Received: 5 April 2021 Revised: 27 June 2021
DOI: 10.1002/er.7138
RESEARCH ARTICLE
Fabrication and experimental investigation of
microencapsulated eutectic phase change
material-integrated polyurethane sandwich tin panel
composite for thermal energy storage in buildings
Amol Tarachand Naikwadi
Department of Polymer and Surface
Engineering, Institute of Chemical
Technology, Mumbai, India
Correspondence
Asit B. Samui, Institute of Chemical
Technology, Matunga (E), Mumbai
400019, India.
Email: absamui@gmail.com
Prakash A. Mahanwar, Institute of
Chemical Technology, Mumbai 400019,
India.
Email: pa.mahanwar@ictmumbai.edu.in
Funding information
Defense Research and Development
Organization (DRDO), Grant/Award
Number: NRB/4003/PG/387
Int J Energy Res. 2021;1–12.
Accepted: 21 July 2021
| Asit B. Samui | Prakash A. Mahanwar
Summary
House sheds, constructed of aluminium tin alloy, are likely to increase the
inside temperature of the room during the day, which in turn causes higher
electricity usage. This temperature rise can be minimized by using foam
insulation. In the present study, polyurethane foam incorporated with
microencapsulated phase change material and sandwiched between tin
panels were prepared for studying their performance towards building
application. In-situ polymerization technique was adopted to synthesize
melamine-formaldehyde (MF) encapsulated lauric acid-palmitic acid eutec-
tic (LA-PA) phase change material (PCM). The rigid polyurethane foam (R-
PUF) composites, sandwiched between two tin metal panels, were gener-
ally used as building walls and roofing material. Thermal energy transfer
rate analysis was used to check the time needed to reach the set tempera-
ture of the PU sandwich tin panels with and without MF/LA-PA microcap-
sules. Morphology, thermal properties, and structural characterization
were done using scanning electron microscopy (SEM), polarised optical
microscopy (POM), differential scanning calorimetry (DSC), ther-
mogravimetric analysis (TGA), and Fourier transform infrared spectros-
copy (FTIR). The melting enthalpy of the MF/LA-PA microcapsule was
found to be 131.57 J/g. The thermal stability of the LA-PA PCM was
increased after microencapsulation. By using a 40 wt% MF/LA-PA micro-
capsule loaded R-PUF between one compartment with heat source and the
other without a heat source. Increased resistance towards the temperature
rise of the compartment without a heat source was observed. This perfor-
mance indicated significant thermal energy storage ability for building
applications.
KEYWORDS
building application, LA-PA eutectic mixture, melamine formaldehyde microcapsules, PU
sandwich tin panels, solar thermal energy storage
wileyonlinelibrary.com/journal/er © 2021 John Wiley & Sons Ltd. 1
2 NAIKWADI ET AL.
1 | INTRODUCTION
In recent years, rapid changes in buildings and
manufacturing have increased carbon emissions
and environmental temperature. Thermal energy storage
can be an essential solution that lowers carbon emissions
and contains temperature rise. In most Asian countries,
house sheds are made of aluminium tin alloy, which, as a
metal, can increase the inside temperature of the building
during the day. This temperature increase can be mini-
mized by the incorporation of PCM in polyurethane
foam. Organic, inorganic mixtures, and eutectic mixtures
are commonly used as PCM.1 However, the applications
in which the PCMs are used may be adversely affected
due to the leakage of unconstrained PCM during thermal
cycles of melting and solidification. Therefore, the micro-
encapsulation technique of PCM is considered one of the
appropriate solutions for containing the PCM.2,3 Various
other approaches are used to avoid leakage, the most
notable of which is form stabilization.4,5 Among other
advantages, the PCM microencapsulation can prevent
PCM leakage and isolation from the environment to
avoid any chemical reactions with other components.6-8
Microencapsulation can be achieved using various
methods, including physical and chemical processes such
as spray drying,9 fluidized bed,10 coacervation,11 emul-
sion polymerization,12 suspension polymerization,13 in-
situ polymerization,14 and interfacial polymerization,15
respectively. These facile use characteristics of these
materials have attracted interest from numerous sectors,
such as solar energy,16,17 energy-saving building,18,19
thermoregulated textiles,20 thermal storage,21,22 and cold
energy storage.23 The polymeric shell materials comprise
polymethyl methacrylate,13 polystyrene,24 urea-
25 26,27
formaldehyde, melamine-formaldehyde, and biode-
gradable polymers such as Gum Arabic,28 and so on. MF
polymer shell is used in several research studies because
of its thermochemical stability.29 Also, the faster reaction
rate, higher polymerization yield, and non-reactivity to
PCMs and the environment promote the use of MF poly-
mer for microencapsulation.30,31
Few fatty acids and their binary eutectic combina-
tions were microencapsulated and studied for their ther-
mal management ability. Fatty acids do not suffer from
deficiencies, such as supercooling and phase separation.
Other advantages of fatty acids are a favorable phase
transition range for low to high thermal energy applica-
tions, ease of availability, and low cost.32 Polyurethane
foams are known for their insulating properties, reduced
thermal conductivity, and light weight, which are used
for thermal insulation in buildings. Previously, studies on
PCMs incorporated into direct PU foam have shown cer-
tain disadvantages, such as leakage from the porous
structure of the foam.33 Microencapsulated PCM-
integrated PU foams have been studied earlier in various
applications such as clothing, buildings,34 medical
devices, solar energy storage,35 thermal regulation,36 heat
insulating material, and so on., for their thermal energy
conservation. Expanded polystyrene foams have been
studied for building applications due to their low cost,
better indoor quality, and insulating properties.37,38 How-
ever, expanded polystyrene foams have several draw-
backs such as self-ignition at specific temperature
conditions, damage from ultraviolet radiation, and poor
resistance to organic solvents, limiting their use in out-
door applications.39
The main benefit of integrating PCM thermal energy
storage units with building technologies includes both
their high storage capacities at a short temperature span
and increased energy efficiency in new and refurbished
buildings in combination with other active systems.
