Applied Thermal Engineering 124 (2017) 346–352

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Applied Thermal Engineering

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

Research Paper

Improving thermal characteristics and stability of phase change material

containing TiO2 nanoparticles after thermal cycles for energy storage
Samaneh Sami, Nasrin Etesami ⇑
Department of Chemical Engineering, Isfahan University of Technology, P.O. Box: 84156-83111, Isfahan, Iran

h i g h l i g h t s

 Thermal characteristics and stability of TiO2/paraffin with surfactant were improved.

 Thermal conductivity of TiO2/paraffin/SSL composite (3 wt%) was increased 47.85%.
 TGA results showed that thermal stability of the nanocomposite with SSL was improved.
 There is no significant variations in thermal properties of nanocomposites after thermal cycles.
 Latent heat of composites showed an optimal value with increasing TiO2 mass ratio.

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

Article history: In this study, thermal characteristics and stability of TiO2/paraffin composites with and without sodium
Received 22 February 2017 stearoyl lactylate (SSL) as a surfactant were evaluated. The TiO2/paraffin composites with 0.5, 0.7, 1, 2, 3,
Revised 11 May 2017 4 wt% were prepared in two series, with and without the SSL. FE-SEM micrographs illustrated that adding
Accepted 7 June 2017
the surfactant to the paraffin matrix could improve the dispersion of the nanoparticles efficiently. DSC
Available online 8 June 2017
analysis showed that the maximum latent heat of 165.1 and 167 J/g for nanocomposites occurs in 1
and 3 wt% for samples of TiO2/paraffin without and with the SSL, respectively. The thermal conductivity
Keywords:
coefficient was enhanced with adding nanoparticles, considerably. An increase of 47.85% in the thermal
Paraffin
Phase change material
conductivity was found for the paraffin containing 3 wt% of nanoparticles with the surfactant.
TiO2 nanoparticles TiO2/paraffin composite with 3 wt% was chosen as an optimal sample to consider the physical and ther-
Thermal cycles mal stability after several thermal cycles. TGA thermograms showed that thermal stability of the
Thermal stability TiO2/paraffin/SSL composite (3 wt%), as compared to pure paraffin and TiO2/paraffin (3 wt%), was
Thermal conductivity improved. It was found that the melting temperature and the latent heat of nanocomposites had inappre-
ciable changes after several thermal cycles. The thermal conductivity of the nanocomposites approached
the initial thermal conductivity of the pure paraffin, after several thermal cycles, while a marked decrease
in thermal conductivity of pure paraffin was apparent.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction storage in various forms such as thermal, chemical and mechanical

Energy storage is a useful tool for increasing energy efficiency
and energy saving. The efficient use of the energy and utilization
of the renewable energies increase because limited fossil fuel
resources and environmental pollutions created by this type of
fuel. Solar energy is one of the types of renewable energy. The
non-uniform and time-dependent nature is the main obstacles in
the use of solar energy. The intensity of sunlight varies during
the day and does not exist energy during the evening. The energy
⇑ Corresponding author.
E-mail address: netesami@cc.iut.ac.ir (N. Etesami).
during the day can overcome these problems [1].
Phase change materials (PCMs) are considered as one of the best
energy storage methods. The paraffins are selected as a suitable
candidate for use in thermal energy storage systems because of
the appropriate latent heat, the good stability and the low cost at
the specific temperature range [2]. Low thermal conductivity of
the paraffins is one of the limited properties of them and reduces
their performance. For this reason, in the recent years many efforts
were conducted to improve the thermal conductivity of the phase
change materials, particularly paraffin [3,4]. Increasing the thermal
conductivity causes to increase the heat transfer rate in the phase
change materials and improve the energy storage efficiency. The
thermal conductivity can be improved by using the metal fins,

