Energy and Buildings 144 (2017) 276–294

Contents lists available at ScienceDirect

Energy and Buildings

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

Synthesis, characterization and applications of microencapsulated

phase change materials in thermal energy storage: A review
Guruprasad Alva, Yaxue Lin, Lingkun Liu, Guiyin Fang ∗
School of Physics, Nanjing University, Nanjing 210093, China

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

Article history: In recent years microencapsulation of phase change materials has become popular in thermal energy stor-
Received 26 September 2016 age field. Commercially produced microencapsulated phase change material (MPCM) is also available in
Received in revised form 24 March 2017 market today. Microencapsulation enhances thermal and mechanical properties of phase change mate-
Accepted 26 March 2017
rials used in thermal energy storage. Microencapsulation can be achieved through different techniques
Available online 29 March 2017
and using different shell materials. As the microencapsulation of PCM is gaining increased attention,
more and more research works on MPCM are getting published. This review attempts to summarize the
Keywords:
available research information on synthesis, characterization, properties and applications of microencap-
Microencapsulation
Phase change materials (PCM) sulated phase change materials for thermal energy storage. The synthesis methods of microencapsulated
Microencapsulated phase change materials phase change materials, such as physical synthesis methods like spray drying, physical chemical synthesis
(MPCM) methods like complex coacervation and sol–gel process, and chemical synthesis methods like suspen-
Thermal properties sion polymerization, emulsion polymerization, interfacial polymerization, in-situ polymerization and
Thermal energy storage (TES) condensation polymerization, are presented. The properties of microencapsulated phase change mate-
rials like physical properties, chemical properties and thermal properties are analyzed. The applications
of microencapsulated phase change materials in buildings, textiles, MPCM slurry and composite foams
are also expounded.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2. The synthesis of microencapsulated phase change materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1.1. Core . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1.2. Shell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1.3. Emulsifier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1.4. Initiator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1.5. Cross-linking agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
2.1.6. Nucleating agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
2.1.7. Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.2. Physical synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.2.1. Spray drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.3. Physical chemical synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.3.1. Complex coacervation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.3.2. Sol–gel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
2.4. Chemical synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
2.4.1. Suspension polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

∗ Corresponding author.
E-mail address: gyfang@nju.edu.cn (G. Fang).

http://dx.doi.org/10.1016/j.enbuild.2017.03.063
0378-7788/© 2017 Elsevier B.V. All rights reserved.
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294 277

2.4.2. Emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

2.4.3. Interfacial polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
2.4.4. In-situ polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
2.4.5. Condensation polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3. The characterization of microencapsulated phase change materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1.1. Encapsulation efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1.2. Microcapsule size distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.1.3. Encapsulation ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.1.4. Shell characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.1.5. Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.2. Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
3.2.1. Fourier transformation infrared spectroscopy (FT-IR) analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
3.2.2. X-ray diffraction (XRD). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .288
3.3. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.3.1. Differential scanning calorimetry (DSC) analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.3.2. Thermogravimetric analysis (TGA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.3.3. Flammability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
3.3.4. Thermal reliability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
3.3.5. Thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
4. Applications of microencapsulated phase change materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
4.1. Buildings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
4.2. Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
4.3. MPCM slurry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
4.4. Composite foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
5. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293

1. Introduction

Phase change materials (PCM) are considered as the best choice

for thermal energy storage. They have a high thermal energy stor-
age density due to their high latent heat of fusion. They can store
and release thermal energy at an almost constant temperature, near
the operating temperature range of many commercial applications
like heating and cooling of buildings, thermal comfort textile and
solar energy systems. However they have a limitation in low ther-
mal conductivity. Moreover as they melt, the liquid phase creates
problems like leakage. MPCM will have a central PCM core around
which a coating is grown of organic or inorganic shell materials.
The different forms of core-shell structure are shown in Fig. 1.
Microcapsules can vary from few microns to millimeter in size.
Microencapsulation helps to overcome low thermal conductivity
by increasing the surface-to-volume ratio for the PCM. This pro-
vides a large heat exchange surface area for each PCM core, thus
increasing the heat transfer. It solves leakage issue, by containing
the melted PCM inside micron sized capsule made up of material
with a higher melting point than PCM.
Currently very few review articles on microencapsulation of
PCM are available. Most of the previous review articles on microen-
capsulation are related to its applications in other areas like
pharmaceuticals, food, agriculture etc. On microencapsulation of
PCM, Zhao and Zhang [1] reviewed their synthesis techniques
and applications. Their focus was mainly on chemical techniques.
Jamekhorshid et al. [2] did a comprehensive review of microen-
capsulation synthesis techniques. Paloma et al. [3] reviewed the
synthesis techniques, characterization and applications of MPCM.
This review attempts to summarize the recent developments in Fig. 1. Morphology of microcapsules [2].

synthesis technologies, characterization and applications of MPCM.

capsulated drugs act as oral and transdermal drug delivery vehicles.
2. The synthesis of microencapsulated phase change They provide an extended drug effect at a relatively low dose due
materials to controlled and prolonged release [4]. In food industry it is used
for coating probiotic bacteria. Microencapsulation protects the pro-
Microencapsulation technique is popular in various industries. biotic bacteria from damage due to external factors like heat, pH
In pharmaceuticals industry it is used for coating drugs. Microen- changes etc during storage and handling and from pH changes and
278 G. Alva et al. / Energy and Buildings 144 (2017) 276–294

bile in human gastrointestinal track until it reaches its destination

intestine alive [5]. In agriculture it is used for coating pesticides.
Microencapsulation is the technique for the controlled release of
pesticide. This reduces the environmental losses of pesticide until
it reaches its target [6]. Microencapsulation of PCM for thermal
energy storage is relatively a recent phenomenon. There are many
different microencapsulation techniques and many different core-
shell materials available for PCM. Broadly these techniques can
be classified under three categories as physical, physical-chemical
and chemical methods. Shell materials can be both organic and
inorganic. Below are the details of most common materials and
synthesis techniques used for producing MPCM.

2.1. Materials

Microencapsulation of PCM requires materials of below listed

types.

2.1.1. Core
PCM is the core material in MPCM. PCM used in MPCM are
mostly organic PCM. Organic PCM have a suitable melting point
near the thermal comfort range of humans which is around 20 ◦ C.
They are chemically inert and show no phase segregation. They are
non toxic and harmless to environment. They do not promote cor-
rosion. They do not have subcooling issue. Organic PCM include
different classes like paraffin (n-alkane), fatty acids, alcohols, east-
ers and polyethylene glycol (PEG) etc. Paraffin class materials of
organic PCM are the most popular choice as core materials. Paraffin
material n-octadecane has suitable melting temperature of 28.4 ◦ C.
It is non-polar and insoluble in water. There for it can easily form
emulsion. On the other hand polyethylene glycol (PEG) is difficult to
be encapsulated. It cannot form emulsion in water because it is sol-
uble in water. Similarly inorganic salts also are rarely encapsulated
due to their solubility in water. They are corrosive and have super-
cooling issue. However there are reports of inorganic hydrated salts
also being encapsulated [7]. The PCM that have been reported to be
microencapsulated are listed in Table 1.
2.1.2. Shell
Shell materials form the capsules that contain the PCM. There
are both organic and inorganic shell materials. There are also hybrid
shell materials made of organic-inorganic combination. Majority
of the shells are organic and prepared through chemical method
like polymerization. Monomers are used for building shell through
polymerization process. Monomers are repeating blocks of a long
polymer chain. Polymer chains can also be formed by more than
one monomer. Sometimes the shell material could be a co-polymer
which is a combination of more than one polymer [8]. Microcapsule
shell can also be built through physical methods like spray drying or
complex-coacervation. A shell material should not undergo chem-
ical reaction with the PCM core and should possess good chemical
stability. The shell material should have thermal stability at high
temperatures. Its surface morphology must be smooth and it should
have minimum porosity and prevent any leakage of PCM at tem-
peratures above the melting point of PCM. Table 2 gives a list of
commonly used shell materials and synthesis techniques associ-
ated. The shell gives the mechanical strength and shape stability to
MPCM. Thicker shells have better mechanical strength. It is desir-
able to have shell material with high thermal conductivity. The shell
material should withstand the repeated mechanical stress cycles
and thermal cycles for at least 1000 cycles and more. The proper-
ties of the shell depends on the type of polymer chosen as shell
material and also conditions during the synthesis process.
Fig. 2. Elementary reactions in conventional free radical polymerization [10].
2.1.3. Emulsifier
Emulsion is a system of two immiscible liquids where one liquid
is dispersed as droplets in the other liquid. Basic microencapsula-
tion technique involves preparation of oil in water (O/W) emulsion
with PCM as the oil phase. PCM is dispersed as micron sized oil
droplets in the continuous aqueous solution using mechanical stir-
rers or ultrasound techniques. However emulsions are unstable due
to the natural tendency (surface tension) of liquid-liquid system
to separate and minimize interfacial area and interfacial energy.
Typical emulsifiers are a class of materials called amphiphiles
(surfactants, synthetic polymers, polysaccharides etc) that have
molecular structure with one end soluble in oil phase and other end
soluble in water phase. There for they form a thin film at the inter-
face between the oil droplets and aqueous solution. They reduce the
surface tension effect by preventing the direct contact between two
different oil droplets. This gives kinetic stability to the emulsion.
Sometimes emulsifiers are also called as stabilizers. Surfactants are
used for emulsification in almost all chemical synthesis techniques
of MPCM. The emulsion stability through the use of mixed surfac-
tants sodium dodecyl sulfate (SDS) and poly vinyl alcohol (PVA)
was studied by Al-Shannaq et al. [9] and compared to a system
where only a single surfactant (PVA) was used. The use of mixed
surfactants induced long-term emulsion stability. They reported
surface morphology and the particle size of the microcapsules are
related directly to the emulsion stability, where the percentage of
surface buckles and dimples on the surface of the microcapsules are
reduced significantly in the case of mixed surfactant. Table 2 gives a
list of commonly used emulsifier materials along with related shell
materials and synthesis techniques.
2.1.4. Initiator
Initiators are used in radical polymerization techniques like sus-
pension polymerization and emulsion polymerization. Different
stages of a radical polymerization process are shown in Fig. 2. In
radical polymerization an initiator decomposes in to two free rad-
icals under the influence of an external trigger like heating, light
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294 279

Table 1
Core materials.

