Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

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Renewable and Sustainable Energy Reviews

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

A review on effect of phase change material encapsulation on the thermal

performance of a system
Pramod B. Salunkhe n, Prashant S. Shembekar 1
Global R&D Center, Dow Chemical International Pvt. Ltd., Panchsheel Tech. Park, Tower ‘C’, 6th Floor, Off Airport Road, Yerwada, Pune 411 006, Maharashtra, India

a r t i c l e i n f o abstract

Article history: This paper presents a detailed review of effect of phase change material (PCM) encapsulation on the
Received 11 September 2011 performance of a thermal energy storage system (TESS). The key encapsulation parameters, namely,
Received in revised form encapsulation size, shell thickness, shell material and encapsulation geometry have been investigated
21 May 2012
thoroughly. It was observed that the core-to-coating ratio plays an important role in deciding the thermal
Accepted 22 May 2012
Available online 4 August 2012
and structural stability of the encapsulated PCM. An increased core-to-coating ratio results in a weak
encapsulation, whereas, the amount of PCM and hence the heat storage capacity decreases with a decreased
Keywords: core-to-coating ratio. Thermal conductivity of shell material found to have a significant influence on the heat
Phase change material exchange between the PCM and heat transfer fluid (HTF). This paper also reviews the solidification and
Encapsulation
melting characteristics of the PCM and the effect of various encapsulation parameters on the phase change
Thermal energy storage
behavior. It was observed that a higher thermal conductivity of shell material, a lower shell size and high
Microencapsulated phase change slurry
temperature of HTF results in rapid melting of the encapsulated PCM. Conduction and natural convection
found to be dominant during solidification and melt processes, respectively. A significant enhancement in
heat transfer was observed with microencapsulated phase change slurry (MPCS) due to direct surface contact
between the encapsulated PCM and the HTF. It was reported that the pressure drop and viscosity increases
substantially with increase in volumetric concentration of the microcapsules.
& 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5604
2. Encapsulation of phase change materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5604
3. Nomenclature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5605
3.1. Encapsulation ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5605
3.2. Encapsulation efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5605
4. Types of PCM encapsulation based on size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5606
5. Performance improvement of a thermal system using encapsulated PCM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5606
6. Effect of core-to-coating ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5608
7. Effect of shell material. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5609
8. Effect of encapsulation geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5610
9. Melting and solidification of PCM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5610
10. Microencapsulated phase change slurry (MPCS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5612
11. Challenges for designing an encapsulated PCM based thermal system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5613
12. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5613
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5613
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5613

Abbreviations: HTF, heat transfer fluid; MPCS, microencapsulated phase change slurry; PCM, phase change material; PCS, phase change slurry; TESS, thermal energy
storage system
n
Corresponding author.
E-mail addresses: [email protected] (P.B. Salunkhe), [email protected] (P.S. Shembekar).
1
Tel.: þ91 20 6626 9674; fax: þ 91 20 6626 9555.

1364-0321/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.rser.2012.05.037
5604 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

Nomenclature y heating/cooling rate, K/min

Z encapsulation ratio
English symbols
d PCM liquid thickness, m

C constant
Subscripts
Cp specific heat, J/kg K
E encapsulation efficiency
app apparent
DH latent heat, J/kg
m melting
k thermal conductivity, W/m K
encap encapsulated
l PCM thickness, m
eq, p predicted equivalent
m mass, kg
f fusion
Nu Nusselt number
p predicted
q heat flow, W
s solidification
q_ volumetric heat generation, W/m3
0 outside
R cylinder radius, m
Ra Rayleigh number
Ste Stefan number Superscripts
T temperature, K
m, n constant
Greek Symbols

b heat generation parameter

1. Introduction above literature survey, it was noticed that the studies on the
effect of various encapsulation parameters, namely, size, shape,
The energy crisis in year 1971 gave an impetus to search for core-to-coating ratio, shell material and shell thickness of the
alternative energy sources as well as other energy saving ways encapsulated PCM on the flow and heat transfer characteristics of
that can fulfill the energy demand. Since then the focus on phase the PCM is missing. In this regard, the objective of the present
change material (PCM) increased. PCMs are the substances that study is to highlight the effect of encapsulation parameters on the
can absorb, store and release large amount of thermal energy. In performance of a TESS as well as on the solidification and melting
1901, Kyle [1] filed a patent on using palmitic acid and stearic acid to characteristics of the encapsulated PCMs. The present review
maintain the required temperature during the manufacturing of tin mainly focuses on but not limited to the building air conditioning
sheets. The total heat addition/release to/from the PCM consists of and solar water heater applications.
sensible heat and latent heat. During sensible heating the thermal
energy is stored up to the initiation of melting process, whereas, the
thermal energy stored during the phase change process is known as 2. Encapsulation of phase change materials
the latent heat. One of the major advantages of the latent heat
storage system is an isothermal release or gain of thermal energy. In Encapsulation is a process of covering the PCM (that forms the
contrast, the temperature decreases/increases during sensible cool- core part of the encapsulated PCM) with a suitable coating or shell
ing/heating. In a typical working temperature range, the latent heat material. This process was first invented by Barrett K Green in the
storage capacity is about 5 to 14 times the conventional thermal 1940s and 1950s [30] according to [31]. A primary purpose of
energy storage materials such as masonry, rock etc. Thus, the prime encapsulation is holding the liquid and/or solid phase of the PCM
advantage of PCM is the substantial reduction in space requirement and keeping it isolated from the surrounding. This ensures correct
for the same energy storage compared to that of conventional composition of the PCM that would have otherwise changed due to
materials. The high energy storage density characteristic of the mixing of the PCM with the surrounding fluid. Other advantages of
PCM has made it a hot topic of research over the last few decades. encapsulation involve reduction in reaction of PCM with the sur-
To this date, enormous work has been carried out to explore the use rounding, flexibility in frequent phase change processes, an increase
of PCMs in various applications, namely, building air conditioning in heat transfer rate and enhancement in thermal and mechanical
[2–5], electronics cooling [6–8], waste heat recovery [9,10], textiles stability of the PCM. It can also improve the compatibility of
[11], preservation of food, milk [12,13], solar energy storage [14–17], hazardous PCMs that cannot be directly used or immersed in certain
fabrics [18] to name a few. applications such as blood transport, food storage, building cooling/
As compared to solid–solid, liquid–gas and solid–gas PCMs, solid– heating, etc.
liquid PCMs have been widely used due to their large heat storage A major concern for the encapsulation of salt hydrates is
capacity and lesser volume change during the phase change process. their corrosive nature with metals and complete solubility in water.
There are multiple review papers [2,19–22] that highlight various In contrast, organic PCMs are non-corrosive and show negligible or
PCMs and their use for thermal energy storage in various applications incomplete solubility in water. The non-corrosive nature and insolu-
as listed previously. Most of the above studies deal with the selection bility in water are the highly desirable characteristics for the PCM.
criteria for a suitable PCM depending upon their application. After about 1000 thermal cycles, the diffusion tightness as well as the
Besides above, there are also numerous studies that report the thermal and structural strength of the encapsulated PCM deteriorates
preparation and characterization of encapsulated PCMs [23–29]. substantially and there is a possibility of absorption of water
From previous studies it is evident that PCM encapsulation has a molecules if the PCM is soluble in water. Hence, encapsulation of
significant influence on the performance of a TESS. Based on the organic PCMs is preferred over salt hydrates [32,33]. Mehling and
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5605

Fig. 1. Structure and working principle of the encapsulated PCM.