http://dx.doi.org/10.1016/j.applthermaleng.2017.06.023
1359-4311/Ó 2017 Elsevier Ltd. All rights reserved.
 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352
the porous matrix and the fibrous materials [5–8]. These methods
are not desirable due to increase in weight and volume of the
energy storage devices. Dispersing fine particles with high thermal
conductivity in the phase change material has been introduced as a
convenient method to increase the effective thermal conductivity.
The thermal conductivity of PCM composites has been improved
by adding the low amount of the metal or the metal oxide
nanoparticles to PCMs in some studies [9,10].
Sohan et al. [11] reported an enhancement of 48% and 60% in
the thermal conductivity for the paraffin containing 10 wt.% and
20 wt.% of iron nanoparticles, respectively. In literature, several
studies show that there is not necessarily a linear relationship
between the mass fraction of nanoparticles and the improvement
in the thermal conductivity [12,13].
Teng and Yu [14] studied on thermal storage properties of the
paraffin including different metal oxide nanoparticles. Alumina,
Titania, silica and zinc oxide were dispersed into three concentra-
tions of 1.0, 2.0, and 3.0 wt%. Their results showed that TiO2 has
more effect on the heat conduction performance and the thermal
storage characteristics of the paraffin. The highest decrement ratio
of the melting latent heat is only 0.46%, compared with that of the
pure paraffin.
Harikrishnan and Kalaiselvam [15] investigated the thermal
characteristics of palmitic acid contain TiO2 during energy storage
and release processes. The results showed, the melting and solidi-
fication times of composites were reduced by 6.43, 14.62, 21.05%
and 6.18, 12.37, 20.11% for 0.1, 0.2 and 0.3 wt% of TiO2 respectively.
In the most previous studies the effect of nanoparticles on the
thermal properties of the PCM has been investigated, while stabil-
ity and the dispersion of nanoparticles in the PCM matrix had not
been considered. Wang et al. [16] synthesized anatse titanium
oxide nanoparticles in 20 nm of diameter and examined the influ-
ences of dispersing of TiO2 on the thermal properties of TiO2/paraf-
fin composites without surfactant. The dispersion of TiO2
nanoparticles in the samples were examined using the polarizing
optical microscope (POM). But the sustainability of the produced
samples after the heating cycles has not been evaluated. Motahar
et al. [17] performed laboratory studies on the thermal and the
rheological properties of the n-octadecane with the TiO2 nano-
additive. The maximum improvement in thermal conductivity
occurred in 3 wt% of nano-particle and the reduction was seen
greater than 4 wt%. They discussed more about the rheological
properties of PCM composites in their study.
Ho and Gao [18] prepared the composite by dispersing Al2O3
nanoparticles with 5 wt% and 10 wt% in n-octadecane by means
of non-ionic surfactant. Thermo physical properties of samples,
such as latent heat of fusion, density, dynamic viscosity, and ther-
mal conductivity, were investigated experimentally. The amount of
nanoparticles and surfactant are the affecting factors on the stabil-
ity of nanoparticles in the PCM matrix.
Nourani et al. [19] studied thermal behavior of paraffin contain-
ing Al2O3 nanoparticles. Sodium stearoyl lactylate (SSL) has been
used as the surfactant to increase stability of Al2O3/PCM samples.
Their results showed that thermal conductivity of composite is
higher than that of pure PCM at phase change temperature of sam-
ple, while heat fusion and melting temperature of obtained com-
posite has no significant variations. In this study, stability of
nanoparticles dispersion in the obtained nanocomposites and their
thermal properties has not been investigated after thermal cycles.
A review of the previous research shows that there is a lack of
studies regarding the effect of adding nanoparticles to paraffin on
the thermal properties of the composites, stability and dispersion
of nanoparticles in the paraffin matrix. Therefore, in this work, tita-
nium oxide nanoparticles were added to paraffin in a wide range of
mass fractions, in the presence and the absence of sodium stearoyl
lactylate (SSL) as an effective surfactant. In addition, the thermal
347
properties of composites, such as melting temperature, latent heat
and thermal conductivity, were evaluated. Also, the changes in the
thermal properties were considered after the alternative thermal
cycles. The thermal stability of the samples was investigated by
the thermogravimetry analysis. The physical stability and the dis-
persion of the nanoparticles in the composites were evaluated for
the first time using the scanning electron microscopy, after and
before the alternative thermal cycles.
2. Materials and methods
2.1. Materials
Paraffin with the melting point about 54–58 °C (Merck, Ger-
many) as phase change material. Sodium stearoyl lactylate (SSL)
with the chemical formula C24H43NaO6 was used as a surfactant
were purchased from Merck Company (Germany). Titanium oxide
nanoparticle was purchased from PlasmaChem Company (Ger-