Type Class PCM Melting point ◦ C Latent heat of Nucleating agents Remarks References
fusion H kJ/kg

Organic Paraffin n-Octadecane 28.4 234 1-octadecanol, Most popular PCM [14,17,21,28]
Sodium Chloride, choice
paraffin
Organic Paraffin Rubitherm-RT21 21 135 1-Octadecanol, [13]
Rubitherm-RT58
Organic Paraffin Paraffin wax 64 189.24 [11,22]
Organic Paraffin n-Hexadecane 20 185 [12,17,29,70]
Organic Paraffin n-Nonadecane 32 194.3 [17]
Organic Paraffin n-Tetradecane 6 202 [19,70]
Organic Paraffin n-Heptadecane 22.6 216.6 [23,63,70]
Organic Paraffin n-eicosane 36.6 214.2 [68]
Organic Fatty acid Palmitic acid 64 208.5 [31]
Organic Fatty acid Capric acid 31 190.21 [24]
Organic Fatty acid Lauric acid 43 200.18 [24]
Organic Fatty acid Myristic acid 53 201.65 [24]
Organic Fatty acid Capric 26.04 176.68 Eutectic mixture [26]
acid(86%) + stearic
acid(14%)
Organic Ester Butyl stearate 23 140 [67]
Organic Alcohol Xylitol 93 248.7 [27]

or ionizing radiation. Free radical initiates the polymerization pro-

cess by attacking the monomer molecule forming a bond with it
and a reactive site on the monomer molecule. Second monomer
molecule reacts with the reactive site of first monomer forming a
polymer chain and regenerating a fresh reactive site on the chain.
Polymerization proceeds (on average adding a monomer unit every
millisecond) exclusively by a reaction between the reactive site on
the growing polymer chain and fresh monomer molecules, with
the regeneration of the fresh reactive site at the end of each growth
step. After about a thousand additions, the growing chains undergo
either chain termination or chain transfer reactions. In the termi-
nation case, a dead polymer chain (i.e. chain without reactive site)
is formed and the reactive site is irreversibly lost. In chain transfer
case, a dead polymer chain is produced but the reactive site is trans-
ferred to another species that can start a new chain [10]. Table 2
gives a list of commonly used initiator materials along with related
shell materials and synthesis techniques.
Fig. 3. DSC curves of non-encapsulated and encapsulated PCM [13].

2.1.5. Cross-linking agent
Cross-linking is a process where a polymer chain on the shell
material is linked to another polymer chain through a chemi-
cal bond. Cross-linking provides better mechanical strength to
the shell materials. Al-Shannaq et al. [9] reported adding a
small amount of cross-linker to the system improves the sur-
face morphology of the microcapsules to be smooth and compact
and produces microcapsules with a much higher PCM content.
Hawlader et al. [11] reported an example of cross-linking in synthe-
sis using complex-coacervation technique of Gum-Arabica/Gelatin
capsules. Authors describe that, carboxylate functional group on
gelatin molecule with a formaldehyde molecule, activates car-
boxylic group to nucleophillic attack. A reaction of such groups
on other gelatin molecules with the first activated carboxylate
cross-links the gelatin. This hardening reaction is catalyzed by OH
(alkaline condition). The change in pH value results in ionization
and deionization of the functional groups [4]. For example car-
boxylic acid group (COOH) are not ionized at low pH of less than
5.5, whereas charged COO groups repulse each other at high pH
of 5.5–7.4 [4]. Increasing the amount of cross-linking agent leads
to an increase in the encapsulation efficiency. However beyond an
optimum 8 ml of cross-linking agent, further increase did not result
in much improvement in encapsulation efficiency [11]. Alay et al.
[12] reported that cross-linker type used for shell polymerization
had an impact on thermal properties, particle size and structure
of microcapsules. In the same study they also used polyurethane
as a cross-linker to fix the microcapsules to cotton and polyester
in thermo-regulated fabrics. Table 2 gives a list of commonly used
cross-linking agents along with related shell materials and synthe-
sis techniques.
2.1.6. Nucleating agent
Normally inorganic PCM have subcooling problem. Organic PCM
do not have serious supercooling issue. However, when organic
PCM are encapsulated in microcapsules, they tend to supercool
severely, most likely due to the absence of nuclei in such small
space. Al-Shannaq et al. [13] reported that due to supercooling,
the onset crystallization temperature of microencapsulated PCM in
differential scanning calorimetry (DSC) graph could be 10 ◦ C lower
than that of non-encapsulated PCM as shown in Fig. 3. This can seri-
ously impact the efficiency of thermal energy storage. Nucleating
agents are added to decrease the super cooling problem in MPCM.
Al-Shannaq et al. [13] verified using nucleating agents supercooling
issue can be eliminated. However the addition of nucleating agents
introduces new problems like decrease in latent heat of fusion of
core PCM, appearance of buckles and dimples on the shell surface
spoiling the smoothness of surface morphology of the shell. Use
of 1-octadecanol as nucleating agent for RT21 increased the shell
permeability resulting in an increased mass loss. However use of
RT58 as nucleating agent for RT21 not only prevented supercool-
 280
Table 2
Shell materials.
Shell materials Type Preparation methods PCM Monomers/polymers Emulsifier (Surfactant) Initiators Cross linking agents Remarks References
Arabic-gum/gelatin Organic Complex-coacervation Paraffin wax arabic-gum Gluteraldehyde, Emulsified at 10,000 rpm [11]
(Polysaccharide), formaldehyde Peak melting temperature:
gelatin powder(Protein) 62.5 ◦ C
Latent heat of fusion:
239.78 kJ/kg
n-Hexadecane arabic-gum Dodecyl sulfate sodium Formaldehyde (H2 CO) Potassium peroxodisulfate [17]
(Polysaccharide), salt (SDS) (K2 O8 S2 ),
gelatin powder(Protein) (C12 H25 OSO2 ONa) Sodium thiosulfate
(Na2 S2 O3 ),
Sodium carbonate (Na2 CO3 )
Are used as electrolytes
Latent heat of fusion:
144.7 kJ/kg
n-Octadecane Latent heat of fusion:
165.8 kJ/kg
n-Nonadecane Latent heat of fusion:
57.5 kJ/kg
Spray drying Paraffin wax arabic-gum Latent heat of fusion: [11]
(Polysaccharide), 216.44 kJ/kg
gelatin powder(Protein)
Low density polyethy- Organic Spray drying Rubitherm-RT27 LDPE (polymer), Peak melting temperature: [16]

