tam Minh Phan: Methodology, Software, Validation, Data cura- 10.1016/j.ijthermalsci.2018.07.014.
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Writing - review & editing. Tri Ho Minh Le: Validation, Data cura- 10.1016/j.apenergy.2016.03.037.
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Declaration of Competing Interest https://doi.org/10.1021/acs.energyfuels.6b01799.
[20] Z. Sun, J. Yi, Y. Huang, D. Feng, C. Guo, Properties of asphalt binder modified by
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[22] M. Bueno, M.R. Kakar, Z. Refaa, J. Worlitschek, A. Stamatiou, M.N. Partl,
Acknowledgements Modification of asphalt mixtures for cold regions using microencapsulated
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