Cabeza [33] reported that till date microencapsulation of only organic Encapsulation of PCM
PCMs has been commercialized. However, most of the organic PCMs
are flammable. The flammability can be reduced by encapsulating the
PCM with an inorganic material [34]. Hart and Work [35] suggested Physical Chemical
that certain additives, namely, decabromodiphenyl oxide, octabromo-
phenyl oxide, antimony oxide etc. can be added to the encapsulated
PCMs as a flame retardant. Due to encapsulation, these PCMs can be Spray Centrifugal Fluidized In-situ Interfacial Complex
directly mixed or suspended in the surrounding medium. drying bed polymeri polyconde- coacervation
Diffusion tight bonding between the PCM and the shell zation nsation
material prevents the spillage of the PCM when it is in liquid
Fig. 2. Flow chart showing different manufacturing techniques of microencapsulated
state. Fig. 1 shows the structure and working principle of the
PCM.
encapsulated PCM. The encapsulated PCM contains PCM as a core
part and shell material as the encapsulant. Sometimes, an addi-
tional air pocket is provided inside the core part to accommodate
the change in volume during phase change process. Cristopia
Energy Systems [36] manufacture such type of nodules. The shell
should be strong enough to sustain the stresses that are generated
due to volumetric changes during the phase change process of the
PCM. The hydrophobic PCMs can prevent the solubility of PCM
into water. This avoids the contamination of the water that would
have otherwise resulted in hazardous effects to the human health.
The thickness of the coating material is one of the critical
parameters in assessing the effectiveness of the encapsulated
PCM. A substantially thin PCM capsule can have inferior structural Fig. 3. Different geometries for encapsulation of PCM (a) spherical (b) tubular
and thermal strengths, whereas, excessive thickness of the coat- (c) cylindrical and (d) rectangular.
ing material can reduce the amount of PCM inside the shell,
thereby increasing the container volume. In subsequent section, a
detailed study of effect of the encapsulation thickness on the 3. Nomenclature
performance of a TESS is presented.
The working principle of the encapsulated PCM as shown in 3.1. Encapsulation ratio
Fig. 1 can be explained as follows. In solid state, the supplied heat
to the PCM increases its temperature until it reaches the melting Encapsulation ratio, Z indicates the effective performance of a
point. The PCM temperature remains constant throughout the PCM inside the capsule [38]. The encapsulation ratio is defined by
melting process. During this phase change process substantial the following formula [34,39]:
amount of heat is stored. The molten PCM transforms to solid
ðDHÞm,encapPCM
when exposed to the surrounding with a temperature lower than Z¼  100 ð1Þ
ðDHÞm,PCM
its melting point. The phase transformation occurs through
release of thermal energy during sensible cooling and the phase
change process from the liquid to solid state. The phase change of 3.2. Encapsulation efficiency
PCM from solid to liquid phase and from liquid to solid phase are
termed as charging and discharging processes, respectively. The encapsulation efficiency, E is given by the following
There are two broad methods, namely, physical and chemical formula [40]
for the manufacture of the microencapsulated PCM. Fig. 2 shows ðDHÞm,encapPCM þ ðDHÞs,encapPCM
the flowchart of different manufacturing techniques of the micro- E¼  100 ð2Þ
ðDHÞm,PCM þ ðDHÞs,PCM
encapsulated PCM. Physical methods result in a relatively
large size, rough surface microcapsules as compared to chemical The melting latent heat and the latent heat of crystallization
methods. Hawlader et al. [31] reported a substantial drop in are identical for a perfectly reversible PCM. The difference
heat storage capacity with the physical methods as compared to between the two arises due to different melting and solidification
that of chemical methods. Among the chemical methods, in points. The difference in melting and solidification point may be
situ polymerization was found to be a favorite choice for the attributed to the effect of subcooling, or incongruent melting.
encapsulation due to its excellent shell structure and smaller Higher encapsulation efficiency is desirable due to its higher
capsule size [37]. mechanical strength and leak proof characteristics. The phase
5606 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

change enthalpy of the encapsulated PCM is a strong function of effective heat transfer [43]. Sari et al. [39] demonstrated that
encapsulation ratio and encapsulation efficiency [38]. Hawlader micro-encapsulated PCMs are thermally more reliable and che-
et al. [31] mentioned that the encapsulation efficiency is a critical mically more stable than that of macro-encapsulated PCMs.
parameter in determining the quantity of PCM to be encapsulated. The only problem with microencapsulated PCM is the possibility of
increase in supercooling [33]. Due to supercooling; PCM retains its
liquid phase even below its freezing point. The supercooling can be
4. Types of PCM encapsulation based on size prevented by incorporating nucleating agents [44]. Fan et al. [45]
demonstrated that separate addition of 6 wt% sodium chloride and
Based on size, encapsulated PCM can be classified as follows 9 wt% 1-octadecanol in core material resulted in prevention of
supercooling, however, the microcapsule surface became rough.
i) macro (above 1 mm), Addition of 20 wt% paraffin yielded no supercooling and dispersa-
ii) micro (0–1000 mm) and bility. It also resulted in excellent surface finish. Biswas [46] added
iii) nano (0–1000 nm) encapsulated PCM. extra water to reduce the intensity of the supercooling.
There are also studies on the nano-encapsulated PCM for
Macroencapsulation is a common way of encapsulating the thermal energy storage [47–49]. The advanced technological
PCM for thermal energy storage applications. The container shape developments have made it possible to encapsulate the PCM at
may be spherical, tubular, cylindrical or rectangular as shown in the nano-scale. Sukhorukov et al. [50] applied the same force on
Fig. 3. Metallic encapsulant is preferred if high heat transfer is the 10 nm and 10 mm size polyelectrolyte capsules and observed that
criteria, else, plastic containers are most widely used. However, deformation for the 10 nm capsule was substantially smaller as
compatibility of both metallic and plastic encapsulants with the compared to that of 10 mm capsule. This shows that nano-
PCM needs to be checked. Climator [41] produces rectangular capsules are structurally more stable as compared to macro and
shape pouches of plastic foil integrated with metallic layers. micro-capsules and there is a great potential in the use of
Rubitherm [42] uses rectangular box to encapsulate the PCM. nanocapsules for thermal energy storage applications. However,
Tin-plated food cans and plastic bottles found to be the cheapest the research on nanocapsule is still at the laboratory level. More
containers for the macroencapsulation. investigations are required to bring nanocapsules into the com-
The manufacturing of microencapsulated PCM is more com- mercial applications. The macro and micro-capsules have been
plex than macroencapsulated PCM as its size falls below 1 mm. successfully commercialized in the market for the TESS applica-
However, microencapsulation result in a higher heat transfer tions. Table 1 shows the product details of the industries that are
rates as compared to that of macroencapsulation [22,31]. This is involved in the manufacture of the encapsulated PCMs.
attributed to a substantially higher surface area to volume ratio,
ability to withstand the change in volume during phase change
process and less chemical reactivity of PCM with the shell 5. Performance improvement of a thermal system using
material. Higher heat transfer rate results in rapid melting and encapsulated PCM
solidification of the micro-encapsulated PCM. For macro-capsules,
the large capsule size results in temperature differential at the This section provides detailed information on the performance
PCM core and boundary. The edge remains solid, whereas, core improvement of a thermal system due to incorporation of PCM.
part may still remain in the liquid form, thus preventing the Maximum heat transfer between the PCM and heat transfer fluid