Therefore, several researchers have studied the incorpo-
ration of PCM in building applications, such as wallboard
building,40-42 building envelope,43-47 wall coatings,48 con-
crete materials,49-51 bricks,52-54 and building roof for
reducing the energy requirements.55
In the present work, rigid polyurethane composites
sandwiched between tin panels are prepared by integrat-
ing MF/LA-PA microcapsules into polyurethane foam.
Melamine formaldehyde shells are chemically and
mechanically stable, have a long shelf life, are compatible
with a wide range of polymeric matrixes, and maintain
inertness towards PCM material. Further, the synthesis
strategy is compatible with the microencapsulation pro-
cess. The present work aims at keeping the houses and
buildings at comfortable temperatures by incorporating
the MF/LA-PA microcapsules into the rigid polyure-
thane foam sandwiched between tin panels. The pur-
pose of the study was to modify the polyurethane foam
sandwiched tin panel by incorporating PCM microcap-
sules to regulate heat accumulation in building applica-
tions within the temperature range of 25 C to 40 C.
Attempts have been made to keep the houses and build-
ings at optimum temperatures by incorporating the
MF/LA-PA microcapsules into the rigid polyurethane
foam sandwiched between tin panels. LA-PA eutectic
PCMs provide greater versatility with rigid polyure-
thane foam to regulate the operating temperature with-
out a supercooling effect. The morphological and
thermal properties of MF/LA-PA microcapsule and R-
PUFs composites were determined by using SEM and
DSC. Furthermore, a thermal cycling experiment has
been conducted to measure the long-term effectiveness
of R-PUF composites. Thermal energy transfer rate of
the sandwiched R-PUFs composites have been studied
in detail with varying thickness.
NAIKWADI ET AL.
2 | MATERIALS AND METHODS
2.1 | Materials
Lauric acid (LA) and palmitic acid (PA), used as PCM,
were supplied by Sigma-Aldrich, India. In addition, the
monomers used are melamine and formaldehyde and
procured from Loba industries, Mumbai, India. Sodium
lauryl suphate (SLS) was used as anionic surfactant and
provided by S.D. Fine Chemicals, India. Triethylamine
(TEA) and Acetic acid (AA), obtained from S.D. Fine
Chemicals, India, were used for pH adjustment. Polyester
polyol and polymeric methylene diphenyl diisocyanate
(MDI) were received from DOW Chemical International
Pvt. Ltd. Juinagar, India.
2.2 | Synthesis of LA-PA eutectic
mixture, MF prepolymer and MF/LA-PA
microcapsule
The LA-PA eutectic mixture has been prepared by follow-
ing the method of Schroder.27,56 The eutectic mixture was
a combination of 77 wt% of LA PCM and 23 wt% of PA
PCM. The eutectic mixture was prepared by mixing the
molten LA PCM with PA PCM for 45 minutes at 70 C.
The eutectic mixture was then allowed to cool to room
temperature before being tested for phase change
properties.
The MF prepolymer was prepared in a 100 mL bea-
ker. In a 100 mL beaker, 50 mL water, 13 mL formalde-
hyde (37%) solution, and 5 g melamine were mixed at
80 C. The mixing was continued until the milky white
liquid became transparent. TEA was then used to adjust
the pH of the MF prepolymer solution to 9.
The in-situ polymerization method was used to syn-
thesize MF/LA-PA microcapsules. The microencapsula-
tion process has been conducted in a 500 mL four-neck
reaction kettle outfitted with a condenser, dropping fun-
nel, stirrer, and temperature controller. In a 500 mL bea-
ker, a eutectic PCM emulsion was formed. For the LA-
PA emulsion, 100 mL of water, 14 g of LA-PA eutectic
PCM, and 0.75 g of SLS have been combined and trans-
ferred to the four-neck reaction kettle. The reaction kettle
was kept in a water thermostat bath at 80 C. The pre-
pared LA-PA emulsion was then agitated at 700 rpm
using a mechanical stirrer, and the emulsion pH was
reduced to 3 after 15 minutes using AA. The MF pre-
polymer was then added dropwise to the eutectic emul-
sion for 1 hour under constant stirring, and the reaction
was then continued for a further 2 hours. After 3 hours of
the reaction, the pH was adjusted to 9 using TEA. The
synthesized microencapsulated emulsion was then
3
centrifuged and dried at 50 C for 1 day to obtain the final
dried MF/LA-PA microcapsules.
2.3 | Fabrication of MicroPCM3
incorporated rigid polyurethane (R-
PU) foam
Polyurethane sandwich tin metal panels have been devel-
oped with and without MF/LA-PA microcapsules, as
shown in Figure 1. The R-PUF composites were produced
using polyester polyol, MDI, water, triton-x 100, and cata-
lyst. The foam was prepared by mixing 130 parts of MDI
into 100 parts of polyol. To the polyester polyol, the
MF/LA-PA microcapsules were added at 0, 10, 15, 20,
30, and 40 wt% with respect to the former, and the mix-
ture was agitated at 700 rpm. MDI was then mixed with
polyester polyol-MF/LA-PA mixture and stirred at
1500 rpm. The mixture was then poured into the galva-
nized tin mould under the fume hood. Prepared foam
composites were then allowed to be post-cured for
24 hours at room temperature and stored at controlled
temperature prior to testing for thermal properties. The
foam composites are titled R-PUF0, R-PUF1, R-PUF2, R-
PUF3, and R-PUF4 for 0, 10, 20, 30, and 40 wt% micro-
capsule loading.
2.4 | Characterization
FTIR-Bruker was employed in ATR mode to identify the
chemical structure of the LA-PA eutectic PCM and
MF/LA-PA microcapsules. At the beginning of the mea-
surement, a blank scan was performed to correct the
ambient noise. Thermogravimetric analysis (TGA Perkin
Elmer-Pyris 1) was utilized to measure thermal degrada-
tion temperatures of LA-PA eutectic PCM, MF polymer,
and MF/LA-PA microcapsules. The temperature range
for TGA analysis was set from 30 C to 500 C with a nitro-
gen gas flow rate of 20 mL/min. The differential scanning
calorimetry (DSC-TA Q100) has been utilized to deter-
mine the melting temperatures, crystallization tempera-
tures, melting enthalpy, and crystallization enthalpy with
a heating and cooling cycle of 5 C/min. Polarized optical
microscopy (POM Olympus-BX41) has been employed to
detect the morphology of the microcapsule. Scanning
electron microscopy (SEM-Hitachi S-4700) examined the
surface morphology and shell shapes of the MF/LA-AP
microcapsules and their distribution in foam matrix. The
heat energy transfer investigation of the R-PUF compos-
ites panel with varying concentrations of microcapsules
has been completed using a customized thermal energy
transfer instrument. The time needed by a compartment
4 NAIKWADI ET AL.