many) with average particle size of 5–20 nm and 50 ± 10 m2/g of
specific surface area.
2.2. Preparation of the samples
Paraffin nanocomposites containing different mass fractions of
the titanium oxide nanoparticles were prepared; weighted amount
of nanoparticles was added to liquid paraffin in several steps and
used magnetic stirrer and ultrasonic processor (Hielsher up
400 s) alternatively for appropriate dispersion in samples. Two ser-
ies of samples; I) without the SSL and II) with the SSL as a surfac-
tant with mass ratio 1:4 for SSL/TiO2, were prepared in different
mass fractions of TiO2 0, 0.5, 0.7, 1, 2, 3 and 4 wt%. Mass ratio of
SSL to TiO2 was selected based on experimental observations in
three mass ratio 1:3.5, 1:4 and 1:4.5.
2.3. Characterization
Differential scanning calorimetry (DSC), Manufacturing BAHR
Thermoanalyse GmbH Germany with the relative standard uncer-
tainty of ±7% was used to determine the thermal characteristics of
the samples such as melting point and the latent heat under nitro-
gen, with heating rate of 5 °C/min in the range temperature of 30–
90 °C. Thermal stability in measurable temperature range was per-
formed by Thermal Gravimetry Analysis (TGA). Thermal analyzer
TGA/DTA Pyris Diamond model was used under nitrogen from
room temperature to 450 ° C temperature for thermal analysis of
the samples. The relative standard uncertainty of thermal analyzer
is ±10%. The Field-Emission Scanning Electron Microscope (FE-
SEM), Mira 3-XMU model was used to evaluate the dispersion of
nanoparticles in phase change material. The thermal conductivity
was measured by KD2 Pro Manufacturing Co. Decagon America
with the relative standard uncertainty of ±3%.
3. Results and discussion
3.1. Evaluation of dispersion of nanoparticles in the samples
Fig.1 shows FE-SEM images of 1 wt% and 3 wt% of TiO2/PCM
samples with (A, B) and without (a, b) the surfactant of SSL. As seen
in the Figs. 1-a and -b, the nanoparticles in the paraffin without
surfactant tended to aggregate together and dispersion of nanopar-
ticles was less significant, while in the presence of SSL (Fig. 1-A and
-B), dispersion of the nanoparticles appropriately occurred due to
reduction in the surface energy of the particles.
It should be noted that TiO2 nanoparticles in mass ratios up to
1 wt% are barely visible in the microscopic images. Wang et al.
348 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352
Fig. 1. FE-SEM images of TiO2/paraffin composites with (a) 1.0 wt% (b) 3.0 wt% and TiO2/paraffin/SSL composites with (A) 1.0 wt% (B) 3.0 wt%.
[16] also found similar results. They also showed that mass ratios
less than 1 wt% of TiO2nanoparticles could not be visible by Polar-
izing Optical Microscope (POM). Fig. 1-b shows the dispersion of
the nanoparticles with the mass ratio of 3 wt% in paraffin without
the surfactant. Probability of aggregation could be enhanced with
increasing the concentrations of TiO2 nanoparticles in the paraffin.
In this case, Van der Waals force acted more powerfully in the
short distance, thereby leading to the aggregation of nanoparticles.
The effect of surfactant on the uniformity of the dispersion of
nanoparticles in the paraffin phase with higher mass ratio of
nanoparticles was more profound (see Fig. 1-B). Fig. 1-B shows that
Fig. 2. Images of 3 wt% of TiO2/paraffin composites (a) with SSL (b) without SSL.
the nanoparticles were uniformly distributed, and without any
agglomeration throughout the sample.
Fig. 2-a and -b show the images of TiO2/paraffin composites
with mass ratio of 3 wt%, with and without surfactant (SSL). Com-
paring of Fig. 2-a and -b shows a better dispersion of the nanopar-
ticles in the paraffin in presence of the surfactant. Sedimentation of
nanoparticles at the bottom of the container for sample without
SSL could be observed in Fig. 2-b.
SSL structure shows that this material decreases surface tension
through the creation of an ionic environment in paraffin. It leads to
increase particle–particle interactions after adding nanoparticles.
The particle wettability and interfacial influence will be effective
on the performance of surfactant. The particle wettability rises
with increasing particle-particle interactions. Therefore, SSL will
have a better performance in the dispersion of nanoparticles.
3.2. Thermal properties
The DSC thermograms of the TiO2/paraffin composites with and
without the surfactant have been illustrated in Figs. 3 and 4. As can
be seen, with the addition of nanoparticles to paraffin for both ser-
ies, with and without the surfactant, the phase change behavior of
samples was similar, both presenting two fusion peaks [20].
The reported melting temperature in this work was the temper-
ature corresponding to the intersection of the tangent, and the left
leg of the DSC curve. Fig. 5 shows the variation in the melting tem-
perature of the paraffin with different mass ratios of the nanopar-
ticles, in the presence and absence of the surfactant. For both
series, the melting temperature was decreased with the mass ratio
 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352 349