Table 1
Manufacturers and their specifications of encapsulated PCMs.

Trademark name/ PCM (s) Shell material (s) Container (s) Average Application (s) Reference
Industry container size

Cristopia Eutectic salts Polyolefin Spherical balls 77 mm Industrial refrigeration, building [36]
conditioning
ClimSel/climator Sodium acetate, – Pouches – Medicine transportation, clothing, [41]
sodium sulphate air-conditioning, electronic
cooling, fire protection
Rubitherm Paraffin, salt hydrate in Aluminum, plastic Box, bag – Storage and transport of food, [42]
granulate, powder and medical equipments, storage
compound forms materials for textile
LatestTM/ TEAP Glauber’s salt, soda Aluminum, steel and Bottles, balls 25.4 mm Hot pads and solar heating, [51]
Energy ash, sodium acetate polyethylene telecom enclosure, back-up air-
and paraffin wax conditioning, cold storage
PCM Products Ltd. Eutectics, salt hydrates, Rubber, HDPE plastic Tube, ball, pouches, 40 mm Space International space station, [52]
organic materials, and plate automotive passive cooling, solar
high temperature salts heating and heat recovery
MPCM/Microtek Paraffin polymer – 17–20 mm Active wear clothing, woven and [53]
Laboratories Inc. non-woven textiles, building
materials, packaging, and
electronics
Micronals/BASF Paraffin wax Polymer Microcapsules 5 mm Building conditioning, surface [54]
impregnated with cooling
gypsum wall boards
DuPontTM Paraffin wax Aluminum Wall panels – Building conditioning, fire [55]
EnergainTM protection
Aegis Inorganic salts High density Panels, spherical balls, 75 mm ball dia., Cold storage, boilers, solar water [56]
polyethylene pouches 145 mm  260 - heaters, transport of blood, frozen
mm size pouch food, fruits and vegetables etc.
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5607

(HTF) or surrounding environment is very essential in order PCM and simplifies the problem with a reasonable accuracy.
to make a system more compact and efficient [57]. However, Bony et al. [69] investigated effect of internal convection inside
most of the PCMs (especially organic PCMs) show a lower thermal the paraffin that was encapsulated using an aluminum container
conductivity, hence, results in a decreased heat transfer rate. of dimensions 8.8 cm  15 cm  0.03 cm. It was observed that
There are numerous studies that explain the techniques for temperature fluctuations were increased during the phase change
enhancement in heat transfer of PCMs [58–60]. These techniques process resulting in increased simulation time.
primarily focus on increasing the thermal conductivity of PCM to Talmatsky and Kribus [70] compared effectiveness of PCM based
improve the system performance. Only a brief overview of these solar water heater with the conventional solar water heater. The
techniques is provided here in the initial part of this section. PCM was encapsulated inside a small cylindrical container. A
Velraj et al. [58] listed heat transfer enhancement techniques number of containers were placed at the top layer of the storage
for the PCM based applications. It was reported that the heat tank. Surprisingly, only a marginal gain in improvement was
transfer can be enhanced by the following ways. observed for the PCM based solar water heater. In few cases,
even a loss in the performance was observed. Ibanez et al. [71]
1. Using fin configuration. performed experimental and numerical studies on improvement in
2. Inserting a high thermal conductivity metal matrix into a PCM. heat storage capacity of a solar hot water storage tank using sodium
3. Dispersing the PCM with a high thermal conductivity particles. acetate trihydrate encapsulated in aluminum bottles of 8.8 cm
4. By micro-encapsulation of the PCMs. diameter and 31.5 cm height. The bottles were placed in the
cylindrical water storage tank. It was observed that the total solar
Ettouney et al. [61] observed a three-fold decrease in Fourier fraction was increased from 4% to 8% due to incorporation of
number and a three-fold increase in Nusselt number (hence the encapsulated PCM. The solar fraction represents the contribution
heat transfer rate) by inserting metal screen/spheres in the paraffin. of solar energy to the total energy that is to be purchased. Later, it
Sari [62] reported that thermal conductivity of paraffin/high density was suggested that merely increase in PCM will not improve the
polyethylene composites can be increased by about 24% by adding performance. There is a critical value, beyond which addition of
3 wt% expanded and exfoliated graphite. Bellemare [63] reported PCM will not improve the thermal performance of the system.
five methods of applying conductive layer on the encapsulated PCM Cabeza et al. [72] investigated the use of sodium acetate trihydrate
to improve its thermal and electrical conductivity. These are encapsulated in a cylindrical aluminum container of size 8.8 cm 
sputtering, evaporation, chemical vapor deposition, electrochemical 31.5 cm for thermal energy storage. The energy density as calcu-
and electroless deposition. Out of these, electroless deposition has lated by using sensible heat of water was marked as a baseline case.
positively influenced the encapsulated PCM. The applied layer of It was reported that the increase in energy densities for 2, 4 and
silver on the micro-encapsulated PCM has substantially improved 6 PCM modules for 1 K temperature difference were 40%, 57.2% and
the thermal and electrical conductivity. 66.7%, respectively. For 8 K temperature difference they were
Regin et al. [64] presented a review on the use of PCM capsules 6%, 12% and 16.4%, respectively. The temperature of the top layers
for thermal energy storage application. It was reported that the in the storage tank was warmer than 54 1C for the duration of
determination of heat transfer during phase change process is about 10–12 h. Mehling et al. [73] used PCM modules of size
complicated due to non-linear operation, change in volume and 10 cm  30 cm filled with a mixture of PCM–graphite composite.
inadequate knowledge of heat transfer mechanism. The above It was observed that the energy density was increased by about 20%
phenomena found to be the major source of inaccurate prediction to 45%, whereas, the hot water storage period was extended by
of performance of a thermal system. Later, Jegadheeswaran and about 50% to 200%.
Pohekar [60] in their review reported that microencapsulation of Tyagi et al. [74] reported that microencapsulation is one of the
PCM not only enhances the heat transfer characteristic due to best ways of utilizing PCM to maintain the thermal comfort
increase in surface area to volume ratio but also alleviates the within a building. The microencapsulated PCM can be mixed
problems that arises due to change in volume and lower thermal with either concrete or gypsum wall. This mixture has the ability
conductivity. It was suggested that there is a need to perform a to reduce the temperature fluctuations especially for the light-
comparative study of the microencapsulated PCM with the pure weight buildings. Schossig et al. [75] described that micro-
PCM to assess its performance. Farid et al. [65] reported that encapsulation of PCMs is the easiest way to tackle the problems
higher heat transfer surface area and the decreased reactivity of raised due to macro-encapsulation or direct immersion. The PCM
the microencapsulated PCM are advantageous for the improve- microcapsules can be directly integrated with the building wall.
ment in thermal performance of a system. Zhao [66] described The micro level size of PCM avoids its destruction during drilling
that microencapsulated PCM has a good potential for thermal the holes in the building wall. Other benefits of micro-encapsula-
energy storage applications. Certain issues that were raised tion are high heat transfer rates and better phase change proper-
related to the encapsulated PCM are instability, agglomeration ties. The PCM microcapsules of 8 mm diameter were integrated
and nano size fabrication. It was reported that more research on with the plaster boards. It was observed that, during day time,
MPCM based thermal energy storage system is required to reduce PCM integrated plaster wall reduced the ambient temperature by
the overall cost of the system. 4 K as compared to plaster wall without PCM. The maximum
Dutil et al. [67] suggested that effect of micro and nanocap- temperature in the PCM room occurred after one hour. During
sules on the effective viscosity of the fluid and thermal dilation night time, the PCM room temperature was increased to maintain
of PCM needs to be investigated. The use of carbon fiber to the thermal comfort condition. Subsequently, Cabeza et al. [43]
improve the thermal conductivity, although it has a poor thermal observed a drop of 2 1C for a microencapsulated PCM filled cubicle
conductivity was questioned. Prakash et al. [68] during his as compared to conventional cubicle. The PCM used was Micronal
numerical simulations reported that movement of solid–liquid PCM (from BASF) with a latent heat of fusion 110 kJ/kg. An
boundary poses a problem to simulate the phase change process improved thermal inertia was observed with the microencapsu-
due to lack of knowledge of the movement speed and the two lated PCM. Castellon et al. [76] carried out similar studies with
phase mixture. The problem becomes severe if the PCM has more two different cubicles, one with a mixture of PCM and concrete and
depth, as it takes more time to move the interface boundary from other with concrete only. The volume of both cubicles was kept the
one end to the other. On the other hand, the numerical studies same. A 4 1C temperature difference was observed between the
can assume a single phase solution inside the micro-encapsulated two cubicles. The peak temperature for the PCM-concrete cubicle
5608 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