G. Alva et al. / Energy and Buildings 144 (2017) 276–294

lene(LDPE)/ethylene EVA(polymer) 28.40 ◦ C
vinyl acetate(EVA) Latent heat of fusion:
98.1 kJ/kg
Acrylonitrile–styrene Organic Phase separation n-tetradecane AS (copolymer) Polyvinyl alcohol (PVA) Dichloromethane(DCM) used [19]
copolymer (AS) as polymer solvent
Latent heat of
fusion:142.3 kJ/kg
Acrylonitrile–styrene– ABS(copolymer) Latent heat of fusion:
butadiene copolymer 107.1 kJ/kg
(ABS)
Polycarbonate (PC) PC(copolymer) Latent heat of
fusion:49.5 kJ/kg
Polyurea Organic Interfacial polymerization n-octadecane Tolylene 2,4-diisocyanate Sodium salt of Ammonium chloride used as [66]
(TDI), styrene–maleic anhydride nucleating agent for
ethylene diamine (EDA) copolymer (SMA) polymerization. It turns the
solution slightly acidic.
Peak melting temperature:
28.16 ◦ C
Latent heat of fusion:
158.7 kJ/kg
Tolylene 2,4-diisocyanate Peak melting temperature:
(TDI), 27.73 ◦ C
diethylene triamine Latent heat of fusion:
(DETA) 165.1 kJ/kg
Tolylene 2,4-diisocyanate Peak melting temperature:
(TDI), 27.04 ◦ C
Amine-terminated Latent heat of fusion:
polyoxypropylene 188.9 kJ/kg
(Jeffamine)
Butyl stearate Toluene-2,4-diisocyanate OP-10 Cyclohexane is used as a [67]
(TDI) (Non-ionic surfactant) reagent.
Ethylene diamine (EDA) Peak melting temperature:
33.8 ◦ C
Latent heat of
fusion:85.92 kJ/kg
®
Polyurethane Organic Interfacial polymerization Xylitol Diphenyl methylene Span 85 (sorbitan Xylitol is used as both core [27]
diisocyanate (MDI), trioleate)-Non-ionic PCM and polyol type
Xylitol (Polyol) surfactant, monomer.
poly(ethylene Latent heat of
glycol)dioleate fusion:196.3 kJ/kg
Polystyrene Organic Emulsion polymerization n-Heptadecane Styrene Triton X-100 Ferrous sulfate Divinylbenzene Peak melting temperature: [23]
heptahydrate 21.48 ◦ C
Ammonium persulphate Latent heat of fusion:
136.89 kJ/kg
Capric acid Styrene Triton X-100 Ferrous sulphate Divinylbenzene Latent heat of [24]
heptahydrate, fusion:86.45 kJ/kg
Ammonium persulfate
Table 2 (Continued)
Shell materials Type Preparation methods PCM Monomers/polymers Emulsifier (Surfactant) Initiators Cross linking agents Remarks References
Lauric acid Latent heat of
fusion:87.21 kJ/kg
Myristic acid Latent heat of fusion:
98.26 kJ/kg
Melamine–formaldehyde Organic In-situ n-Octadecane Melamine, Styrene-maleic anhydride Triethanolamine used for ph [14]
Formaldehyde copolymer (SMA) control.
Latent heat of fusion:
160 kJ/kg
n-eicosane Melamine, Sodium Sodium hydroxide and acetic [68]
Formaldehyde dodecylbenzenesulfonate acid used for pH control
(SDBS) Latent heat of
fusion:162.4 kJ/kg
n-octadecane Melamine, Sodium 1,3-Benzenediol Acetic acid (acidic pH) and [28]
Formaldehyde salt of styrene-maleic (resorcinol) triethanolamine (basic pH) is
anhydride copolymer used for maintaining basic
(SMA) pH. Ammonium chloride used
as nucleating agent for
polymerization.
Peak melting temperature:
26.91 ◦ C
Latent heat of fusion:
146.5 kJ/kg
Polyurea-formaldehyde In-Situ n-hexadecane Urea Sodium Resorcinol (1,3 dihydroxy Ammonium chloride is the [29]
(NH2)2C O, salt of styrene-maleic benzene) polymirization reaction
Formaldehyde initiator. Acetic acid

G. Alva et al. / Energy and Buildings 144 (2017) 276–294

anhydride copolymer
(H2CO), (SMA) (CH3 COOH) for adjusting pH.
Poly(vinyl alcohol) (PVA), Peak melting temperature:
Triton X100 22 ◦ C
Latent heat of fusion:
115 kJ/kg
n-octadecane Peak melting temperature:
33.4 ◦ C
Latent heat of fusion:
153 kJ/kg
PMMA Organic Suspension Paraffin Methyl methacrylate Polyvinyl alcohol Benzoyl peroxide Penta erythritol tetra Peak melting temperature: [13]
(poly-methyl polymerization Rubitherm-RT21 (MMA) (PVA)-Nonionic, acrylate (PETRA) 22.28 ◦ C
methacrylate) Sodium dodecyl Latent heat of fusion:
sulfate(SDS)- ionic 153 kJ/kg
Disodium hydrogen Methyl methacrylate sorbitan trioleate Dibenzoyl peroxide Acetone, toluene, carbon [7]
phosphate hepta-hydrate (MMA), (Span-80) tetrachloride and chloroform
(Na2 HPO4 ·7H2 O) ethyl acrylate (EA) were used as organic solvent.
Hydroquinone mono-methyl
ether is used as inhibiter
Peak melting temperature:
51 ◦ C
Latent heat of fusion:
150 kJ/kg
Emulsion polymerization n-Heptadecane Methylmethacrylate Triton X-100 Ferrous sulphate allyl methyl acrylate Latent heat of fusion: [63]
(MMA) (FeSO4.7H2O) 81.5 kJ/kg
n-Octacosane Sodium thio-sulphate Peak melting temperature: [25]
(Na2 S2 O7 ) 50.6 ◦ C
Tert-butyl hydroperoxide Latent heat of fusion:
86.4 kJ/kg
n-Hexadecane ethylene glycol Peak melting temperature: [12]
dimethacrylate 17.34 ◦ C
Latent heat of fusion:
145.61 kJ/kg
Capric acid, Stearic acid Methylmethacrylate Triton-X100 Ammonium persulphate, Ethylene glycol Latent heat of [26]
(Eutectic Mixture) (MMA) Ferrous sulphate dimethacrylate fusion:116.25 kJ/kg
Silica (SiO2 ) Inorganic Sol-gel n-Octadecane Sodium silicate Poly( Hydrochloric acid (pH [21]
ethylene control)
oxide-b-propylene Peak melting temperature:
oxide-b-ethylene oxide) 27.96 ◦ C
tri-block copolymer Latent heat of fusion:
(EO27-PO61-EO27) 87.4 kJ/kg
Paraffin Tetraethoxysilane (TEOS) Sodium Anhydrous ethanol and [22]
(Si(OC2 H5 )4 ) dodecyl sulfate (SDS) distilled water used as
solvent. Hydrochloric acid
used as the activator.
Peak melting temperature:
58.37 ◦ C
Encapsulation ratio: 87

281
Latent heat of
fusion:165.6 kJ/kg
 282
Table 2 (Continued)
Shell materials Type Preparation methods PCM Monomers/polymers Emulsifier (Surfactant) Initiators Cross linking agents Remarks References
Tris Tetraethoxysilane (TEOS), Sodium dodecyl sulfate Cyclohexane used as solvent. [32]
(hydroxymethyl)methyl (3- (SDS), Tris is a solid-solid phase
aminomethane Aminopropyl)triethoxysilane SPAN 80 change material.
(APTS) Peak melting temperature:
130 ◦ C
Latent heat of
fusion:146 kJ/kg
Stearic acid Tetraethoxysilane (TEOS) Sodium dodecyl sulfate Hydrochloric acid used for pH [65]
(SDS) control
Peak melting temperature:
53.5 ◦ C
Latent heat of fusion:
171.0 kJ/kg
Titania shells(TiO2 ) Inorganic Sol-gel Palmitic acid Tetra-n-butyltitanate Sodium dodecyl sulfate Anhydrous ethanol and [31]
(SDS) distilled water used as
solvent. Hydrochloric acid
used for pH control.
Peak melting temperature:
61.7 ◦ C
Latent heat of fusion:

G. Alva et al. / Energy and Buildings 144 (2017) 276–294

63.3 kJ/kg
Spray drying n-Octadecane Titanium Peak melting [15]
tetra-isopropoxide (TTIP) temperature:28.7 ◦ C
Latent heat of fusion:
97.0 kJ/kg
n-Butylmethacrylate-co- Organic Suspension n-Octadecane n-butyl methacrylate styrene-maleic anhydride 2,2-Azobisisobutyronitrile Pentaerythritol triacrylate Peak melting temperature: [69]
polymers polymerization (BMA) copolymer (SMA) (AIBN) (PETA) 30.9 ◦ C
(Co-polymer) n-butyl acrylate(BA) Latent heat of fusion:
116.4 kJ/kg
n-butyl Peak melting temperature:
methacrylate(BMA) 32.8 ◦ C
methacrylic acid (MAA) Latent heat of fusion:
144.3 kJ/kg
n-butyl Peak melting temperature:
methacrylate(BMA) 27.6 ◦ C
acrylic acid (AA) Latent heat of fusion:
141.5 kJ/kg
n-butyl Peak melting temperature:
methacrylate(BMA) 30.9 ◦ C
n-butyl acrylate(BA) Latent heat of fusion:
methacrylic acid (MAA) 136.3 kJ/kg
Poly(styrene-co- Organic Emulsion polymerization Tetradecane Styrene, Ethyl Acrylate Triton X-100 Ammonium Ethylene glycol Peak melting temperature: [70]
ethylacrylate) (EA)(C5 H8 O2 ) peroxodisulfate dimethacrylate 7.97 ◦ C
(Co-polymer) Ferrous sulphate Latent heat of fusion:
(FeSO4 .7H2 O) 182.68 kJ/kg
Pentadecane Sodium thiosulfate Peak melting temperature:
(Na2 O3 S2 ) 11.60 ◦ C
Latent heat of fusion:
121.83 kJ/kg
Hexadecane Peak melting temperature:
20.38 ◦ C
Latent heat of fusion:
196.08 kJ/kg
Heptadecane Peak melting temperature:
24.04 ◦ C
Latent heat of fusion:
140.51 kJ/kg
PMMA-co-SiO2 Hybrid Interfacial/sol-gel/self- paraffin Methyl methacrylate Sodium dodecyl benzene Ammonium persulfate Peak melting temperature: [64]
(Co-polymer) assembly (MMA), Tetraethoxysilane sulfonate (SDBS) 26.8 ◦ C
(TEOS) Latent heat of fusion: 71 kJ/kg
n-Octadecyl Organic Suspension n-octadecane n-octadecyl methacrylate Sodium Benzoyl peroxide (BPO) Divinylbenzene (DVB) A novel co-polymer that [8]
methacrylate Polymerization (ODMA), salt of styrene-maleic Allyl methacrylate (AMA) decreases degree of super
(ODMA), Methacrylic acid (MAA) anhydride copolymer cooling.
methacrylic acid (SMA) Peak melting temperature:
(MAA) 21.1 ◦ C
(Co-polymer) Latent heat of fusion: 91 kJ/kg
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
ing but also decreased the mass loss. Fan et al. [14] experimented
with three different nucleating agents sodium chloride, ammo-
nium chloride, 1-octadecanol and paraffin for n-octadecane PCM.
They found paraffin to be most suited nucleating agent with no
impact on surface morphology. Table 1 gives a list of commonly
used nucleating agents along with the related PCM.
2.1.7. Others
Other than the above listed materials additional materials can
be used in the synthesis process. For example solutions of NaOH,
hydrochloric acid, triethanolamine and acetic acid are used for
controlling the pH during polymerization. Sometimes after the
microcapsule shells have polymerized, during the post-processing
step inhibiters like hydroquinone monomethyl ether are added to
prevent further polymerization reaction [7]. Monomers as supplied
by company may contain inhibitors which may inhibit shell poly-
merization. In such cases monomers are pre-washed in solutions
like NaOH and deionized water to remove inhibitors and neutral-
ize the monomer before microencapsulation process. In emulsions,
water is the most used solvent. However other solvents like ace-
tone, toluene, carbon tetrachloride and chloroform are also in use.
2.2. Physical synthesis methods
In a physical process the ingredients that make up the shell
do not undergo any chemical reaction. They retain their original
chemical composition. The shells are formed by physical processes
like binding due to drying (dehydration), adhesion etc. In food and
pharmaceutical industries many purely mechanical techniques like
pan coating, air suspension coating, spray drying etc are in use for
microencapsulation, but only spray drying technique is most used
for microencapsulating PCM.
2.2.1. Spray drying
In this synthesis technique, first an emulsion of PCM in a solu-
tion containing the shell material like gelatin is prepared with
mechanical stirring at a high rpm like 10,000. A binder like gum-
arabica will be added in drops while a suitable temperature and
pH will be maintained [11]. This emulsion will then be fed to
an atomizing nozzle at a particular feed rate. At the atomizer a
high pressure carrier gas (nitrogen or air), sprays the feed solution
as small droplets into a drying chamber. At the drying chamber,
sprayed droplets comes into contact with the hot drying gas (nitro-
gen or air), and evaporation takes place in the droplet’s surface
until the moisture content becomes too low to diffuse through
the dried droplet surface. Thus a shell is formed around the core
producing MPCM. Finally, the recovery of dried MPCM is carried
out either in the cyclone, filter bag or electrostatic precipitator.
Fig. 4 shows a sample spray drying equipment. Desired particle
size distribution can be achieved through suitable atomizer design
and the process can be easily controlled and scaled-up. Hawaldar
et al. [11] microencapsulated paraffin-wax with gelatin and gum-
arabica as shell materials using spray-techniquedrying technique.
They reported producing microcapsules with spherical shape and
uniform size distribution. The surface morphology of the shells
was smooth with no sharp edges or dents. Microcapsules had a
high heat storage capacity up to 216 kJ/kg. The microencapsulation
efficiency decreased with increasing core-to-coating ratio, where
as heat storage capacity increased with increasing core-to-coating
ratio. Fei et al. [15] used spray-drying technique for synthesizing
n-octadecane microcapsules with inorganic titania shell material.
They reported synthesizing microcapsules with 0.1–5.0 microme-
ter size range. Borreguero et al. [16] microencapsulated commercial
®
wax, paraffin Rubitherm RT27, using low density polyethylene
(LDPE) and ethylvinylacetate copolymer (EVA) as shell materials
through spray drying technique. They reported an average parti-
283
Fig. 4. Spray drying equipment [15].
cle size of 3.9 micrometers, high encapsulation efficiency (63 wt%),
high heat storage capacity and good thermal stability over 3000
cycles. However they also reported the problem of agglomeration
of microcapsules in the drying chamber. Sometimes, the microcap-
sules have a complex morphology, such as poly-nuclear or matrix
type. Use of large amounts of core material can lead to uncoated
particles.
2.3. Physical chemical synthesis methods
Physical chemical processes are hybrid process that use combi-
nation of physical and chemical methods. Physical processes like
phase separation, heating, cooling etc are combined with chem-
ical processes like hydrolysis, cross-linking, condensation etc to
achieve microencapsulation. For microencapsulation of PCM most
commonly used physical chemical techniques are complex coacer-
vation and sol–gel.
2.3.1. Complex coacervation
This method is also called phase separation method. This
method is typically used for organic shell material combinations
like gelatin/gum-arabic, agar-agar/gum-arabic, chitosan/gum-
arabic, chitosan/silk-fibroin etc. In this method the shell polymer
material is dissolved in a solvent to form solution. Then an emul-
sion is prepared with PCM material as the oil phase dispersed
in the above solution. The dissolved shell is then made to pre-
cipitate on the PCM droplet’s surface by evaporating the solvent
and then forming a shell around the PCM. Alternately the same
can be achieved by coalescing (due to electrostatic attraction) of
two different organic polymers around the PCM droplet’s sur-
face and then dropping the temperature and pH of the emulsion
to initiate phase-separation. This results in two different phases,
one around the PCM droplet surface which is rich in colloids
concentration and other in the aqueous phase poor in colloids con-
centration. The colloid-rich phase coalesces to form a coacervate
layer forming a shell around PCM. Gum arabic is a complex and
variable mixture of polysaccharides and glycol-proteins [17]. It is
negatively charged above pH of 2.2. Gelatin is a heterogeneous
mixture of single or multi-stranded polypeptides, each contain-
ing between 300 and 4000 amino acids [17]. The final step is
hardening and filtering of microcapsules. The hardening step is
carried out using the cross-linking agent like formaldehyde or
gluteraldehyde solution. Filtered microcapsules will be washed in
deionized water or ethanol and dried in a vacuum oven. Santos
et al. [18] microencapsulated xylitol using gum-arabica and gelatin
as shell materials. They verified that during complex-coacervation,
the carboxyl groups of polysaccharides interact with the amino
284 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
groups of proteins to form a complex containing an amide bond.
Fourier transformation infrared spectroscopy (FT-IR) analysis ver-
ified the formation of amides in the microcapsules, confirming the
occurrence of complex-coacervation. The peak that appeared at
3313 cm−1 in the gelatin spectrum is characteristic of amine groups
(positively charged), and the peak that appeared with low intensity
at 2939 cm−1 in the gum-arabic spectrum is characteristic of car-
boxylic groups (negatively charged). The binding of positive and
negative charges (i.e., amino and carboxyl groups) is expected to
promote the process of coacervation and the formation of amides.
They observed a peak at approximately 1651 cm−1 in the spec-
trum, which indicated the presence of an amide, confirming the
formation of this complex. Hawalder et al. [11] microencapsu-
lated paraffin-wax with gelatin and gum-arabica as shell materials
using complex-coarcervation technique. They reported producing
microcapsules with spherical shape and uniform size distribu-
tion. The surface morphology of the shells was smooth with no
sharp edges or dents. Microcapsules had a high heat storage capac-
ity up to 239.78 kJ/kg. The influence of emulsifying time and
cross-linking agent concentration on encapsulation efficiency were
also reported. They found 8 ml of cross-linking agent and 10 min
emulsifying time to be optimal with maximum encapsulation effi-
ciency. Yang et al. [19] carried out successful microencapsulation
of n-tetradecane with different shell materials by phase sepa-
ration method. They used acrylonitrile-styrenecopolymer (AS),
acrylonitrile–styrene–butadiene copolymer (ABS) and polycarbon-
ate (PC) as shell materials. Among them, AS was found to be the
most suitable one, with highest encapsulation efficiency (84.5%)
and greatest heating enthalpy (142.3 kJ/kg). Garcia et al. [20]
observed growth of microorganisms after one month on MPCM
prepared with food grade gelatin, using complex-coacervation
technique. The microorganism growth was avoided by substituted
to sterilized gelatin instead.
2.3.2. Sol–gel process
In this technique, first a sol solution is prepared which when
added to PCM emulsion, produces a gel of discrete microcapsules
containing PCM droplets inside. This method is typically used for
inorganic shell materials like silica and titanium oxide. The sol
solution is prepared through hydrolysis of precursor compound
like tetraethoxysilane (TEOS or Tetraethylorthosilicate), sodium
silicate, methyl triethoxysilane etc. Low pH (2–3) condition is main-
tained in sol solution to promote hydrolysis reaction. After that the
silicate sol solution is added to a PCM O/W emulsion drop by drop
while emulsion is kept stirring to prevent formation of any contin-
uous gel and allowing the formation of only discrete silica gel walls
around PCM droplets. The silica shell will be formed on the surface
of the PCM droplets by the condensation polymerization of the sil-
ica solid particles. High pH (9–10) condition is maintained in the
emulsion to promote condensation reaction. Fig. 5 shows a sample
sol–gel process. Organic polymers are usually toxic and flammable,
and compared to inorganic polymers, they have poor heat transfer
performance and thermal stability. Due to these disadvantages of
organic polymers, recently inorganic polymer materials such as sil-
ica, titanium dioxides etc have got more attention as shell materials.
He et al. [21] microencapsulated n-octadecane through sol–gel syn-
thesis using sodium silicate as a silica precursor. They researched
on the effect of pH value on the porosity of the silica shell and found
the best anti-osmosis property at pH 2.95–3.05 due to the formation
of compact silica wall. Fang et al. [22] microencapsulated paraffin
with SiO2 shell using sol–gel method.
2.4. Chemical synthesis methods
These methods are purely chemical in nature. Here the poly-
merization can be started by free radicals that attack the monomers
when a trigger like heating or pH change is initiated. This type of
polymerization technique is called radical polymerization. There
are 2 types of radical polymerization namely suspension poly-
merization and emulsion polymerization. Microencapsulation of
PCM has also been achieved through other commonly used chem-
ical synthesis techniques like interfacial polymerization, in-situ
polymerization and condensation polymerization. Sometimes a
combination of multiple chemical techniques is used to achieve
microencapsulation. More details on each of the synthesis tech-
niques are provided below.
2.4.1. Suspension polymerization
This method is preferred when both monomers and initiators
are either insoluble or poorly soluble in aqueous phase solvent.
Water is the most used liquid as a solvent. There for in this method
during emulsification, PCM, monomers and initiators form the
oil phase and are suspended in the continuous aqueous phase
as discrete droplets. Emulsification can be aided by adding sur-
factants (emulsifiers) and continuous mechanical stirring. This is
a radical polymerization process. Initiators trigger the polymer-
ization when they release free radicals in to the system after a
trigger like heat is supplied. Typical initiators used in suspension
polymerization are benzoyl peroxide, 2,2-Azobisisobutyronitrile
(AIBN) etc which are poorly soluble in water. This method is
typically used for organic shell material like polymethylmethacry-
late (PMMA). Huang et al. [7] microencapsulated inorganic PCM
Na2 HPO4 ·7H2 O which is a hydrated salt using PMMA polymer shell
using suspension polymerization technique. They reported that use
of inhibiters at the post-processing phase gives a smooth, spheri-
cal and compact shell surface, while without inhibiters the shell
surface was non-spherical with deformed lump shape. They also
reported improvement in supercooling problem of the inorganic
PCM after microencapsulation. Tang et al. [8] microencapsulated
n-octadecane with n-octadecyl methacrylate (ODMA) –methacrylic
acid (MAA) co-polymer (PODMAA). They reported that this novel
co-polymer reduces the supercooling issue in microencapsulation.
The onset crystallizing temperatures of microcapsules were only
4 ◦ C below that of n-octadecane. Many small alkyl nano-domains
are formed when PODMAA crystallizes through n-octadecyl side
chain packing. During the cooling process, these small alkyl nano-
domains located on the inner wall of microcapsule act as crystal
nuclei and subsequently induce the heterogeneous nucleation of
n-octadecane. This decreases the degree of supercooling of n-
octadecane cores.
2.4.2. Emulsion polymerization
This method is preferred when the monomers are either insol-
uble or poorly soluble in aqueous phase solvent but initiator is
soluble in aqueous phase solvent. Water is the most used liq-
uid as a solvent. There for in this method during emulsification,
only the PCM and monomers form the oil phase, dispersed in the
continuous aqueous phase as discrete droplets. Initiators will be
dissolved in the aqueous phase. Emulsification can be aided by
adding surfactants (emulsifiers) and continuous mechanical stir-
ring. This is a radical polymerization process. Initiators trigger the
polymerization when they release free radicals in to the system
after a trigger like heat is supplied. Typical initiators used in suspen-
sion polymerization are ferrous sulphate, ammonium persulphate,
sodium thiosulphate etc which are easily soluble in water. This
method is typically used for organic shell materials like PMMA and
polystyrene. Many researchers [12,23–26] have successfully done
microencapsulation using this technique.
2.4.3. Interfacial polymerization
This method is preferred if we have two (or more) monomers
associated with the final shell polymer and also if one monomer is
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294 285