FIGURE 1 Process flow diagram for making a eutectic mixture, microcapsule synthesis, and foam fabrication

adjacent to a hot compartment and separated by PCM

loaded sandwich tin panel to reach a set temperature
range of 45 C was recorded by a thermocouple (TB).
Heating and cooling ramps were set at 20 C/h.

3 | R ESULTS A ND DISCUSSIONS

3.1 | FTIR characterization of LA-PA

PCM and microcapsule

Figure 2 demonstrates the FTIR spectra of pure LA-PA

PCM and MF/LA-PA microcapsules. In the pure LA-PA-
eutectic PCM spectra, the peaks at 2913 and 2847 cm 1
indicate symmetric and asymmetric stretching vibrations of
alkyl C H, and the peak at 1432 cm 1 is assigned to plane
bending of the CH. The peak appearing at 1700 cm 1 repre- F I G U R E 2 FTIR spectra of LA-PA PCM and MF/LA-PA
sents the stretching vibration of a COOH group. In the microcapsules

MF/LA-PA microcapsule, the presence of C N component

is indicated by the band value at 1550 cm 1. The peaks
at 1470 and 1365 cm 1 correspond to C H bending vibra-
tions of methylene linkages. The spectrum observed at
3450 cm 1 is due to the stretching of N H group of the MF
polymer shell. Thus, the above-mentioned stretching and
bending vibration peaks of the LA-PA eutectic PCM are
found in the MF/LA-PA microcapsules. This ensures effec-
tive encapsulation and no structural alteration of the LA-
PA eutectic PCM after encapsulation.
3.2 | Thermal properties of eutectic
PCM, microcapsule
Figure 3 demonstrates the phase change properties of the
pure LA-PA PCM and the MF/LA-PA microcapsule. Pure
LA-PA PCM undergoes a phase transition from solid-
state to liquid state at 36 C during heating with the latent
heat of melting of 171.73 J/g and solidifies at 30 C during
NAIKWADI ET AL.
F I G U R E 3 DSC curves of pure LA-PA eutectic PCM and
MF/LA-PA microcapsule
cooling with the latent heat of crystallization of 170.97 J/
g. The MF/LA-PA microcapsules exhibit endothermic
and exothermic peaks at 35.81 C and 29.97 C, respec-
tively. The melting enthalpy and crystallization enthalpy
of the MF/LA-PA microcapsules are found to be
131.37 J/g and 130.95 J/g, respectively. The DSC values
indicate that the phase change temperatures of the LA-
PA eutectic PCM and MF/LA-PA microcapsules are simi-
lar. It ensures that the melting and crystallization of the
eutectic PCM are not obstructed even after the MF poly-
mer shell has constrained them. This confirms that there
is no chemical modification of LA-PA PCM after micro-
encapsulation. It is found that the crystallisation enthalpy
and melting enthalpy of MF/LA-PA capsules are
decreased by 23.50% and 23.40% with respect to the pure
LA-PA PCM. This is due to a reduction in the mass % of
LA/PA PCM because of the presence of MF polymer
shell. The encapsulation ratio is calculated to be 76.50%.
Based on the results of thermal energy storage, MF/LA-
PA is selected as the appropriate microcapsule to be inte-
grated for building application in the PU foam.
3.3 | Thermal stability of eutectic PCM,
microcapsule, and MF polymer shell
Figure 4 presents the TGA curves for LA-PA PCM, MF
polymer, and MF/LA-PA microcapsules. Table 1 contains
different thermal parameters, such as maximum weight
loss temperature, one-step and two-step degradation tem-
peratures, and char yield. It can be seen from the curve
that the LA-PA eutectic mixtures decompose in a single
step. In the LA-PA PCM, degradation starts at
5
F I G U R E 4 TGA (a) analysis of LA-PA PCM, MF/LA-PA
microcapsule, and MF polymer
approximately 195 C and completing its weight loss at
around 230 C with a char content of 0.15%. Similarly, an
initial weight loss of MF polymer shell material is observed
around 381 C and ended around 473 C with a char con-
tent of 12.3%. The MF/LA-PA microcapsule has a two-step
decomposition with onset degradation temperature of the
first step at 235 C and ended at 305 C, which is associated
with the evaporation of the LA-PA eutectic in the micro-
capsule. The rate of weight loss of the MF/LA-PA micro-
capsule is found to be lower than that of the LA-PA PCM.
The second step degradation of the microcapsules begins
at 370 C and is completed at 440 C, which refers to the
degradation of the MF shell material. After degradation of
the microcapsule, the char content remained at 7.2%. The
results show a substantial increase in the thermal stability
of the LA-PA PCM after microencapsulation due to the
protective layer of the MF shell.
3.4 | Morphology of MF/LA-PA
microcapsule
Figure 5 shows the SEM micrographs of MF encapsulated
LA-PA PCM. The shape, compact design, and shell tex-
ture of the microspheres were investigated using SEM
analysis. It is seen from Figure 5A that MF/LA-PA micro-
capsule has a globular shape with capsule diameter in
the range of 5 to 30 μm. SEM micrographs illustrated the
globular and regular shape of the MF/LA-PA microcap-
sules with a compact design. Figure 5B represents the
MF polymer shell surface at high magnification.
The shell morphology is observed to be rough, originat-
ing from the accumulation of colloidal particles due to
electrostatic interaction between the positive MF polymer
shell and the negatively charged colloidal particles. This
shell roughness can be reduced by conducting after
6 NAIKWADI ET AL.