occurred 2 h later than the concrete cubicle. Douglas [77] demon- especially, thermal comfort using coat or vest. Melamine–
strated the use of encapsulated paraffin (octadecane) in the floor formaldehyde was used as a shell material for micro-encapsula-
tile for residential building cooling during day time and heating tion of octadecane. The microcapsule size was varied from 2 mm
during night time. It was found that, using micro-encapsulated PCM to 40 mm, whereas, macrocapsule size was in the range of 1 mm
of 21 mm diameter, the thermal energy storage was about 2.02 MJ/ to 10 mm. Ma et al. [86] used microcapsules of size 0.5–2 mm
m2 for a half inch floor tile. Corresponding increase in solar saving containing paraffin as a PCM. The encapsulation was carried out
and annual cost saving were 17.3% and $100.34, respectively. with PMMA. It was reported that microencapsulated PCM has
Castellon et al. [78] reported that use of micro-encapsulated good potential for thermal energy storage applications. A good
PCM in a sandwich panel resulted in increased thermal inertia thermal reliability was observed as the phase change properties
and decreased energy demand for the building construction were marginally changed even after 1000 thermal cycles.
application. Li et al. [79] used microencapsulated paraffin and a Zhang et al. [87] performed experiments on n-octadecane
composite mixture of high density polyethylene and wood flour micro-encapsulated with urea–melamine–formaldehyde with dif-
for the latent heat storage. The micro-encapsulation of the PCM ferent mole ratios to assess its phase change properties and
prevented it to mix with the composite mixture. The average thermal stability. The best performance was achieved at mole
particle size of the PCM was 7.29 mm. The thermal conductivity of ratios of urea–melamine–formaldehyde in the order of 0.2:0.8:3
the form-stable PCM was increased by 17.7% by adding 8.8 wt% that resulted in enhanced thermal stability up to 163 1C.
micro-mist graphite. It was observed that the addition of micro- The stability was further increased up to 200 1C by adding
mist graphite has not deteriorated the mechanical properties of cyclohexane. Later, Salaun et al. [88] demonstrated the effect of
the form-stable PCM. The mechanical test revealed the leak proof ratio of formaldehyde/melamine (F/M) on the mechanical proper-
characteristics of the molten PCM. The form-stable PCM was ties of paraffin encapsulated with amino resin. It was reported
found to be thermally stable after subjecting it to 100 melt– that a lower F/M ratio results in a smooth encapsulation surface
freeze cycles. Subsequently, Kenisarin and Kenisarina [80] pre- with a significant reduction in the structural strength of the
sented the developments in form-stable PCMs for thermal energy microcapsule. Conversely, at higher F/M ratio, better mechanical
storage applications. The suggested structure supporting materials properties of the encapsulated PCM were observed.
for the form-stable PCM are high-density polyethylene, styrene–
butadiene–styrene triblock copolymer, poly vynil chloride and poly
vynil alcohol. The form-stable PCMs represent the solid–solid phase 6. Effect of core-to-coating ratio
transition materials. It was reported that the form-stable PCMs
are free from certain issues, such as, supercooling, instability, high Core-to-coating ratio is a critical parameter that decides the
volume change etc. that may incur during solid–liquid phase mechanical strength of the encapsulated PCM. A lower core-to-
transition. coating ratio leads to excessive shell thickness, which in turn
Nallussamy et al. [81] reported the use of paraffin encapsu- reduces the amount of PCM contained, whereas, the encapsulated
lated with a high density polyethylene. The encapsulated sphe- PCM strength deteriorates and the chances of PCM spillage
rical capsule has a diameter of 55 mm and thickness of 0.8 mm. increases for a higher core-to-coating ratio. A review of effect of
The 264 capsules occupied about 50% of the storage tank space. It core-to-coating ratio on the structural and thermal stability of the
was observed that batch wise discharge of water with combined encapsulated PCM is given here in detail.
energy storage system (sensible heatþlatent heat) resulted in fast Su et al. [89] investigated effect of various core-to-shell mass
charging period as compared to continuous discharge with only ratios on the performance of an encapsulated PCM. Lauryl alcohol
sensible heat storage. Esen et al. [82] numerically investigated and melamine–formaldehyde resin were used as core and shell
two cases, first, PCM packed in the cylinder with a parallel fluid materials, respectively. The encapsulated PCM diameter was in
flow over it (mode 1) and second, the fluid flows through cylinder the range of 5–10 mm. The core-to-shell mass ratio was varied
that is immersed in the PCM (mode 2). Between these two, mode from 1:1 to 4:1 in the step of 1:1. It was reported that higher core
2 found to be the best heat transfer mechanism resulting in a material is always essential to store and release more thermal
substantially reduced melting time for the PCM. Kousksou [83] energy. However, for a higher core size, a decreased shell thick-
reported that efficiency of a thermal storage system can be ness can adversely affect the mechanical properties of the
improved by arranging the layers of spherical capsules containing encapsulated PCM. The core-to-shell mass ratio of 3:1 was found
different PCMs in a particular order. The PCMs used were PCM28, to be the optimum. It was also observed that the mechanical
PCM30 and PCM32 encapsulated in a 60 mm spherical capsule properties of double-shell micro-encapsulated PCM were excel-
and placed in a cylindrical tank of height 1.5 m. PCM28, PCM30 lent as compared to that of single-shell. Subsequently, Hawlader
and PCM32 represent the PCMs with the melting point of 28 1C, et al. [31] reported that a lower coating thickness results in poor
30 1C and 32 1C, respectively. Two cases were studied; (i) PCM28, performance of a micro-encapsulated PCM. A higher core-to-
PCM30 and PCM32 arranged in equal layers in the order of bottom coating ratio leads to an increased micro-encapsulation efficiency
to top of the tank and (ii) the reverse order as given in (i). In the and hence, rapid storage and release of thermal energy.
former case, the PCM32 placed in the top layer could not melt, Ohtsubo et al. [90] investigated breaking behavior of the
however, in the latter case, the PCM28 placed in the top layer was microcapsule based on the mass mean diameter (D) and wall
successfully melted. Hence, thermal performance with the latter thickness (T). The capsule was microencapsulated with polypro-
case was improved by restructuring the layers of the PCMs. pylene. It was reported that at large (D/T) ratio, a small force is
Song et al. [84] demonstrated an increase in wall strength of enough to break the 50% of the microcapsule. Roy and Sengupta
the microencapsulated bromo-hexadecane due to addition [91] performed experimental studies on micro-encapsulated
of silver nano-particles. The thermal and structural stability of PCMs for the higher heat transfer rates. Two PCMs under study
PCM microcapsules incorporated with silver nano-particles was were n-eicosane and stearic acid with two different shell thick-
substantially higher as compared to conventional PCM micro- nesses of 15% and 30% of the total microcapsule volume. The
capsules. This was attributed to the increase in strength and structural and thermal stability of microcapsules were investi-
toughness due to addition of silver nano-particles. Davis et al. [85] gated using thermal cycling and radiation test. It was observed
used macrocapsules containing plurality of microcapsules suspended that the PCM with lower shell thickness (15% of the total
in a gelling agent for the thermal energy storage applications, microcapsule volume) failed to sustain the repeated thermal
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5609