Fig. 5. Sol–gel method [21].

Fig. 6. Types of polymerization (a) interfacial, (b) suspension and (c) emulsion [2].

hydrophobic and the other is hydrophilic. Water is the most used
liquid as a solvent. During emulsification, PCM and hydrophobic
monomers form the oil phase. Hydrophilic monomers are dissolved
in the aqueous phase. Hence we have two reactive monomers sepa-
rated in two immiscible mediums which react only at the interface
between two solutions creating a thin film at the surface. But as
the polymerization continues, the polymer film becomes a barrier
to slow the polymerization process. Thus the shell thickness pro-
duced in this type could be very thin. This method is typically used
for organic shell materials like polyurea and polyurethane. Polyurea
is formed from a reaction of an isocyanate with a multifunctional
amine. Polyurethane is formed from a reaction of an isocyanate
with a polyol. In this synthesis technique, first the isocyanate will be
prepared as oil phase organic solvent with PCM. Then this oil phase
is poured in to water to prepare an O/W emulsion. After stirring
for few minutes, the water soluble monomer, which is diluted in
distilled water before, will be added to the emulsion system slowly
and the mixture is heated. Then the interfacial polymerization reac-
tion takes place between isocyanate and water soluble monomer at
the oil–water interface. The reaction may last for about 2–3 h. The
resultant microcapsules will be filtered, washed and dried. Salaün
et al. [27] microencapsulated xylitol (sugar alcohol PCM core) in
polyurethane shell using interfacial polymerization technique. Also
they used W/O type emulsion instead of the usual O/W type emul-
sion. Fig. 6 shows the difference between interfacial, suspension
and emulsion polymerization.
2.4.4. In-situ polymerization
In this synthesis technique, instead of monomers, chemi-
cal compounds that produce precursors to polymers are used.
Before the polymerization step, the precursors (pre-polymers like
oligomers) are prepared in-situ through hydrolysis of the par-
ent chemical compound. Later this precursor polymerizes to form
a shell around the PCM droplet. The precursors will be part of
aqueous phase and will not be present in the oil phase. This
method is typically used for organic shell materials like melamine-
formaldehyde and polyurea-formaldehyde. It should be noted
that formaldehyde is toxic and creates environmental and health
problems. In a typical synthesis process melamine-formaldehyde
pre-polymer is prepared in distilled water with a mixture of
melamine and formaldehyde with pH maintained at around 9.
Parallely an emulsion of PCM is prepared in a separate beaker.
The emulsion is homogenized for about an hour at high revo-
lutions per minute (rpm). The PCM emulsion will be gradually
added to the pre-polymer solution and pH of the solution will
be maintained at around 4 and continuously stirred for around
2 h. Once the microcapsules are formed pH is adjusted back to
around 9 which terminate the polymerization reaction. Microcap-
sules are filtered, washed with distilled water and dried. Zhang
et al. [28] compared three different emulsifiers, sodium salt of
styrene-maleic anhydride copolymer (SMA/anionic), sodium dode-
cyl sulfate (SDS/anionic) and polyvinyl alcohol (PVA/nonionic)
during in-situ polymerization of melamine-formaldehyde. They
286 G. Alva et al. / Energy and Buildings 144 (2017) 276–294

Fig. 7. Synthesis of MPCM with n-octadecane core and melamine–formaldehyde shell through in-situ polymerization [28].

found SMA producing smooth shell morphology with regular

spherical shape of microcapsules and no visible disfigurement on
shell surface. Using SDS resulted in irregular shapes of microcap-
sules with a thicker shell. Using PVA resulted in irregular shapes of
microcapsule and also problem of agglomeration of microcapsules
was noticed. Sarier et al. [29] microencapsulated n-hexadecane
or n-octadecane core materials with urea-formaldehyde polymer
shell using in-situ polymerization technique. They were success-
ful in depositing silver nanoparticles on the polymer shell using
adhesive forces which exist between silver particles and polymer
shells containing amide and carbonyl functional groups via metal-
dipole interaction. They concluded that the depositing silver nano
particles improve the thermal conductivity. They also reported
agglomeration of microcapsules due to increased cohesive forces
between capsule shells incorporated with silver nanoparticles.
Fig. 7 shows the in-situ polymerization of melamine-formaldehyde Fig. 8. Condensation polymerization [22].
shell around n-octadecane core.