Fig. 3. DSC curves of the TiO2/paraffin composites without SSL. Fig. 6. The latent heat changes of TiO2/paraffin composites with different mass
ratio of TiO2 nanoparticles with and without the SSL.

and without SSL surfactant. By increasing the mass ratio of

nanoparticles up to 1 wt% for nanocomposites without the surfac-
tant and 3 wt% for samples with the surfactant, the latent heat
value was enhanced.
Adding nanoparticles to the paraffin could increase the interac-
tion between the paraffin molecules and the nanoparticles, result-
ing in the enhancement of the latent heat capacity of the
nanocomposite. When the dispersion of nanoparticles in the paraf-
fin matrix was more uniform, the improvement in the latent heat
could be higher. The samples prepared with the surfactant showed
a maximum latent heat at the higher mass ratio of nanoparticles
compared with the nanocomposite without surfactant. However,
further increase of nanoparticles could be followed by replacing
Fig. 4. DSC curves of the TiO2/paraffin composites with SSL.
the paraffin molecules with nanoparticles and absorbing more
energy during the melting process of composites [16]. Therefore,
the latent heat capacity of nanocomposites was decreased.

3.3. Thermal conductivity of the TiO2/paraffin composites

Thermal conductivity plays an effective role in the rate of the

energy storage or release for both solid and liquid phases. The ther-
mal conductivity for the pure paraffin and TiO2/paraffin compos-
ites, with and without the surfactant in a liquid state (at 70 °C),
have been shown in the Fig. 7.
It can be seen that the thermal conductivity of the composites
was increased with increasing the mass ratio of TiO2 nanoparticle
due to the very high thermal conductivity of TiO2, as compared
to paraffin. The presence of the SSL as a surfactant in the compos-
ites led to the more thermal conductivity.

Fig. 5. Melting temperature of TiO2/paraffin versus mass ratio of the TiO2

nanoparticles with and without surfactant.

of the nanoparticles. But, by increasing the mass ratio of the

nanoparticles from an optimal amount, the melting temperature
started to increase.
The optimal mass ratio of the nanoparticles was seen in 1wt%
for samples without surfactant. Similar results have been reported
by Wang et al. [16]. Adding SSL as a surfactant to the composite
caused to increasing the optimal mass ratio of the nanoparticles
to 3wt% due to uniform dispersion of nanoparticles in the matrix
and stabilization of composite. Adding nanoparticles more than
3wt% led to increasing the possibility of the aggregation of the par-
ticles and reduction of the interaction between the paraffin mole-
cules and the nanoparticles. Therefore, the melting point was
increased.
Fig. 6 illustrates the variation of the latent heat of TiO2/paraffin
Fig. 7. Thermal conductivity of nanocomposites versus different TiO2 mass ratio in
composites with different mass ratios of TiO2 nanoparticles, with presence and absence of SSL surfactant.
350 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352

Table 1
Comparison between the results of thermal conductivity enhancement in this study and the previous studies.