washing of the microcapsules. It is also found that higher
agitation does not lead to shell breaking.
3.5 | POM analysis of MF/LA-PA
microcapsule
POM analysis was done to get the morphological character-
istics of the MF/LA-PA microcapsules. POM micrographs
indicate that the capsules are globular in shape and uniform
in size (Figure 6A,B). The capsule diameter is found to be
in the range of 5 to 30 μm, which is comparable to that
observed in SEM analysis. The spherical morphology and
the compactness are also confirmed. Furthermore, no leak-
age of the LA-PA PCM was observed in the microcapsule
during heating above the melting temperature. This con-
firms the ability of the MF polymer shell to retain the LA-
PA PCM in both the solid and the liquid state.

TABLE 1 Thermal stability of eutectic PCM, MF polymer and MF/LA-PA microcapsule

First step degradation Second step degradation

Sample Onset ( C) End ( C) Onset ( C) End ( C) Char yield (%)

LA-PA Eutectic PCM 195 230 - - 0.15
MF polymer shell 381 473 - - 12.3
MF/LA-PA microcapsule 235 305 370 440 7.2

FIGURE 5 Morphological analysis of MF/LA-PA microcapsules (A) 500 magnification and (B) 100 magnification

F I G U R E 6 POM micrographs of
MF/LA-PA microcapsules
NAIKWADI ET AL. 7

3.6 | Thermal properties of R-PUF composites are not substantially different (1 ± 0.2 C)
composites from that of the MF/LA-PA microcapsule and the pure
LA-PA PCM. Thermal analysis results suggest that the R-
Thermal properties of R-PUF composites are determined PUF4 composite has a capability for thermal energy stor-
by DSC study and presented in Figure 7. Phase change age applications in the building sector.
temperatures, crystallization, and melting enthalpy of R-
PUF0, R-PUF1, R-PUF2, R-PUF3, and R-PUF4 are evalu-
ated by DSC. As expected, the R-PUF0 foam composites 3.7 | Thermal energy transfer rate
do not exhibit any phase change characteristics. The
melting temperatures of the composites R-PUF1, R- The thermal energy transfer rate through the rigid poly-
PUF2, R-PUF3, and R-PUF4 are observed at 35.92 C, urethane foam composites with and without microcap-
35.71 C, 35.85 C, and 35.81 C, whereas the solidification sules was evaluated by employing customized thermal
temperatures are detected at 29.62 C, 29.91 C, 29.87 C, energy transfer rate measuring instruments, as shown in
and 29.93 C, respectively. The melting and crystallization Figure 8. In this experiment, the temperature profiles
temperatures of the R-PUF composites are similar to that noted by the TB thermocouple are plotted against time, as
of the LA-PA PCM and MF/LA-PA microcapsules. The shown in Figure 9. The primary goal of the analysis was
melting enthalpies of the composites R-PUF1, R-PUF2, to determine the time required to attain set temperature
R-PUF3, and R-PUF4 are found to be 11.23, 19.51, 27.83, by a compartment adjacent to the compartment with
and 39.91 J/g, respectively. The melting enthalpy is
observed to rise with the microcapsule loading. The crys-
tallization enthalpies of the R-PUF1, R-PUF2, R-PUF3,
and R-PUF4 composites are found to be 11.81, 19.73,
27.13, and 39.59 J/g, respectively. It is observed that the
crystallization and melting enthalpies of the R-PUF4
composite are higher than those of other composites due
to higher MF/LA-PA loading but lower than those of the
pure LA-PA PCM and MF/LA-PA microcapsule.
The lower melting and crystallization enthalpy of the
composites compared to the pure LA-PA PCM and
MF/LA-PA PCM are due to the porous structure and,
more importantly, the weight addition due to the pres-
ence of the foam matrix. Further study was conducted
with R-PUF40 samples. Also, it can be noticed that the
melting and crystallization temperatures of the R-PUF FIGURE 8 Thermal energy transfer rate apparatus and model