3. The characterization of microencapsulated phase change

materials

3.1. Physical properties

2.4.5. Condensation polymerization 3.1.1. Encapsulation efficiency

In condensation polymerization, the polymerization occurs with
the release of simple molecules like water and methanol as by
product. The monomers or precursors used in this type of polymer-
ization reaction normally have functional groups like OH (alcohol),
NH2 (amino), COOH (carboxylic group) etc. In microencapsulation
of PCM condensation polymerization is a part of other synthetic
techniques like sol–gel, in-situ and interfacial polymerization. Fig. 8
shows an example condensation process.
Microencapsulation efficiency is the ratio of mass of micro-
capsules with fully formed shells in the sample to total mass
of microcapsules in the sample. It measures the yield of the
microencapsulation synthesis process. Hawlader et al. [11] mea-
sured encapsulation efficiency using the following method. One
gram of dried microcapsules (test sample) is washed with 25 ml of
toluene. Unencapsulated PCM or partially encapsulated PCM will
be dissolved in toluene. The encapsulation efficiency is calculated
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
Fig. 9. PSD diagram [26].
as the ratio of the weight of undissolved capsules to the original
weight of sample.
Weight of undissolved microPCM
(%) = × 100
Total weight of dry sample microPCM
Salaün et al. [27] used a different approach. Encapsulation effi-
ciency was calculated as the ratio of weight of xylitol filled particles
(MPCM) obtained after correction of xylitol content determined by
DSC to total weight of used monomer and xylitol. In this case xyli-
tol is used both as shell monomer and PCM core. It is expressed as
follows:
mmicroparticles − mxylitol
(%) =  × 100 (2)
mmonomers
3.1.2. Microcapsule size distribution
The particle size distribution (PSD) of the microcapsules is
measured using a laser diffraction analyzer. A small sample of
micro-capsules is suspended in deionized water bath and this sus-
pension is passed through laser beam which gets scattered. Size is
estimated based on the angle of deflection. Each sample is analyzed
for multiple times and the average is taken. Fig. 9 shows a sample
particle size distribution graph.
3.1.3. Encapsulation ratio
This is the ratio of core PCM to shell material. The latent heat
capacity of MPCM is dependent on the mass fraction of its PCM core
to total mass. Latent heat is obtained from differential scanning
calorimeter (DSC) curve. Encapsulation ratio is calculated using
below formula, where Hmicro-PCM (kJ/kg) is the latent heat of the
microcapsule containing PCM and HPCM (kJ/kg) is the latent heat of
pure PCM.
Hmicro−PCM
R= × 100%
HPCM
3.1.4. Shell characterization
3.1.4.1. Surface morphology. Particle size and morphology of the
microcapsule shell surface can be observed using scanning elec-
tron microscope (SEM) or optical microscope (OM) or transmission
electron microscopy (TEM). Dried MPCM powder is used as sample
for observing the morphology. OM is the simplest to use with least
sample preparation requirement. TEM is used for microcapsules
smaller than 1 ␮m size. Fig. 10 shows sample images from SEM
and TEM showing shell surface morphology of the microcapsules.
We can observe the condition of microcapsules as listed below:
• If shell surface is smooth and compact with no dents, deformities,
pores and ruptures (shown in Fig. 10(c)).
• If the shape of MPCMs is spherical and regular (if all capsules are
consistently spherical) (shown in Fig. 10(e)).
287
• Diameter of the microcapsules.
• Thickness of the shell wall (shown in Fig. 10(d)).
• If clustering of microcapsules exists.
3.1.4.2. Leakiness. Loose and porous shell structure makes the shell
wall fragile and results in leaking of core material. If the shell wall
is very thin, the shell can be easily broken upon slight external agi-
tation causing PCM core leakage. However thick shell wall means
reduction in encapsulation ratio(R) and there for an optimum shell
thickness should exist. Leakage can be tested using centrifugal
shear force test. In this test, sample microcapsules are put in a test
tube with water. Test tubes are then centrifuged at room temper-
ature at 400 rpm for 4 h. Then using an optical microscope the any
breakage and leakage of microcapsules is inspected. Al-Shannaq
et al. [13] tested the permeability of PCM through the shell of micro-
capsules via mass loss analyses. This was performed by placing a
known mass of dried microcapsules into an aluminum pan and
putting it into a drying oven at 50 ◦ C. The mass of the microcapsules
was periodically measured over 25 days. Also, the mass loss of bulk
PCM was measured under the same conditions for comparison. The
(1)
percent mass loss was calculated by the following equation.
Initial mass − Final mass
% mass loss = × 100 (4)
Initial mass
3.1.4.3. Shell thickness. Shell thickness is measured using
SEM/OM/TEM. Shell thickness provides both mechanical strength
and thermal stability. Tang et al. [8] investigated the effect of
core/shell mass ratio on thermal stability. They reported by
increasing the mass ratio of monomers to PCM, shell thickness can
be increased. Increased shell thickness results in higher thermal
stability. They used the temperature for occurrence of weigh loss
of 5% (Td5% ) for measuring thermal stability. They reported thermal
stability of MPCM as a function of the shell thickness.
3.1.4.4. Shell strength. Mechanical strength and shape stability
of the microcapsule is provided by the shell material. Stronger
the shell, more rigid will be the microcapsule. During repeated
charging–discharging cycles, MPCM slurries are circulated through
heat exchanger ducts. They are subjected to mechanical stresses
leading to abrasion and rupture of shell wall and subsequent loss
of effectiveness. There for shell strength is very important. Bor-
reguero et al. [16] used atomic force microscope (AFM) to measure
the mechanical strength of microcapsules. Individual microcap-
sules were fixed to a substrate surface using commercial adhesive
(Poxipol). AFM was used to image the sample and locate the micro-
capsules using semi-contact imaging. AFM probe was brought into
contact with an isolated microcapsule on the substrate surface. Z-
(3) piezo cantilever extension of the AFM pushes the probe into the
microcapsule. It resulted in bending of the AFM cantilever attached
to the AFM probe. The recorded cantilever bending was used for cal-
culating the force and plotting a force-displacement graph. Fig. 11
shows the force-displacement curve of atomic force microscope.
The total deformation behavior of an individual microcapsule was
recorded continually with increasing applied force to give resultant
force-displacement curves. This procedure was done five times to
check the reproducibility of the experiments, selecting microcap-
sules of the same particle size.
3.1.5. Density
MPCM when dried takes the form of a powder. In case of bulk
solids we measure the bulk density. But for powders it is measured
as apparent density which is a ratio of dry specimen mass to the
apparent volume. The apparent volume also includes the air gap
between the individual microcapsules in the powder. Krupa et al.
288 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
Fig. 10. SEM (a,c,e) and TEM(b,d,f) images [15].
Fig. 11. Atomic force microscope force–displacement curve [16].
[30] measured density of the microcapsules using a pycnometer
according to ASTM D153 standards.
3.2. Chemical properties
3.2.1. Fourier transformation infrared spectroscopy (FT-IR)
analysis
Chemical composition of PCM and MPCM is analyzed using
fourier transform infrared spectroscopy (FT-IR) method. Fig. 12
shows a sample FT-IR spectra graph. Table 3 provides hints to
identify the appropriate functional group corresponding to each
absorption peak. Based on this it is verified that no chemical reac-
tion has taken place between PCM and shell materials. It is also
verified, if the polymerization of the shell material has completed
successfully and MPCM contains both PCM and shell materials.
3.2.2. X-ray diffraction (XRD)
Chemical composition can also be identified by using the charac-
teristic diffraction peaks of PCM and shell materials. XRD is typically
used when the shell material is inorganic. Fei et al. [15] analyzed
pure PCM (n-octadecane), pure shell materials (titania crystals) and
micro encapsulated PCM samples separately with X-ray powder
diffraction. Using this method first they were able to know that
in MPCM synthesized with spray-dry method, titania in the shell
wall was amorphous. The MPCM were given a hydrothermal post-
Table 3
FT–IR Spectrum Functional Groups.

Functional Bond Vibration type Intensity Wave Wave Material Remarks References
group length from length to

alkane C H Bending 820 894 PCM [17,27,29,66]

Alkane C H Stretching Strong 2800 3100 PCM [8,15,17,18,19,21,23,24,26,
(CH3 ,CH2 ,CH) 27,29,31,32,63,64,65,66]
Alkane C H Rocking Weak 717 728 PCM [8,17,19,21,25,28,31,66]
(CH3 and CH2 )
Alkane C H Deformation Medium 1295 1488 PCM [15,19,21,23,25,27,28,29,31,32,63,64,68]
(CH3 and CH2 )
Silica Si O Bending 1083 1156 Silica [22,32,64,65]
Silica Si O Bending 766 798 Silica [22,32]
Silica Si O Bending 420 465 Silica [21,22,65]
Silica Si OH Bending 952 960 Silica [21,22]
Carboxylic C O Stretching Strong 1600 2000 Gum arabica, Usually [8,17,19,24,26,27,29,31,65,66]
group PMMA, polyurea, appears after