cycles through melting point. However, microcapsules with thermal characteristics not only improves the performance of a
higher shell thickness found to be structurally and thermally system but also increases the number of thermal cycles that the
sound for at least 100 cycles. Zhang and Wang [40] performed encapsulated PCM withstands.
microencapsulation of n-octadecane using polyurea as a shell An ideal shell material should have following properties:
material. The investigations were carried out at different core-to-
shell weight ratios of 70/30 and 75/25. The mean particle sizes at 1. It should have sufficient structural and thermal strength to
these two core-to-shell ratio were 6.9 mm and 7.1 mm, respec- withstand the phase change process of PCM.
tively. For a higher core-to-coating ratio (i.e., 75/25), an early 2. It should retain all the thermophysical properties at the micro
spillage of the PCM was observed at a temperature of about and nano-level size.
200 1C. A better thermal stability of microencapsulated PCM with 3. It should be leak proof.
a lower core-to-coating ratio was observed. The microcapsule 4. It should not react with the enclosed PCM.
synthesized using Jeffamine resulted in higher encapsulation 5. It should be a good water diffusion barrier.
efficiency and better phase change properties as compared to 6. It should have higher thermal conductivity to ease the heat
synthesized using ethylene diamine and diethylene triamine. exchange between the PCM and its surrounding.
Wei et al. [92] investigated the effect of PCM diameter (2 mm,
3 mm, 4 mm and 5 mm) on the heat transfer characteristics. Common materials that can be used for encapsulation are
A rapid heat release was observed for the smallest PCM diameter polypropylene, polyolefin, polyamide, silica, polyurea, urea–
(i.e., 2 mm), and gradually decreased with increase in diameter. formaldehyde, copper, aluminum etc. A survey on effect of shell
This was attributed to the high surface area to volume ratio of the material on the heat transfer characteristics is presented below.
small diameter encapsulated PCM. The effect of shell thickness Werner [95] performed experiments on thermal energy sto-
(0.2 mm and 0.4 mm thickness) on heat release showed that a rage using a phase change mixture of 90% myristic and 10% lauric
higher shell thickness resulted in modestly improved capsule acid. Three different shell materials, namely, polypropylene,
performance. However, due to increased shell thickness, the polyethylene and polyamide were used during the experiment.
amount of core material reduces and hence affects the heat It was observed that first two containers (polypropylene and
storage capacity. In contrast to the results of Wei [92], Ettouney polyethylene) showed diffusion with paraffin, whereas, there was
et al. [93] observed that increase in diameter and number of no chemical reaction between the PCM and the polyamide. It was
beads placed inside a spherical capsule result in enhanced heat also reported that encapsulation of organic PCM is more difficult
transfer characteristics. Materials used for the spherical capsule than inorganic PCM. This was attributed to the similar structure
and bead were copper and stainless steel, respectively. The of the organic PCM and the plastic container that leads to a
spherical capsule diameter was kept at 30 mm and bead dia- diffusion or initiation of chemical reaction. Sun and Zhang [96]
meters were varied to 4 mm, 5 mm and 6 mm. investigated effect of different coating materials, namely, melamine–
An overview of key parameters of encapsulated PCM as used formaldehyde, urea–formaldehyde and gelatin on the mechanical
by various researchers and their result is shown in Table 2. strength of the microcapsule. It was observed that melamine–
formaldehyde and urea–formaldehyde ruptured under the compres-
sion test, whereas, gelatin was found to be structurally stable. The
7. Effect of shell material gelatin capsule was elastic up to the deformation of 50%.
Zhang et al. [40] demonstrated that polyurea has good physical
Shell material plays an important role in deciding the heat properties and chemical stability. It is also completely insoluble in
transfer characteristics as well as mechanical strength of the water and other solvents. Therefore, it was reported that polyurea
encapsulated PCM. A high strength shell material with good has a great potential to become one of the best shell material for

Table 2
Summary of major encapsulation parameters as used during various investigations.