F I G U R E 7 DSC thermograms of R-PUF composite with and F I G U R E 9 Temperature rise (Thermocouple TB) of
without MF/LA-PA microcapsules compartment adjacent to compartment with heating sorce vs time
8 NAIKWADI ET AL.
heat sources (electrical heater with a 20 C/h heating
ramp) and separated by a composite panel of 20 mm
thickness. TA thermocouple indicates the temperature of
the heated chamber, while the TB thermocouple shows
the temperature of the adjacent compartment. The tem-
perature cycle was set from 25 ± 2 C to 45 ± 2 C. The
time periods required to attain the defined equilibrium
temperature (TB thermocouple) for the R-PUF0, R-PUF1,
R-PUF2, R-PUF3, and R-PUF4 composites are 110 ± 5,
145 ± 5, 170 ± 5, 190 ± 5, and 230 ± 5 minutes, respec-
tively. It is observed that the time needed for MF/LA-PA
microcapsules loaded rigid polyurethane foam is higher
than that of foam composite without microcapsules. The
time taken by the TB thermocouple with R-PUF4 foam
composite separator to attain set temperature is 230
± 5 minutes, which is significantly higher than that of R-
PU1, R-PU2, and R-PU3 composites for obvious reason.
3.8 | Effect on thermal energy transfer
rate with varying PU sandwich tin panels
thickness
The thermal energy transfer rate panels with varying
thickness and constructed model are shown in Figure 10.
The prepared PU sandwich tin panels with varying thick-
ness were used for solar heat transfer analysis. In most
Asian countries, tin panels are typically used for roofing
and building wall materials. The structural rigidity of the
roof and wall material can be improved by using PU
sandwich tin metal sheets. Solar roof panels and PU wall
panels in sizes from 30 mm to 200 mm are commercially
available for cold room applications. We have developed
MF/LA-PA microcapsules integrated into rigid
F I G U R E 1 0 Thermal energy transfer rate panels and
constructed model
polyurethane foam composite tin panels in the present
work. The PU sandwich tin panels with a thickness of
20, 30, and 40 mm have been prepared and tested for
thermal energy transfer analysis. R-PUF4 composite with
20, 30, and 40 mm thickness show 230 ± 5, 270 ± 5, and
290 ± 5 minutes, respectively, to attain the set tempera-
ture. This indicates that with the increasing thickness of
the sandwich panel, there is an increase in the time taken
to reach the thermal equilibrium. This is due to the pres-
ence of the increasing amount of MF/LA-PA microcap-
sules in polyurethane foam and an increase in the area of
heat dissipation. The R-PUF4 composite, 20 mm thick,
demonstrated promising thermal energy storage, low-
weight, and structural rigidity.
3.9 | Thermal cycling test
Long-term applicability of the MF/LA-PA microcapsules
incorporated rigid polyurethane foam is investigated with
a number of heating and cooling cycles. R-PUF4 compos-
ite is evaluated for 1, 50, and 100 thermal cycles as it
exhibits higher melting and crystallization enthalpy com-
pared to all other R-PUFs composites. Figure 11 depicts
the phase change curves of the R-PUF4 composite for
1, 50, and 100 thermal cycles. The composite melting
temperatures at 1, 50, and 100 thermal cycles are
observed at 35.81 C, 35.57 C, and 35.71 C and the crys-
tallization temperatures at 29.93 C, 29.81 C, and
29.91 C, respectively. This indicates that the melting
and crystallization temperatures are not significantly
influenced by the number of cooling and heating cycles.
R-PUF4 composites at 1, 50, and 100 thermal cycles show
melting enthalpy of 39.91, 39.77, 39.82 J/g, and crystalli-
zation enthalpy of 39.59, 39.61, and 39.33 J/g,
FIGURE 11 Thermal cycling test of R-PUF4 composites
NAIKWADI ET AL.
FIGURE 12 SEM micrographs of (A) R-PUF0, (B) R-PUF1, (C) R-PUF2, (D) R-PUF3, and (E) R-PUF4 composites
respectively. Thus the R-PUF4 foam composite does not
exhibit any significant variations in phase change tem-
peratures and melting and crystallization enthalpies.
3.10 | Morphology of the R-PUFs
composites
The morphology of rigid polyurethane foam with and
without microcapsules is investigated by SEM analysis
and shown in Figure 12. SEM micrographs of R-PUF0, R-
PUF1, R-PUF2, R-PUF3, and R-PUF4 composites are
shown in Figure 12. Figure 12A shows that the R-PUF0
composite is a polyhedral comb-like structure with a
larger closed-cell structure. Figure 12B,C,D,E represents
the morphological features of R-PU1, R-PU2, R-PU3, and
R-PUF4 composites. It can be easily seen from the SEM
micrographs that the MF/LA-PA microcapsules are uni-
formly distributed and dispersed all over the foam cell
surface. It is observed that when the MF/LA-PA micro-
capsules are introduced during the foaming process, the
honeycomb-like closed-cell structures become smaller.
This is due to the nucleating effect of the microcap-
sule.57,58 In Figure 12B,C,D,E, it can be seen that the par-
ticles of MF/LA-PA microcapsules do not fully fill the
9
foam cells of the R-PU. Instead, they are distributed over
the outer surface of the closed cells, allowing the cell
spaces to remain free and, therefore, not adversely affect-
ing the thermal dissipation mechanism. The physical
behavior, size, and structure of R-PUF1, R-PUF2, R-
PUF3, and R-PUF4 foam composites with microcapsules
loading do not change significantly compared to the R-
PUF0 foam composite. The loading of microcapsule parti-