G. Alva et al. / Energy and Buildings 144 (2017) 276–294

polyurethane polymeriza-
tion. Indicates
presence of
amides
Carboxylic OH Stretching 2400 3400 Gum arabica [18]
group
Carboxylate C O Stretching 1530 1580 Palmitic acid [31]
group
Ester bond C O Stretching Strong 950 1381 PMMA, n-octadecyl [8,15,19,24–26,27,29,32,64,68]
methacrylate
(ODMA), Titanium-
tetra-isopropoxide,
Tris, formaldehyde
Amine N H Stretching Weak 3100 3500 Gelatin, polyurea, [18,27,29,66–68]
polyurethane,
melamine
Amine N H Bending Medium 1500 1655 Gelatin, polyurea, [17,18,27,29,66]
polyurethane
Amine C N Stretching Medium 1000 1250 Polyurethane, [27–29,68]
melamine
Benzene ring C C Stretching 1462 1522 Polysterene,Polyurea, Vanishes after [23,24,28]
Resorcinol polymerization
Nitrite CN Stretching Sharp 2237 2260 Acrylonitrile–styrene- [19]
copolymer
TiO2 Ti O 420 TiO2 [15]
Isocyanate N C O 2200 2280 Polyurea, Vanishes after [27,66,67]
polyurethane polymerization
Hydroxyl OH Stretching Strong 3000 3700 Water [17,18,22,24,27,28,29,31,32]
Hydroxyl OH In-plane Medium 1290 1700 Water, stearic acid [15,22,27,31,65]
Bending
Hydroxyl OH Out of plane Weak 650 1150 Water [8,31,65]
bending
Triazine ring C N Stretching 1500 1600 Melamine [28,68]
Triazine ring C N Out of plane Sharp 800 820 Melamine [28,68]
deformation

289
290 G. Alva et al. / Energy and Buildings 144 (2017) 276–294

Fig. 12. FT–IR spectra (a) shell material, (b) PCM and (c) MPCM [23].

process. After that the XRD pattern verified the formation of titania
crystallites. Fang et al. [22] used XRD to verify the successful encap-
sulation of PCM. The diffraction pattern of a mixture is a simple
sum of the scattering from each component phase. They found the
microencapsulated PCM’s diffraction pattern as superimposition of
pure PCM XRD pattern over the nearly flat XRD pattern of amor-
phous SiO2 . Fan et al. [14] used XRD to study the effect of nucleating
agents on crystallographic system on n-octadecane. In this case the
shell material melamine-formaldehyde was amorphous. Melamine
formaldehyde does not interfere, as it has a flat XRD pattern with no
characteristic peaks of its own. The nucleating agents did not affect
the crystallographic system of n-octadecane. Cao et al. [31] by ana-
lyzing XRD pattern verified that the crystal structure of the PCM
remained unchanged after encapsulation in the TiO2 shell. Thus it
is concluded that there was no chemical reaction with the PCM Fig. 13. XRD patterns of the (a) SiO2 , (b) paraffin and (c) MEPCM [22].
during microencapsulation. Wu et al. [32] used XRD to study the
re-crystallization of Tris(hydroxymethyl)methyl aminomethane (a PCM with that of MPCM. The key thermal properties that the DSC
solid–solid PCM) during the period of thermal cycling. They found curves provide are below:
an increase in the intensity of the diffraction peak which indicated
increase in the crystal size with number of thermal cycles. Fig. 13 • Tmo : The onset temperature on DSC heating run.
shows a sample XRD spectra graph. • Tmp : The peak temperature on DSC heating run.
• Tco : The onset temperature on DSC cooling run.
• Tcp : The peak temperature on DSC cooling run.
3.3. Thermal properties • Hm : Enthalpy on DSC heating run (latent heat of melting).
• Hc : Enthalpy on DSC cooling run (latent heat of crystallization).
3.3.1. Differential scanning calorimetry (DSC) analysis
DSC analysis is used for measuring thermal properties of pure 3.3.2. Thermogravimetric analysis (TGA)
PCM and MPCM. DSC curves show the phase change behaviors dur- TGA thermographs are used for analyzing thermal stability of
ing heating and cooling periods as shown in Fig. 3. The figure shows MPCM. In this test the MPCM sample is subjected to an increas-
two sample DSC curves for one each for complete cycle of heat- ing temperature and at every step the weight loss of the sample
ing and cooling of a pure PCM and MPCM. The DSC curve shows is measured. Fig. 14 shows the TGA curves for PCM, shell material
two different phase changes (smaller solid–solid peak and larger and MPCM. It can be seen that start point of the degradation for
solid–liquid peak). Supercooling of MPCM is easily observed using both PCM and MPCM is almost same, indicating that weight loss is
DSC curve by comparing the crystallization temperatures of pure mainly due to evaporation of PCM and shell material is stable at that
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
Fig. 14. TGA curve [23].
point. This temperature where degradation of MPCM starts should
be well above the operating temperature of the thermal energy
storage system.
3.3.3. Flammability
As organic PCM are moderately flammable, strict building safety
laws restrict their use in buildings. The fire safety aspects of a mate-
rial include its tendency to ignite, heat release rate (HRR) during
burning and toxicity of the smoke due to release of harmful chem-
icals. The flash points of most organic PCM are just above 100 ◦ C
where as flash points of polymers such as polystyrene are above
300 ◦ C. There for microencapsulation of PCM will improve its fire
safety aspect. For polymers there are different testing methods
currently in use for measuring flammability like cone calorime-
ter, limiting oxygen index (LOI), vertical/horizontal flammability
testing. For form stable PCM, flammability has been tested using
cone calorimeter [33] and using LOI [34]. For textile fibers micro-
scale combustion calorimeter has been used to study their heat
release rate [35]. However currently there is not much research
data available on fire safety aspect of MPCM.
3.3.4. Thermal reliability
Thermal reliability is analyzed by subjecting the MPCM to
repeated very large number of thermal cycles. After repeated melt-
ing and freezing cycles if the thermal properties and chemical
composition do not change much, then MPCM is considered as reli-
able. This test may involve subjecting MPCM to up to 5000 thermal
cycles and then using DSC, FT-IR, XRD and TGA to check the changes
in thermal properties and chemical composition.
3.3.5. Thermal conductivity
MPCM as produced exists in powdered form. However during
its usage, it is in composite form with other materials like gypsum,
water etc. Currently there is not much information available on
the measurement of thermal conductivity of MPCM powders. There
are few studies on the thermal conductivity of MPCM slurries and
theoretical estimation of single MPCM particle. Zhang and Zhao [36]
used hot disk instrument to measure thermal conductivity of MPCM
slurry. The thermal conductivity of the single microcapsule was
estimated using the theoretical formula [36–38] using composite
sphere approach as below:
1 1 dp − dc
= +
kp dp kc dc kw dp dc
where kc is the thermal conductivity of the MPCM core material,
kw is the thermal conductivity of the MPCM shell material, dc is
the diameter of the MPCM core material, dp is the diameter of the
single MPCM particle, kp is the thermal conductivity of the single
MPCM particle.
291
The thermal conductivity of the MPCM slurry is calculated as
below using the Maxwell’s relation [38] for static dilute solution.
2kf + kp + 2cv (kp − kf )
kb = · kf (6)
2kf + kp − cv (kp − kf )
where kb is the bulk thermal conductivity of the MPCM slurry,
kf is the thermal conductivity of the working fluid and cv is the
volumetric concentration of the MPCM in the slurry.
Zhang and Zhao [36] reported that the thermal conductivity and
specific heat decreased with the increase of MPCM concentration
due to the lower thermal conductivities and specific heat of the
MPCM particles compared to the base fluid, water. Chen et al. [38]
also had similar results while studying the thermal conductivity of
MPCM slurry.
Maxwell’s relation is also used by Lecompte et al. [39] for
theoretical estimation of thermal conductivity of concrete and
mortar containing MPCM. They also compared the theoretical
value against the experimental value measured using hot plate
experimental setup. They reported that maxwell model correctly
predicts the effective thermal conductivities of the MPCM mix-
tures. The effective thermal conductivities decreased with the
increase of MPCM volume fraction. These results were in agree-
ment with the theoretical predictions and were due to the low
thermal conductivity of microencapsulated paraffin. Inorganic shell
materials have relatively better thermal conductivity than organic
shell materials. Wu et al. [32] attempted microencapsulating
Tris(hydroxymethyl)methyl aminomethane (a solid–solid phase
change material) with silica. They reported an improvement in
thermal conductivity of Tris from 0.211 W/(m.K) to 0.478 W/(m.K).
4. Applications of microencapsulated phase change
materials
MPCM has applications in passive systems like buildings, ther-
mal comfort textiles, composite foams etc. It also has applications
in active systems like heat exchangers, thermal control systems and
thermal storage systems.
4.1. Buildings
According to IEA estimates in year 2010 the building sector
(residential and commercial) used approximately 115EJ of energy
globally, accounting for 32% of global energy demand [40]. Out
of that space heating and cooling constituted 32–33% of the total
energy used in buildings. There for any improvement in efficiency
of this sector has a big impact on the global energy demand and can
reduce the environmental pollution. One way to improve the effi-
ciency of space heating and cooling in buildings is by incorporating
the concept of thermal mass into building designs, which provides
inertia against temperature fluctuations. Phase change materials
with their high thermal energy storage density near the thermal
comfort temperature range are ideal for increasing the thermal
inertia for the same mass of buildings. MPCM are embedded
into flooring, drywalls, concrete, ceilings, panels, gypsum boards,
insulation panels, wallboards etc. Although PCM without microen-
capsulation (i.e. direct impregnation) is a low cost option but long
term stability of the unprotected PCM and negative impact of the
PCM on building materials is a concern. For example in concretes
with presence of Ca(OH)2, high alkalinity impacts the stability of
(5) PCM like fatty esters and fatty alcohols. Inorganic PCM are corro-
sive and therefore they negatively impact the building materials.
Organic materials are flammable and may release toxic fumes dur-
ing combustion. Moreover the porous nature of building materials
like mortar which contain the PCM leads to leakage issues when the
temperature is above the melting point of PCM. Direct impregna-
tion of PCM in concrete may also weaken the mechanical strength.
292 G. Alva et al. / Energy and Buildings 144 (2017) 276–294