Author PCM type Nano particle Surfactants Thermal conductivity enhancement

Jiang et al. Paraffin Al2O3 – Thermal conductivity increasing by 27% using 16 wt% nano particle in the solid
[21] state
Ho et al. [18] Paraffin Al2O3 Non-ionic The thermal conductivity increasing by 2% and 6% respectively, using 5 wt.% and
surfactant 10 wt.% of nanoparticles in the solid state
Nourani et al. Paraffin Al2O3 SSL The thermal conductivity enhancement ratios for the sample containing 10.0 wt.
[19] % nano-Al2O3 were 31% and 13% in the solid and liquid states, respectively
Shi et al. [22] Paraffin Graphene – Thermal conductivity increasing by 55% using 1 wt% nano particle in the liquid
nanoplatelet (GNP) state
Yu et al. [23] Paraffin GNP – Thermal conductivity increasing by 20% using 1 wt% nano particle in the liquid
state
Jeon et al. Paraffin GNP – The thermal conductivity for the sample containing 5 wt.% and 3 wt% GNP
[24] respectively, was enhanced by 101% and 76%
Zhao et al. Paraffin Halloysite nanoclay, Thermal conductivity of wax-halloysite-graphite (45/45/10%) composite showed
[25] Graphit, Carbon increased conductivity of 1.4 W/mK (3 times higher than the base wax-halloysite
nanotubes composite)
Harikrishnan Lauric acid (LA) and stearic TiO2, ZnO and CuO – Thermal conductivity increasing by 34.85%, 46.97% and 62.12% using 1 wt% TiO2,
et al. [26] acid (SA) mixture ZnO and CuO nanoparticles, respectively
composite
Chaichan Paraffin Al2O3, TiO2 – Thermal conductivity increasing by 65% and 40% using 5 wt% Al2O3 and TiO2
et al. [27] nanoparticles, respectively
This study Paraffin TiO2 SSL Thermal conductivity increasing by 49.6% and 38.8% using 4 wt% TiO2
nanoparticles, with and without the surfactant, respectively

Fig. 8. TGA thermograms of paraffin and 3 wt% of TiO2 /paraffin composites with and without SSL.

As shown in Fig. 7, an enhancement of 49.6% and 38.8% in the
thermal conductivity was found for the paraffin containing 4 wt%
of nanoparticles, with and without the surfactant, respectively.
This amount of improvement in the thermal conductivity could
be substantial when is compared to the results which were
reported by Motahar et al. [17]. They showed an enhancement of
4.5% in thermal conductivity of n-octadecane containing 4wt% tita-
nium oxide nanoparticles. The results obtained about the enhance-
ment of thermal conductivity in the present work could be made
by application of smaller particle size and an appropriate disper-
sion of nanoparticles due to a significant sonication method in
the current study. Motahar et al. [17] dispersed TiO2 nanoparticles
in n-octadecane using the ultrasonic bath without any evaluation
of dispersion quality. Table 1 shows a comparison between the
present results and the summary of the studies about the thermal
conductivity of nano-paraffin composites in recent years. Similar
results were obtained by Chaichan et al. [27]. They reported an
enhancement of 65% and 40% in thermal conductivity of paraffin
containing Al2O3 and TiO2 nanoparticles, respectively.
3.4. Thermal and structural stability of the samples
As mentioned in the previous sections, the nanocomposite of
TiO2/paraffin with 3 wt% in the presence of the surfactant showed
a more uniform dispersion of the nanoparticles, the maximum
latent heat and the appropriate melting temperature. Also, there
was an enhancement of 18.33% in the thermal conductivity, as
compared to the pure paraffin with 3 wt% mass fraction of
nanoparticles. An important question arising is whether the
obtained composites can retain their thermal and structural stabil-
ity in consecutive thermal cycles.
Fig. 8 compares the behavior of the thermal degradation of the
pure paraffin and the 3wt% TiO2/paraffin composites in presence
and absence of SSL. According to TGA thermograms, the pure paraf-
fin, TiO2/paraffin composite and TiO2/paraffin/SSL composite
showed the weight reduction of about 91.64%, 92.56% and
87.11%, respectively, in 217–385 °C temperature range. In the other
words, mass reduction of nanoparticles/paraffin/SSL composite
was less than other samples in the same temperature range. There-
fore, the thermal stability of the nanoparticles/paraffin/SSL com-
posite was improved, as compared to pure paraffin and the
nanoparticles/paraffin composite with 3wt% of nanoparticles.
In the case of TiO2/paraffin composite without SSL, due to non-
uniform distribution of nanoparticles in the paraffin matrix, as
clearly shown in FE-SEM micrographs (Fig. 1), the structural
arrangement of the paraffin somewhat was disturbed by nanopar-
ticles staying among paraffin molecules. It could be postulated that
the inappropriate distribution of nanoparticles caused the reduc-
 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352 351

Table 2
Melting temperature (Tm) and latent heat (Ls) of the phase change materials composites after thermal cycles.

Samples Cycle No.