Sr. no. PCM Method Type Coating Capsule wall Capsule size Remark Refer-ence
material thickness

1. n-Octacosane Emulsion Micro Polymethyl – 0.25 mm Good energy storage [39]

polymerization methacrylate potential
(PMMA)
2. n-octadecane Interfacial Micro Polyurea shell – Core/shell ratio High encapsulation [40]
polycondensation (wt:wt)¼ 70:30 efficiency
3. Octadecane – Micro Polyester – 21 mm Annual saving increased [77]
by 24%
4. Bromo- Polymerization Nano Silver nano-particles 40–60 nm core/shell High thermal and [84]
hexadecane technique ratio¼ 5:1 structural stability of
PCM due to addition of
silver nano-particles
5. n-octadecane In situ Micro Urea—melamine— Core/shell ratio 0.2–5.6 mm Thermal stability [87]
polymerization formaldehyde (wt:wt)¼ 78:22 enhanced by 10 1C
6. n-eicosane – Micro Cross-linked 15–30% 50 mm–250 mm Thicker wall resulted in [91]
and stearic polyvinyl alcohol good thermal and
acid structural stability
7. Paraffin wax – Macro Stainless steel 0.4 mm 2 mm Spherical shape resulted [92]
in highest heat transfer
rate
8. Paraffin Injection or – Polyethylene – – PET shell performed [94]
blowing process terephthalate (PET) better compared to
polyolefin and
polycarbonate
5610 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

the microencapsulation of the PCMs. In the subsequent studies, energy storage. The microcapsules were stored in the microtubule
Zhang et al. [38] reported that silica posses a substantially higher of length 0.1–50 mm and diameter 0.1–1000 mm, encapsulated
thermal conductivity of 1.296 W/m-K as compared to polymeric using polymer. It was reported that due to high hollowness and
materials (k ¼0.2 W/m K). The phase change properties, thermal micro-size diameter, the microtubules can efficiently and rapidly
conductivity, encapsulation efficiency and antiosmosis properties transfers the heat. Agyenim et al. [19] reported that cylindrical
were significantly enhanced due to micro-encapsulation of octa- and rectangular shapes are the most commonly used container
decane with the silica shell. The encapsulation with silica has shapes for the enhanced heat transfer between the PCM and HTF.
improved the thermal conductivity from 0.1505 W/m K to A shell and tube arrangement found to give the minimal heat loss.
0.6213 W/m K. Later, Fang et al. [34] as well reported that silica Darkwa and Su [99] performed simulation studies on the thermal
has excellent physical properties to be qualified as a good shell performance of a microencapsulated PCM board by varying the
material. It has good chemical and thermal stability, significantly encapsulation geometry (rectangular, triangular and pyramidal).
higher thermal conductivity and high storage capacity. The silica It was observed that the thermal response time for the rectan-
shell provides sufficient mechanical strength and prevents leak- gular and triangular geometries were half that of pyramidal
age of the molten PCM. The difference between melting and geometry. The microencapsulation resulted in ten times increase
solidifying temperature was found to be marginal for the silica in thermal conductivity as compared to that of pure PCM.
encapsulated paraffin as compared to paraffin. This was attrib- However, the energy storage density was reduced by about 48%.
uted to the silica shell that acts as a nucleating agent.
Alkan et al. [29] carried out experiments on preparation,
characterization and thermal analysis of microencapsulated doc- 9. Melting and solidification of PCM
osane with PMMA as a coating material. After 1000, 3000 and
5000 thermal cycles, a substantially improved thermal reliability Performance of a PCM based thermal system is significantly
was observed in terms of change in temperature and enthalpy. affected by the melting and solidification characteristics of the
Garcia et al. [26] assessed thermal stability of microcapsules PCM. Depending upon the geometry and the flow and heat
synthesized by different shell compositions, namely, Sterilized transfer characteristics, one or more dimensionless parameters
Gelatine/Arabic Gum (SG/AG) and Agar-Agar/Arabic Gum (AA/AG). amongst Nusselt number (Nu), Rayleigh number (Ra), Stefan
The results of Thermogravimetric analyses showed that the micro- number (Ste) and Grashof number (Gr) may play an important
capsules decomposed in a more gradual manner for the AA/AG role during the phase change process. The Stefan number is the
method, whereas, for the SG/AG method, the microcapsules break ratio of sensible heat to the latent heat of the PCM as given by the
and decomposed at the same time. Hatfield [97] used polyurethane- following equation.
urea to encapsulate polyethylene glycol 8000 using interfacial
C P ðT f T 0 Þ
polymerization. It was reported that the shell material must be Ste ¼ ð3Þ
elastomeric to accommodate the change in volume during the phase DH
change process. A minimal loss in latent heat of fusion was observed For higher melting rate a lower Stefan number is desirable,
due to encapsulation of the PCM. whereas, a higher Stefan number can improve the solidification rate.
Although melamine–formaldehyde and urea–formaldehyde Accurate prediction of the flow and heat transfer character-
are one of the most commonly used shell materials, the health istics during melting and solidification of PCM is a very compli-
and environmental hazard issues have been observed due to cated task due to moving interface boundary. The speed of this
emission of formaldehyde [29,34]. Therefore, the recent trend is boundary is not known a priori. Josef Stefan was the first who
inclined towards the use of formaldehyde-free shell materials. reported this problem, hence, it is also known as the ‘Stefan
Zhang et al. [38] suggested that use of combination of organic– problem’ or the moving boundary problem [100]. Analytical
inorganic materials as a shell material can be an optimistic choice. solution for this problem is available only for one-dimensional
Organic material offers structural flexibility and easier processing, case with very simplified boundary conditions. The unknown
whereas, inorganic materials are well known for good chemical speed of the solid–liquid boundary and the highly non-linear
and thermal stability, excellent flame retardancy, higher struc- phase change characteristics makes it difficult to achieve the
tural strength and substantially higher thermal conductivity. analytical solution for the complex cases. However, numerical
Jegadheeswaran and Pohekar [60] suggested the use of low methods can be used with a reasonable accuracy to tackle the
density high thermal conductivity additives, such as carbon fibers, above challenges. Teng and Akin [101] explained that enthalpy
that have lower weight, excellent corrosion resistance, compat- and capacity are the two most commonly used fixed domain
ibility with most of the PCMs and thermal conductivity almost methods to deal with such problems.
equal to that of aluminum and copper. For proper functioning of a PCM based thermal system, rapid
melting and solidification of the PCM is always desirable. The
variation of thermophysical properties during melting and soli-
8. Effect of encapsulation geometry dification depends upon the PCM chosen. The thermophysical
properties can be assumed to be independent of temperature but
It is observed that encapsulation geometry has substantial effect different for solid and liquid phases [102,103]. Dwarka and Kim
on the heat transfer characteristics of the PCM. A brief description [104] considered the constant thermophysical properties during
of commonly used encapsulation geometries is given in Section 4 phase change process except the specific heat. Long [105]
(see Fig. 3). A survey of effect of various encapsulation geometries assumed constant thermophysical properties during phase
on the heat transfer characteristics is provided below. change process. The effect of natural convection in the liquid
Wei et al. [92] performed numerical and experimental studies phase was neglected. This section provides a survey on the effect
on various geometries of encapsulated PCMs, namely, sphere, of mass flow rate of HTF, inlet and initial temperature of HTF,
cylinder, plate and tube to improve the heat transfer rate. It was various shell materials and container shapes on the flow and heat
reported that the spherical shape resulted in the highest heat transfer characteristics of the PCM during the solidification and
transfer rate. For other geometries, the heat transfer rate melt processes.
decreased in the order of cylinder, plate and tube. Zhang et al. Veerappan et al. [106] analyzed the effect of encapsulation
[98] described the application of microtubule PCMs for thermal size, initial PCM temperature and external fluid temperature on
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5611