Attempts to use macro-encapsulated PCM were not much success-

ful due to the poor conductivity of PCM. When it was time to regain
the heat from the liquid phase, the PCM solidified around the edges
and prevented effective heat transfer. Solution to counter these
issues is use of MPCM which is ignition resistant and leak proof.
Microencapsulation of PCM increases the compatibility of PCM with
the building materials, increases its long term stability and also
with small dimensions mitigates thermal conductivity problem.
Cabeza et al. [41] tested the inclusion of commercial Micronal PCM
(from BASF) in the concrete. The concrete mixture with 5% PCM in
weight was tested for mechanical strength and thermal behavior.
They concluded that mechanical strength was satisfactory for struc-
tural purposes and that there was no negative impact of MPCM on
concrete even after six months of observation. They reported that
in comparison with conventional concrete without phase change Fig. 15. PCM microcapsules coated on the surface of fabric [47].
materials, concrete walls with embedded MPCM improved thermal
inertia and resulted in lower temperatures in the room. Lecompte
et al. [39] studied the thermal and mechanical characteristics of
hardened concrete and mortar mixes containing MPCM and com-
pared with classical civil engineering models. The MPCM behave
as voids decreasing the mechanical strength of the concrete and
mortar mixes. They reported the preparation of concrete mix with
MPCM requires additional water up to 10% of MPCM mass. Great
care must be taken during the concrete mix preparation to avoid the
breakage of microcapsules. They concluded that by maintaining the
MPCM volume fraction below 14.8% in mortar, and 8.6% in concrete
and by increasing the cement content in the mixture it is possi-
ble to achieve mechanical strength of the same order as normal
cement-based materials with no MPCM. Cao et al. [42] studied the
thermal performance of Portland cement concrete and geopolymer
concrete enhanced with MPCM. They concluded that addition of
Fig. 16. PCM microcapsules embedded within fiber [47].
MPCM results in significant loss of concrete compressive strength.
For Portland cement concrete addition of 3.2 wt% MPCM resulted
in reduction of compressive strength by 42% and for geopolymer 4.3. MPCM slurry
concrete addition of 2.7 wt% MPCM resulted in reduction of com-
pressive strength by 51%. They concluded that at these low weight Active thermal energy systems like heat exchangers, thermal
ratios of MPCM, although the loss of concrete compressive strength control systems and thermal storage systems use heat transfer fluid
was significant it still satisfied the European regulations. Energy (HTF). By enhancing the HTF such as water to a two phase fluid by
consumption for heating and cooling to maintain the indoor tem- emulsifying it with PCM, the heat carrying capacity of the HTF can
perature reduced by 11% for Portland cement concrete with 3.2 wt% be increased. Advantages from this technique are many:
MPCM and by 15% for geopolymer concrete with 2.7 wt% MPCM.
Authors also noted that further increasing the MPCM concentra- • Better heat transfer rate.
tions causes a too low workability of the concretes to produce • Heat transfer at nearly a constant temperature.
usable samples. • Reduced mass flow for the same heat transfer rate.
Yeliz et al. [43] in their review on use of MPCM in building • Possibility of usage as both thermal energy transport and storage
applications have listed a few research studies on mechanical and medium.
thermal properties of cement mortars, concretes and gypsum plas-
ters containing MPCM. Simen et al. [44] in their review on use Although suspended PCM droplets may impact the fluidity of
of PCM in building applications provided a comprehensive list HTF and increase pumping power requirement it will be within
of commercial products and manufacturers for both macro and acceptable limits. However PCM slurries there are few issues to be
microencapsulated PCM. Use of PCM in bricks [45] and tiles [46] resolved. The suspended PCM droplets could solidify on ducts of
for passive cooling has also been reported. heat exchangers and cause clogging. Stability of the PCM emulsion
is not good above the melting temperature of PCM and gradually
smaller PCM droplets can coalesce to form completely separated
layers of PCM and HTF. There for instead of direct PCM slurry with
4.2. Textiles HTF, MPCM slurry with HTF is used which has all the benefits of
PCM suspension and it has no coalescing problem as the shell mate-
PCM capsules have application in thermo-regulating textiles. rial prevents the contact between PCM droplets. MPCM slurry has
It is used for protection from extreme cold weathers in outdoor potential applications as a HTF for microchannel heat exchangers,
wear such as parkas, vests, snowsuits, trousers, ski wear, hunting solar energy collectors, thermal power plants etc [48,49]. A review
clothing, ear warmers, boots, gloves and in-house cloths such as on characterization of MPCM slurry was done by Chen et al. [50].
blankets, duvets, mattresses and pillowcases [47]. Textiles contain- There are many experimental studies done on the thermal and rhe-
ing PCM also help to combat overheating. There are two ways to ological properties of MPCM slurry [51–55]. It is found that wall
embed MPCM into fabric. PCM microcapsules were coated on the temperatures of the heat exchanger pipes decrease with the use
surface of fabric as shown in Fig. 15, and were directly embedded of MPCM slurry [38]. There are also theoretical studies done to
within fiber as shown in Fig. 16. analyze the influential parameters that affect the heat transfer char-
 G. Alva et al. / Energy and Buildings 144 (2017) 276–294
acteristics [56–60]. Studies have shown that Stefan number and
volumetric concentration of the MPCM in the slurry are the most
influential parameters on the laminar flow heat transfer rate [56].
Numerical study predicted the Nusselt number for the MPCM slurry
to be 1.5–4 times higher than that of single phase fluid [56]. Goel
et al. [61] experimentally analyzed different influencing parame-
ters like Stefan Number, volumetric concentration, microcapsule
to duct diameter ratio, Reynolds number and the homogeneity of
suspension etc.
4.4. Composite foams
Applying MPCM in polyurethane foam can improve its heat-
insulating ability. Polyurethane foams find application in areas like
automotive interiors, medical products etc. You et al. [62] fabricated
polyurethane composite foam containing n-octadecane/melamine-
formaldehyde MPCM. However there are few challenges involved
in fabrication of foams with MPCM as fillers. As the MPCM may con-
tain traces of formaldehyde, emulsifiers etc which are left behind
during synthesis process, these impurities can cause defoaming
effect. Heat treatment of MPCM eliminates water and formalde-
hyde. Heat treatment also helps in cross-linking the shell polymer.
Test results showed that higher the MPCM content in the composite
foam, the higher is the heat storage ability of the foam. However for
MPCM content beyond 12.59 wt%, the quality of foam was affected
[62].
5. Conclusions and outlook
MPCM has applications in buildings, textiles, thermal energy
storage, heat transfer fluids and heat insulating foams. MPCM has
a huge potential for energy savings in buildings. MPCM has been
embedded in to building materials in many innovative ways for
passive thermal energy storage. Experimental studies have been
conducted on embedding MPCM into cement mortar, concrete,
gypsum plaster, bricks, floor tiles, walls, ceiling, roof, windows and
shutters, glasses, insulation panels etc. There is scope for further
research into performance of MPCM in various building materi-
als and innovative applications of MPCM in building materials.
MPCM slurry is not only a good heat transfer fluid but also a
good heat storage medium. Therefore, MPCM slurry is the best
suited option for active thermal energy storage applications. Cur-
rently a wide range of synthesis options are available for producing
MPCM. Organic PCM normally do not have supercooling issue,
but when microencapsulated show supercooling which is unde-
sirable. Recently MPCM synthesis with inorganic shell materials,
and numerical and experimental study on performance of MPCM
slurry in circular tube, microchannel heat sink etc is gaining good
attention of researchers. Microencapsulation of inorganic PCM has
not got much attention so far. non-volatile organic solvents can be
tried for emulsifying inorganic PCM in place of the usual water sol-
vent. Microencapsulation of organic eutectic mixtures also has not
got much attention so far. Currently MPCM is mainly used in sys-
tems operating at low temperatures in the human thermal comfort
range. Although shell materials have thermal stability at a much
higher temperature than PCM, MPCM thermal stability is close to
thermal stability of PCM. Porosity of the shell adversely affects the
performance of MPCM at high temperature. Fire safety of MPCM
is an important aspect for its building application, where there is
scope for further research as currently there is not much informa-
tion available.
293
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (Grant no. 51676095, 51376087) and the Priority
Academic Program Development of Jiangsu Higher Education Insti-
tutions. The authors also wish to thank the reviewers and editor for
kindly giving revising suggestions.
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