cles is optimized to a maximum of 40 wt% as it takes lon-
ger foaming time. It is also noted that the microcapsules
are not agglomerated during filling and have higher
efficiency.
4 | CONCLUSIONS
In this study, effective encapsulation of LA-PA was per-
formed using in-situ polymerization method. The LA-PA
eutectic combination resulted in a melting enthalpy of
171.73 J/g at a corresponding melting temperature
of 36 C. MF/LA-PA microcapsules showed 131.37 J/g
melting enthalpy, and these microcapsules were inte-
grated into rigid polyurethane foam for building applica-
tion. The SEM analysis demonstrated a spherical
morphology of microcapsules with a capsule diameter in
10
the range of 5 to 30 μm. The DSC test results revealed that
the R-PUF composite with 40 wt% microcapsule loading has
higher melting and crystallization enthalpy as compared to
that of 10, 20, and 30 wt% microcapsule loadings, respec-
tively. The prepared microcapsules were found relatively sta-
ble regarding thermal and mechanical properties even after
100 thermal cycles. SEM morphology of the R-PUF compos-
ite indicated the decrease in cell size of foam with increasing
microcapsule loading. The PU sandwich tin panel composite
with 40 wt% microcapsule loading showed minimum tem-
perature rise in the building room that promotes its potential
thermal energy storage application in buildings.
ACK NO WLE DGE MEN TS
The authors would like to thank the Institute of Chemi-
cal Technology, Mumbai, for availing all-instrumental
facilities required for the work. This was supported by
Defense Research and Development Organization
(DRDO), New Delhi, India (Grant number: NRB/4003/
PG/387 dated January 17, 2017).
CONFLICT OF INTEREST
The authors declare no conflicts of interest.
E TH IC S A P PR O V A L S T A TE M E N T
We have read and followed the instructions.
DATA AVAILABILITY STATEMENT
Data sharing is not applicable to this article as no new
data were created or analyzed in this study.
ORCID
Amol Tarachand Naikwadi https://orcid.org/0000-
0002-3094-5668
Asit B. Samui https://orcid.org/0000-0003-2964-1365
Prakash A. Mahanwar https://orcid.org/0000-0002-
6530-7113
R EF E RE N C E S
1. Su W, Darkwa J, Kokogiannakis G. Review of solid-liquid
phase change materials and their encapsulation technologies.
Renew Sustain Energy Rev. 2015;48:373-391. https://doi.org/10.
1016/j.rser.2015.04.044
2. Milian YE, Gutiérrez A, Grageda M, Ushak S. A review on
encapsulation techniques for inorganic phase change materials
and the influence on their thermophysical properties. Renew
Sustain Energy Rev. 2017;73:983-999. https://doi.org/10.1016/j.
rser.2017.01.159
3. Schossig P, Henning HM, Gschwander S, Haussmann T.
Micro-encapsulated phase-change materials integrated into
construction materials. Sol Energy Mater Sol Cells. 2005;89(2–
3):297-306. https://doi.org/10.1016/j.solmat.2005.01.017
4. Sundararajan S, Samui AB, Kulkarni PS. Versatility of polyeth-
ylene glycol (PEG) in designing solid-solid phase change
NAIKWADI ET AL.
materials (PCMs) for thermal management and their applica-
tion to innovative technologies. J Mater Chem A. 2017;5(35):
18379-18396. https://doi.org/10.1039/c7ta04968d
5. Yang J, Zhang E, Li X, Zhang Y, Qu J, Yu ZZ.
Cellulose/graphene aerogel supported phase change compos-
ites with high thermal conductivity and good shape stability for
thermal energy storage. Carbon. 2016;98:50-57. https://doi.org/
10.1016/j.carbon.2015.10.082
6. Qiu X, Lu L, Wang J, Tang G, Song G. Solar energy materials &
solar cells preparation and characterization of
microencapsulated n-octadecane as phase change material
with different n-butyl methacrylate-based copolymer shells. Sol
Energy Mater Sol Cells. 2014;128:102-111. https://doi.org/10.
1016/j.solmat.2014.05.020
7. Farid MM, Khudhair AM, Ali S, Razack K. A review on phase
change energy storage: materials and applications. Energy Con-
vers Manag. 2004;45:1597-1615. https://doi.org/10.1016/j.
enconman.2003.09.015
8. Bao J, Zou D, Zhu S, Ma Q, Wang Y, Hu Y. A medium-temper-
ature, metal-based, microencapsulated phase change material
with a void for thermal expansion. Chem Eng J. 2021;415:
128965. https://doi.org/10.1016/j.cej.2021.128965
9. Borreguero AM, Valverde JL, Rodríguez JF, Barber AH,
Cubillo JJ, Carmona M. Synthesis and characterization of
microcapsules containing Rubitherm®RT27 obtained by spray
drying. Chem Eng J. 2011;166(1):384-390. https://doi.org/10.
1016/j.cej.2010.10.055
10. Ushak S, Judith Cruz M, Cabeza LF, Grageda M. Preparation
and characterization of inorganic PCM microcapsules by fluid-
ized bed method. Materials. 2016;9(1):1-11. https://doi.org/10.
3390/ma9010024
11. Peng G, Dou G, Hu Y, Sun Y, Chen Z. Phase change material
(PCM) microcapsules for thermal energy storage. Adv Polym
Technol. 2020;2020:1-21. https://doi.org/10.1155/2020/9490873
12. Sarı A, Alkan C, Bilgin C. Micro/nanoencapsulation of some
paraffin eutectic mixtures with poly (methyl methacrylate )
shell: preparation, characterization and latent heat thermal
energy storage properties. Appl Energy. 2014;136:217-227.
https://doi.org/10.1016/j.apenergy.2014.09.047
13. Huang J, Wang T, Zhu P, Xiao J. Preparation, characterization,
and thermal properties of the microencapsulation of a hydrated
salt as phase change energy storage materials. Thermochim