0 10 20 30 40 50 60 70 80 DTm (0–80)
Melting temperature (Tm) after the thermal cycles (°C)
Paraffin 58.9 58.8 58.54 58.21 57.92 57.78 57.31 56.62 56.31 2.59
Paraffin + 3 wt% TiO2 60.64 60.59 60.56 60.51 60.2 59.71 59.85 58.51 58.34 2.3
Paraffin + 3 wt% TiO2 + SSL 56 55.86 55.65 55.71 55.34 55.11 54.96 54.87 54.82 1.18
Latent heat (Ls) after the thermal cycles (J/g)
0 10 20 30 40 50 60 70 80 DLs (0–80)
Paraffin 137.8 137.75 137.6 137.1 136.61 136.25 135.87 135.55 135.61 2.19
Paraffin + 3 wt% TiO2 136.4 136.17 135.5 135.42 135.3 135 134.94 134.88 134.71 1.69
Paraffin + 3 wt% TiO2 + SSL 167 166.91 166.82 166.64 166.55 166.32 166.19 166.11 166.05 0.95

Table 3
Thermal conductivity of the phase change materials composites after thermal cycles.

Samples Cycle No.

0 10 20 30 40 50 60 70 80 Dk (0–80)
Thermal conductivity after the thermal cycles (W/m °C)
Paraffin 0.147 0.146 0.141 0.139 0.137 0.124 0.116 0.086 0.08 0.067
Paraffin + 3 wt% TiO2 0.18 0.18 0.176 0.173 0.168 0.161 0.147 0.139 0.131 0.049
Paraffin + 3 wt% TiO2 + SSL 0.195 0.195 0.192 0.188 0.187 0.181 0.170 0.162 0.143 0.052

Fig. 9. FE-SEM images of (a) 3 wt% of TiO2/paraffin/ (b) 3 wt% of TiO2/paraffin/SSL after 80 thermal cycles.