the solidification time. The encapsulated PCM diameter was The heat generation parameter is given by:
varied from 4 cm to 12 cm. It was observed that a large size
_ 2
qR
PCM requires more time to solidify and vice versa. The initial b¼ ð6Þ
kðT 0 T f Þ
temperature found to have negligible effect on the solidification
time. Wu et al. [107] observed that inlet temperature of HTF, The presence of heat generation within the encapsulated PCM
porosity of packed bed and flow rate of HTF have a significant significantly increases the solidification time and accelerates the
influence on the complete solidification and melting time than melting process. It was also observed that increasing the capsule
the effect of capsule diameter of the PCM. A higher HTF inlet radius substantially rises the complete solidification time. This is
temperature resulted in substantially reduced melting time, attributed to the rise in heat generation parameter due to increase
whereas, higher HTF flow rate and higher porosity of packed in radius of the cylinder as evident from Eq. (6).
bed led to a substantial decrease in the solidification and melting Stritih [112] performed experimental studies on solidification
time. Arkar and Medved [108] reported that heat capacity of a and melting characteristics of paraffin (Rubitherm RT 30) inside a
PCM is a function of temperature. A significant change in specific rectangular container of size 650 mm  500 mm  120 mm.
heat was observed during the phase change process. An apparent The heat transfer correlations for solidification and melting are
heat capacity for the PCM is given by the following equation. given respectively as follows.
qðTÞ Nus ¼ 7  1013 Ra0:9364 ð7Þ
C app ðTÞ ¼ þ Cp ð4Þ
mPCM y
Zukowski [109] formulated a mathematical model of thermal Num ¼ 8  1012 Ra1:0392 ð8Þ
energy storage for heating application wherein a specific heat From above equations, it can be observed that natural convec-
capacity approach was proposed to simulate the model for tion during melting is almost ten times higher than that during
solidification and melting process. The natural convection during solidification. Subsequently, Tan et al. [113] computationally and
melt process was simulated using equivalent thermal conductivity experimentally demonstrated that the conductive heat transfer
as given by the following equation. was dominant in the initial stage of the phase change process.
 m However, with the progress in melting process, natural convec-
keq,p d
¼ CRan ð5Þ tion became dominant. Ettouney et al. [114] observed that natural
kp l
convection was dominant during melting for upward flow of HTF,
It was observed that the charge cycle time was higher than the whereas, for downward flow, the natural convection was negli-
twice as that of discharge cycle. Zivkovic and Fujii [110] per- gible. The solidification process found to be dominated by con-
formed computational and experimental investigations to deter- duction and independent of flow direction of HTF. Cho and Choi
mine the effect of encapsulating container shape on the melting [115] reported the phase change characteristics of paraffin (40%
time of calcium chloride hexahydrate. The model assumed neg- n-tetradecane and 60% n-hexadecane) during melting and solidi-
ligible effects of conduction in the direction of HTF and natural fication and compared it to water. The spherical capsule had a
convection in the molten PCM. The containers were rectangular high-density polyethylene shell with a diameter of 24.5 mm and
(100 mm  100 mm  20 mm) and cylindrical, both made of thickness of 0.8 mm. The spherical capsules were piled up in
stainless steel. In order to compare, the volume and heat transfer seven layers. A shorter melting time was observed for the first
area of both of the containers were kept equal. A marginal layer placed near the edge of the storage tank. This was attributed
difference in melting time was observed at smaller volume. to the lower porosity at the center of the tank that results in
However, at large volume, the rectangular container has halved reduced heat transfer rates. The effect of increased inlet tempera-
the melting time of PCM as compared to that of cylindrical ture showed that the phase change period during solidification
container. was significantly higher than that of melting process. In contrast,
Zalba et al. [3] demonstrated the use of PCM for free-cooling of Zukowski et al. [116] in their first ever attempt to use paraffin
building. It was observed that the thickness of encapsulation, inlet wax (RT-56) encapsulated with the polyethylene bag observed
air temperature and air flow have significant influence on the that the charging period was substantially long, whereas, dis-
solidification process, whereas, during melting process, the inlet charge period (cooling process) was significantly reduced.
air temperature showed more influence as compared to the Ismail and Henriquez [117] performed a detailed study on the
encapsulation thickness. Kalaiselvam et al. [111] analytically effect of shell material, shell thickness, capsule diameter and initial
and experimentally studied the solidification and melting char- PCM temperature on the total solidification time of the PCM. The
acteristics of a PCM (60% n-tetradecane þ40% n-hexadecane) results are shown in Table 3. It was observed that a shell material
encapsulated in a copper cylinder of size 70 mm  350 mm  with high thermal conductivity, smaller capsule size and lower
1 mm. It was reported that solidification and melting processes external surface temperature results in reduced time for the
are dominated by conduction and natural convection, respec- complete solidification. The critical radius for copper, PVC and glass
tively. The solidification time depends upon Stefan number and for a fixed capsule diameter of 0.05 m were found to be 17.46 m,
heat generation parameter (b), whereas, melting time is a func- 0.003 m and 0.054 m, respectively. Increasing the capsule radius
tion of equivalent thermal conductivity. until the critical radius increases the heat transfer rate, hence,

Table 3
Effect of various parameters on the solidification time of PCM [117].