Acta. 2013;557:1-6. https://doi.org/10.1016/j.tca.2013.01.019
14. Zhang H, Wang X. Fabrication and performances of
microencapsulated phase change materials based on n-
octadecane core and resorcinol-modified melamine-
formaldehyde shell. Colloids Surf A Physicochem Eng Asp.
2009;332(2–3):129-138. https://doi.org/10.1016/j.colsurfa.2008.
09.013
15. Liang C, Lingling X, Hongbo S, Zhibin Z. Microencapsulation
of butyl stearate as a phase change material by interfacial poly-
condensation in a polyurea system. Energy Conver Manag.
2009;50(3):723-729. https://doi.org/10.1016/j.enconman.2008.
09.044
16. Kenisarin M, Mahkamov K. Solar energy storage using phase
change materials. Renew Sustain Energy Rev. 2007;11(9):1913-
1965. https://doi.org/10.1016/j.rser.2006.05.005
17. Li Y, Chen Y, Huang X, Jiang S, Wang G. Anisotropy-
functionalized cellulose-based phase change materials with
NAIKWADI ET AL.
reinforced solar-thermal energy conversion and storage capac-
ity. Chem Eng J. 2021;415:129086. https://doi.org/10.1016/j.cej.
2021.129086
18. Zhou Z, Zhang Z, Zuo J, Huang K, Zhang L. Phase change
materials for solar thermal energy storage in residential build-
ings in cold climate. Renew Sustain Energy Rev. 2015;48:692-
703. https://doi.org/10.1016/j.rser.2015.04.048
19. De Masi RF, Gigante A, Vanoli GP. Numerical analysis of
phase change materials for optimizing the energy balance of a
nearly zero energy building. Sustain Cities Soc. 2020;63:102441.
https://doi.org/10.1016/j.scs.2020.102441
20. Iqbal K, Sun D. Development of thermo-regulating polypropyl-
ene fiber containing microencapsulated phase change mate-
rials. Renew Energy. 2014;71:473-479. https://doi.org/10.1016/j.
renene.2014.05.063
21. Fu Z, Su L, Li J, et al. Elastic silicone encapsulation of n-
hexadecyl bromide by microfluidic approach as novel
microencapsulated phase change materials. Thermochim Acta.
2014;590:24-29. https://doi.org/10.1016/j.tca.2014.06.008
22. Zhang H, Liu Z, Mai J, et al. Super-elastic smart phase change
material (SPCM) for thermal energy storage. Chem Eng J. 2021;
411:128482. https://doi.org/10.1016/j.cej.2021.128482
23. Riahi A, Kavian S, Mosleh HJ, Shafii MB. Evaluation of a
cooling system integrated with different phase change mate-
rials and its effect on peak load shaving. Int J Energy Res. 2021;
45:10425-10449. https://doi.org/10.1002/er.6530
24. Kahraman Dögüşcü D, Kızıl Ç, Biçer A, Sarı A, Alkan C.
Microencapsulated n-alkane eutectics in polystyrene for solar
thermal applications. Sol Energy. 2018;160:32-42. https://doi.
org/10.1016/j.solener.2017.11.072
25. Konuklu Y, Erzin F. Preparation of pentadecane/poly(mela-
mine-urea-formaldehyde) microcapsules for thermal energy
storage applications. Int J Energy Res. 2019;43(12):6322-6326.
https://doi.org/10.1002/er.4346
26. Naikwadi AT, Samui AB, Mahanwar PA. Solar energy
materials and solar cells melamine-formaldehyde
microencapsulated n- Tetracosane phase change material for
solar thermal energy storage in coating. Sol Energy Mater Sol
Cells. 2020;215:110676. https://doi.org/10.1016/j.solmat.2020.
110676
27. Srinivasaraonaik B. Microencapsulation of a eutectic PCM
using in situ polymerization technique for thermal energy stor-
age. Int J Energy Res. 2020;44:3854-3864. https://doi.org/10.
1002/er.5182
28. Özonur Y, Mazman M, Paksoy HÖ, Evliya H. Microencapsula-
tion of coco fatty acid mixture for thermal energy storage with
phase change material. Int J Energy Res. 2006;30(10):741-749.
https://doi.org/10.1002/er.1177
29. Yuan L, Liang G, Xie J. Synthesis and characterization of
microencapsulated dicyclopentadiene with melamine-
formaldehyde resins. Colloid Polym Sci. 2007;285:781-791.
https://doi.org/10.1007/s00396-006-1621-5
30. Su J, Wang X, Dong H. Influence of temperature on the defor-
mation behaviors of melamine-formaldehyde microcapsules
containing phase change material. Mater Lett. 2012;84:158-161.
https://doi.org/10.1016/j.matlet.2012.06.074
31. Chen Z, Wang J, Yu F, Zhang Z, Gao X. Preparation and prop-
erties of graphene oxide-modified poly(melamine-formalde-
hyde) microcapsules containing phase change material
11
n-dodecanol for thermal energy storage. J Mater Chem A. 2015;
3(21):11624-11630. https://doi.org/10.1039/c5ta01852h
32. Kant K, Shukla A, Sharma A. Ternary mixture of fatty acids as
phase change materials for thermal energy storage applica-
tions. Energy Rep. 2016;2:274-279. https://doi.org/10.1016/j.
egyr.2016.10.002
33. Yang C, Fischer L, Maranda S, Worlitschek J. Rigid polyure-
thane foams incorporated with phase change materials: a state-
of-the-art review and future research pathways. Energy Build.
2015;87:25-36. https://doi.org/10.1016/j.enbuild.2014.10.075
34. Amaral C, Vicente R, Ferreira VM, Silva T. Polyurethane foams
with microencapsulated phase change material: comparative
analysis of thermal conductivity characterization approaches.
Energy Build. 2017;153:392-402. https://doi.org/10.1016/j.
enbuild.2017.08.019
35. You M, Zhang X, Wang J, Wang X. Polyurethane foam con-
taining microencapsulated phase-change materials with
styrene-divinylbenzene co-polymer shells. J Mater Sci. 2009;44
(12):3141-3147. https://doi.org/10.1007/s10853-009-3418-7
36. Liao H, Liu Y, Chen R, Wang Q. Preparation and characteriza-
tion of polyurethane foams containing microencapsulated