tion of the thermal stability of the TiO2/paraffin composite, while
adding SSL to this structure resulted in the uniform dispersion of
the nanoparticles in the paraffin matrix (see Fig. 1-B) and the
enhancement of the interactions between paraffin molecules with
nanoparticles and together.
The maximum degradation rate in the pure paraffin, the
nanoparticles/paraffin/SSL composite with 3 wt% nanoparticles
and the nanoparticles/paraffin composite with 3 wt% occurred at
temperature of about 321.42, 323.87 and 324.12 °C, respectively.
The thermal stability of the nanoparticles/paraffin composite
and the effect of the presence of the SSL on the stability of the sam-
ple were evaluated by measuring the melting temperature and
latent heat after several heating and cooling cycles. For this pur-
pose, the melting temperature (Tm) and the latent heat (Ls) of the
3 wt% TiO2/paraffin composite with and without surfactant were
measured after several thermal cycles by DSC analysis. The results
are summarized in Table 2.
The results showed that the amount of change in the melting
temperature for the pure paraffin, nanoparticle/paraffin and
nanoparticle/paraffin/SSL after 80 thermal cycles was 2.59, 2.3
and 1.18 °C, respectively. Also, the amount of change in the latent
heat for these samples after 80 thermal cycles was 2.19, 1.16
and 0.95 J/g, respectively.
The changes in the melting temperature and the latent heat of
the samples after the 80 thermal cycles showed that the presence
of the nanoparticles in the PCM made lower changes in the melting
temperature and the latent heat due to the interaction between
paraffin molecules and nanoparticles. For TiO2/paraffin/SSL com-
posite, the attraction between the organic functional groups of
paraffin and SSL cause to increase in the interactions between
paraffin molecules and nanoparticles due to better dispersion
could make higher stability and lower changes in the thermal char-
acteristics of paraffin after several thermal cycles.
The thermal conductivity of nanocomposite samples with 3wt%
nanoparicles after several melting/freezing cycles in Table 3 shows
thermal conductivity of the nanocomposites has reached the initial
thermal conductivity of the pure paraffin (0.147 W/m °C), after 80
thermal cycles. While the thermal conductivity of pure paraffin has
352 S. Sami, N. Etesami / Applied Thermal Engineering 124 (2017) 346–352
sharply fallen to around half of 0.147 W/m °C after 80 thermal
cycles.
According to the last column of Table 3, the thermal conductiv-
ity change (Dk) of the nanocomposites after 80 thermal cycles
were less than that of pure paraffin due to dispersion of TiO2
nanoparticles. This showed that the presence of nanoparticles in
PCMs results in reduction of decreasing rate of the thermal conduc-
tivity of PCM nanocomposites in several thermal cycles.
FE-SEM images after 80 thermal cycles have been illustrated in
Fig. 9. Comparing these images with their corresponding ones in
Fig. 1 showed that although the dispersion of nanoparticles in
the samples was decreased somewhat, but the distribution of
nanoparticles in the sample with the SSL was still better than that
in the sample without the surfactant. Thus the conductivity of the
sample with the SSL could be more than that of the sample without
the SSL.
4. Conclusions
The effect of the sodium stearoyl lactylate (SSL) as a surfactant
in the production of the stabilized paraffin/TiO2 composites was
evaluated. Thermal characteristics and stability of the prepared
composites after the thermal cycles were studied. Electron micro-
scopy images showed that the presence of SSL makes a uniform
dispersion of TiO2 nanoparticles in paraffin matrix. DSC analysis
showed that the lowest melting temperature and the maximum
latent heat capacity for nanocomposite samples without SSL occurs
in 1 wt%, while for nanocomposite with SSL, this occurs in 3 wt%.
The thermal conductivity of the liquid TiO2/paraffin composites
was higher for samples with surfactant owing to more uniform dis-
persion. TGA analysis showed the higher thermal stability for
TiO2/paraffin/SSL composite compared with pure paraffin and
TiO2/paraffin composite. The results showed that adding nanopar-
ticles to PCM causes to reduction of the variations in the melting
temperature and the latent heat of samples in several thermal
cycles. Thermal conductivity coefficient of the nanocomposites is
approach to the primary thermal conductivity coefficient of the
pure paraffin (0.147 W/m °C) after 80 thermal cycles, while the
thermal conductivity of pure paraffin was dropped sharply
(0.08 J/g), after 80 thermal cycles. Comparing of FE-SEM images
before and after 80 thermal cycles shows that the dispersion of
nanoparticles in the nanocomposites somewhat was decreased.
But the distribution of nanoparticles in the nanocomposite with
SSL surfactant was still better than that of the nanocomposite
without that. It is postulated that the presence of SSL causes to
delay in instability and improve the properties of samples. The
thermal conductivity of the nanocomposite with SSL was more
than that of the nanocomposite without SSL, after thermal cycles.
References
[1] B. Zalba, J.M. Marin, L.F. Cabeza, H. Mehling, Review on thermal energy storage
with phase change: materials, heat transfer analysis and applications, Appl.
Therm. Eng. 23 (2003) 251–283.
[2] E.B.S. Mettawee, G.M.R. Assassa, Thermal conductivity enhancement in a latent
heat storage system, Solar Energy 81 (2007) 839–845.
[3] A. Tinti, A. Tarzia, A. Passaro, R. Angiuli, Thermographic analysis of
polyurethane foams integrated with phase change materials designed for
dynamic thermal insulation in refrigerated transport, Appl. Therm. Eng. 70
(2014) 201–210.
[4] H. Fauzi, H.S.C. Metselaar, T.M.I. Mahlia, M. Silakhori, H.C. Ong, Thermal
characteristic reliability of fatty acid binary mixtures as phase change
materials (PCMs) for thermal energy storage applications, Appl. Therm. Eng.
80 (2015) 127–131.
[5] A. Babapoor, M. Azizi, G. Karimi, Thermal management of a Li-ion battery using
carbon fiber-PCM composites, Appl. Therm. Eng. 82 (2015) 281–290.
[6] S. Harish, D. Orejon, Y. Takata, M. Kohno, Thermal conductivity enhancement
of lauric acid phase change nanocomposite with graphene nanoplatelets, Appl.
Therm. Eng. 80 (2015) 205–211.
[7] Y. Li, B. Guo, G. Huang, S. Kubo, P. Shu, Characterization and thermal
performance of nitrate mixture/SiC ceramic honeycomb composite phase
change materials for thermal energy storage, Appl. Therm. Eng. 81 (2015) 193–
197.
[8] H.K. Shin, M. Park, H.Y. Kim, S.J. Park, Thermal property and latent heat energy
storage behavior of sodium acetate trihydrate composites containing
expanded graphite and carboxymethyl cellulose for phase change materials,
Appl. Therm. Eng. 75 (2015) 978–983.
[9] A. Babapoor, G. Karimi, Thermal properties measurement and heat storage
analysis of paraffin-nanoparticles composites phase change material:
comparison and optimization, Appl. Therm. Eng. 90 (2015) 945–951.
[10] X.L. Zhang, X.D. Chen, Q.Z. Zhao, L. Ding, The research on the dispersion effect
improvement for nano-copper in erythritol, J. Mater. Res. Innov. 19 (1) (2015)
9–13.
[11] N. Sahan, M. Fois, H. Paksoy, Improving thermal conductivity phase change
materials-A study of paraffin nanomagnetite composites, Solar Energy Mater.
Solar Cells 137 (2015) 61–67.
[12] C.H. Li, G.P. Peterson, Experimental investigation of temperature and volume
fraction variations on the effective thermal conductivity of nanoparticle
suspensions (nanofluids), J. Appl. Phys. 99 (2008) 084314–084318.
[13] H.A. Mintsa, G. Roy, C.T. Nguyen, D. Doucet, New temperature dependent
thermal conductivity data for water-based nanofluids, Int. J. Therm. Sci. 48
(2009) 363–371.
[14] T.P. Teng, C.C. Yu, Characteristics of phase-change materials containing oxide
nano-additives for thermal storage, Nanoscale Res. Lett. 7 (2012) 611 (10pp).
[15] S. Harikrishnan, S. Kalaiselvam, Experimental investigation of solidification
and melting characteristics of nanofluid as a PCM for solar water heating
system, Int. J. Emer. Technol. Adv. Eng. 3 (2013) 628–635.
[16] J. Wang, H. Xie, Z. Guo, L. Guan, Y. Li, Improved thermal properties of paraffin
wax by the addition of TiO2 nanoparticles, Appl. Therm. Eng. 73 (2014) 1541–
1547.
[17] S. Motahar, N. Nikkam, A.A. Alemrajabi, R. Khodabandeh, M.S. Toprak, M.
Muhammed, Experimental investigation on thermal and rheological
properties of n-octadecane with dispersed TiO2 nanoparticles, Int. Commun.
Heat and Mass Transfer 59 (2014) 68–74.
[18] C.J. Ho, J.Y. Gao, Preparation and thermophysical properties of nanoparticle-in-
paraffin emulsion as phase change material, Int. Commun. Heat and Mass
Transfer 36 (2009) 467–470.
[19] M. Nourani, N. Hamdami, J. Keramat, A. Moheb, M. Shahedi, Thermal behavior
of paraffin-nano-Al2O3 stabilized by sodium stearoyl lactylate as a stable
phase change material with high thermal conductivity, Renew. Energy 88
(2016) 474–482.
[20] M. Mehrali, S. Tahan Latibari, M. Mehrali, H.S.C. Metselaar, M. Silakhori, Shape-
stabilized phase change materials with high thermal conductivity based on
paraffin/graphene oxide composite, Energy Convers. Manage. 67 (2013) 275–
282.
[21] X. Jiang, R. Luo, F. Peng, Y. Fang, T. Akiyama, S. Wang, Synthesis,
characterization and thermal properties of paraffin microcapsules modified
with nano-Al2O3, Appl. Energy 137 (2015) 731–737.
[22] J.N. Shi, M.D. Ger, Y.M. Liu, Y.C. Fan, N.T. Wen, C.K. Lin, N.W. Pu, Improving the
thermal conductivity and shape-stabilization of phase change materials using
nanographite additives, Carbon 51 (2013) 365–372.
[23] Z.T. Yu, X. Fang, L.W. Fan, X. Wang, Y.Q. Xiao, Y. Zeng, X. Xu, Y.C. Hu, K.F. Cen,
Increased thermal conductivity of liquid paraffin-based suspensions in the
presence of carbon nano-additives of various sizes and shapes, Carbon 53
(2013) 277–285.
[24] J. Jeon, S.G. Jeong, J.H. Lee, J. Seo, S. Kim, High thermal performance composite
PCMs loading xGnP for application to building using radiant floor heating
system, Solar Energy Mater Solar Cells 101 (2012) 51–56.
[25] Y. Zhao, S. Thapa, L. Weiss, Y. Lvov, Phase change insulation for energy
efficiency based on wax-halloysite composites, in: 2nd international
conference on structural nano composites 20-21 May 2014, Madrid, Spain.
[26] S. Harikrishnan, M. Deenadhayalan, S. Kalaiselvam, Experimental investigation
of solidification and melting characteristics of composite PCMs for building
heating application, Energy Convers Manage. 86 (2014) 864–872.
[27] M.T. Chaichan, S.H. Kamel, A.M.N.M. Al-Ajeely, Thermal conductivity
enhancement by using nano-material in phase change material for latent
heat thermal energy storage systems, SAUSSUREA 5 (2015) 48–55.