phase change materials for thermal energy storage and thermal
regulation. Polym Int. 2020;70:619-627. https://doi.org/10.1002/
pi.6145
37. Ramli Sulong NH, Mustapa SAS, Abdul Rashid MK. Applica-
tion of expanded polystyrene (EPS) in buildings and construc-
tions: a review. J Appl Polym Sci. 2019;136(20):1-11. https://doi.
org/10.1002/app.47529
38. Kostic R, Pukhkal V, Vatin N, Murgul V. Application of Styro-
foam in the elements of building constructions. Appl Mech
Mater. 2015;725–726:396-402. https://doi.org/10.4028/www.
scientific.net/amm.725-726.396
39. Doroudiani S, Omidian H. Environmental, health and safety
concerns of decorative mouldings made of expanded polysty-
rene in buildings. Build Environ. 2010;45(3):647-654. https://
doi.org/10.1016/j.buildenv.2009.08.004
40. Xie J, Wang W, Liu J, Pan S. Thermal performance analysis of
PCM wallboards for building application based on numerical
simulation. Sol Energy. 2018;162:533-540. https://doi.org/10.
1016/j.solener.2018.01.069
41. Kuznik F, Virgone J, Roux JJ. Energetic efficiency of room wall
containing PCM wallboard: a full-scale experimental investiga-
tion. Energy Build. 2008;40(2):148-156. https://doi.org/10.1016/
j.enbuild.2007.01.022
42. Hasan MI, Basher HO, Shdhan AO. Experimental investigation
of phase change materials for insulation of residential build-
ings. Sustain Cities Soc. 2018;36:42-58. https://doi.org/10.1016/
j.scs.2017.10.009
43. Qiao Y, Yang L, Bao J, Liu Y, Liu J. Reduced-scale experi-
ments on the thermal performance of phase change material
wallboard in different climate conditions. Build Environ.
2019;160:106191. https://doi.org/10.1016/j.buildenv.2019.
106191
44. Xiang B, Yang Z, Zhang J. ASA/SEBS/paraffin composites as
phase change material for potential cooling and heating appli-
cations in building. Polym Adv Technol. 2021;32(1):420-427.
https://doi.org/10.1002/pat.5097
45. Al-Yasiri Q, Szab o M. Incorporation of phase change materials
into building envelope for thermal comfort and energy saving:
12
a comprehensive analysis. J Build Eng. 2021;36:102122. https://
doi.org/10.1016/j.jobe.2020.102122
46. Ji R, Zou Z, Liu L, Wei S, Qu S. Development and energy evalu-
ation of phase change material composite for building energy-
saving. Int J Energy Res. 2019;43(14):8674-8683. https://doi.org/
10.1002/er.4867
47. Alqahtani T, Mellouli S, Bamasag A, Askri F, Phelan PE. Experi-
mental and numerical assessment of using coconut oil as a
phase-change material for unconditioned buildings. Int J Energy
Res. 2020;44(7):5177-5196. https://doi.org/10.1002/er.5176
48. Karlessi T, Santamouris M, Synnefa A, Assimakopoulos D,
Didaskalopoulos P, Apostolakis K. Development and testing of
PCM doped cool colored coatings to mitigate urban heat Island
and cool buildings. Build Environ. 2011;46(3):570-576. https://
doi.org/10.1016/j.buildenv.2010.09.003
49. Xu T, Chen Q, Zhang Z, Gao X, Huang G. Investigation on the
properties of a new type of concrete blocks incorporated with
PEG/SiO2 composite phase change material. Build Environ.
2016;104:172-177. https://doi.org/10.1016/j.buildenv.2016.05.003
50. Zhang D, Li Z, Zhou J, Wu K. Development of thermal energy
storage concrete. Cem Concr Res. 2004;34(6):927-934. https://
doi.org/10.1016/j.cemconres.2003.10.022
51. Yeon JH, Kim KK. Potential applications of phase change
materials to mitigate freeze-thaw deteriorations in concrete
pavement. Construct Build Mater. 2018;177:202-209. https://
doi.org/10.1016/j.conbuildmat.2018.05.113
52. Alawadhi EM. Thermal analysis of a building brick containing
phase change material. Energy Build. 2008;40(3):351-357.
https://doi.org/10.1016/j.enbuild.2007.03.001
53. Zhang C, Chen Y, Wu L, Shi M. Thermal response of brick wall
filled with phase change materials (PCM) under fluctuating
outdoor temperatures. Energy Build. 2011;43(12):3514-3520.
https://doi.org/10.1016/j.enbuild.2011.09.028
NAIKWADI ET AL.
54. Mahdaoui M, Hamdaoui S, Ait Msaad A, et al. Building bricks
with phase change material (PCM): thermal performances.
Construct Build Mater. 2020;269:121315. https://doi.org/10.
1016/j.conbuildmat.2020.121315
55. Zhang Y, Huang J, Fang X, Ling Z, Zhang Z. Optimal roof
structure with multilayer cooling function materials for build-
ing energy saving. Int J Energy Res. 2020;44(3):1594-1606.
https://doi.org/10.1002/er.4969
56. Shilei L, Neng Z, Guohui F. Eutectic mixtures of capric acid
and lauric acid applied in building wallboards for heat energy
storage. Energy Build. 2006;38(6):708-711. https://doi.org/10.
1016/j.enbuild.2005.10.006
57. Borreguero AM, Rodríguez JF, Valverde JL, Arevalo R, Peijs T,
Carmona M. Characterization of rigid polyurethane foams con-
taining microencapsulated Rubitherm® RT27: catalyst effect.
Part II. J Mater Sci. 2011;46(2):347-356. https://doi.org/10.1007/
s10853-010-4824-6
58. Amaral C, Pinto SC, Silva T, et al. Development of polyure-
thane foam incorporating phase change material for thermal
energy storage. J Energy Storage. 2020;28:101177. https://doi.
org/10.1016/j.est.2019.101177
How to cite this article: Naikwadi AT,
Samui AB, Mahanwar PA. Fabrication and
experimental investigation of microencapsulated
eutectic phase change material-integrated
polyurethane sandwich tin panel composite for
thermal energy storage in buildings. Int J Energy
Res. 2021;1-12. https://doi.org/10.1002/er.7138