Shell material Copper Stainless steel Teflon PVC

Solidification time Short Short Large Largest

Capsule diameter (mm) 20 100 200 400

Solidification time Shortest Short Large Largest

External surface temperature (1C) 5  10  20 –

Solidification time Shortest Short Large –
5612 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

Table 4 great potential in the PCS in terms of increase in heat transfer

Melting time for various shell materials as observed by Ismail and Henriquez rate. The Nusselt number for PCS varies from 1.5 to 4 times the
[118].
Nusselt number for single phase fluid. The MPCS can be analyzed
Shell material Copper Aluminum Polyethylene Acrylic PVC as a lumped system if the Biot number is less than 0.1. For this,
there should be negligible resistance to the conduction as com-
Melting time (h) 7 7 8 9 9.3 pared to resistance to the heat transfer between MPCS system and
the surrounding [131]. Chen and Fang [132] presented a review
on heat transfer characteristics of MPCS flowing in a horizontal
decreases the time required for the solidification. Therefore, heat circular tube. It was reported that the heat transfer rate of the
transfer rate can be increased by increasing the diameter of copper MPCS increases with reduction in supercooling and increase in mass
and glass capsules. However, for PVC, as the critical radius was less fraction and the Reynolds number of the slurry. Zhang et al. [133]
than the capsule size of 0.05 m, any increase in capsule size would reported that thermophysical properties of MPCS play an impor-
have decreased the heat transfer rate. Later, Ismail and Henriquez tant role in the heat transfer process. It was suggested to add
[118] demonstrated effect of various shell materials, namely, copper, certain amount of nano-particles to improve the thermal con-
aluminum, acrylic, PVC and polyethylene on the solidification and ductivity of the MPCS. In order to treat the slurry as the New-
melting time of PCM encapsulated in a 77 mm diameter spherical tonian fluid, it was recommended that the total volume fraction of
capsule of thickness 2 mm. The spherical capsule contained water the MPCS should fall below 25%. Beyond certain limit, the
and ethylene glycol of 30% volumetric concentration. Copper and increased volumetric concentration of the MPCS results in rapid
aluminum shells resulted in the shortest time for the melting of the increase in viscosity, pressure drop and decrease in convective
PCM. Table 4 shows the melting time for all the shell materials. The heat transfer [127,134]. Choi et al. [128] observed that melting of
melting time required for polyethylene was modestly good, PCS particles resulted in substantial reduction in local pressure
whereas, PVC experienced a longer melting time of about 9.3 h. It drop and significant variation in local heat transfer coefficient
was also observed that with decrease in working fluid entry from inlet to outlet. Alvarado et al. [135] showed an increase in
temperature, there was a significant reduction in time required for heat storage capacity of MPCS even at low mass fractions. The
both charging and discharging process. Similar studies were carried microcapsules found to be durable when smaller than 10 mm.
out by Ismail and Moraes [119] using a mixture of water–glycol as a Yang et al. [136] provided MPCS and phase change emulsion as
PCM. It was reported that a higher thermal conductivity of the shell two kinds of HTFs. It was demonstrated that encapsulation of
material, smaller capsule size and lower HTF temperature reduces tetradecane with polymethyl methacrylate (PMMA) and polyethyl
the total solidification time. methacrylate (PEMA) resulted in better heat storage capacity as
Akgun et al. [120] investigated effects of mass flow rate and compared to polystyrene.
HTF temperature on the solidification and melting characteristics Zeng et al. [129] reported that during phase change process,
of paraffin in a tube in shell heat exchanger. It was observed that Stefan number (Ste) and dimensionless phase change temperature
the increase in HTF temperature results in increased solidification range (Mr) are the two most important parameters that influence
time. The effect of HTF mass flow rate found to be negligible at the the Nusselt number fluctuation. It was observed that the Nusselt
tube inlet. However, far upstream from the tube inlet, the increase number fluctuation increases with decrease in both Ste and
in HTF mass flow rate showed higher HTF temperature and hence Mr. Wang et al. [137] proposed a new correlation for predicting
the reduced melting time. Subsequently, Regin et al. [121] as well local heat transfer coefficient for laminar MPCS. An increase in
reported that increase in HTF temperature and mass flow rate slurry particle fraction resulted in the improvement in local
resulted in the lower melting time. The paraffin wax was used as Nusselt number. The local heat transfer coefficient for MPCS
a PCM contained within the spherical capsule. The investigations was higher than that of pure water. Chen et al. [138] reported
performed with various capsule diameters showed the substan- that using MPCS, the improvement in effective specific heat and
tially reduced melting and solidification time for smaller diameter heat transfer rate were 28.1% and 23.6%, respectively. As com-
capsules as compared to that of large diameter. Due to lower heat pared to water, the saving in pumping cost was about 67.5% due
transfer coefficient during solidification process, the time to increased heat transfer rate. Zhang et al. [139] investigated
required for complete solidification was significantly higher as natural convection heat transfer characteristics of microencapsu-
compared to that of melting process. The above results found to lated PCM in a rectangular heat storage tank. An easier initiation
be in line with the measurements of Wu and Fang [122]. of the natural convection was observed at higher mass concen-
tration of the slurry. A local maximum heat transfer coefficient
was observed during the phase change process.
10. Microencapsulated phase change slurry (MPCS) Hu and Zhang [140] proposed a modified form of conventional
Nusselt number correlation for laminar flow MPCS in a circular tube
The encapsulated phase change material can be dispersed in with constant heat flux. It was demonstrated that Stefan number and
the HTF (commonly water) to increase the heat transfer rate. PCM volumetric concentration of microcapsules are the most influencing
can then be pumped back to store or release the thermal energy. parameters on the heat transfer enhancement of MPCS. Along with
Such a mixture of encapsulated PCM and HTF is termed as the these, initial supercooling, phase change temperature range and
phase change slurry (PCS). The mixture is termed as the micro- microcapsule diameter also found to have considerable effects on
encapsulated phase change slurry (MPCS) in case the encapsula- the heat transfer enhancement. Sabbah et al. [141] showed that for a
tion is at the micro level. The MPCS not only acts as an energy micro-channel heat sink, a significantly higher heat transfer coeffi-
storage device but also as a heat transport system. Due to this, cient can be obtained by using MPCS instead of water only. The low
MPCS is commonly used in secondary loop heat transfer systems concentration high velocity slurry resulted in better heat transfer
such as the refrigeration system. The suspended microcapsules rates. Zhang et al. [142] carried out experimental studies on MPCS in
store and transport large amount of thermal energy as compared a horizontal rectangular enclosure heated from the bottom. It was
to microcapsules that are not in direct contact with the HTF. observed that an increase in mass concentration of the slurry
Substantial investigations have been carried out to determine improved the heat storage capacity and the completion time of heat
the heat and fluid flow characteristics of the PCS [123–129]. storage. Rapid heat storage and high heat transfer coefficient were
Charunyakorn et al. [130] for the first time reported that there is a observed only in the beginning of the heating process. This is
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5613

attributed to a substantially higher temperature difference between aluminum or steel can be a good choice. The metallic shell
the HTF and the MPCS in the beginning of the heating process. materials can also be useful for high temperature PCM appli-
cations. However, their microencapsulation is a challenge.
3. For organic PCMs, the inorganic shell materials can be a good
11. Challenges for designing an encapsulated PCM based choice due to their excellent thermal conductivity, high
thermal system mechanical strength and good diffusion barrier characteristics.
Silica exhibits the above mentioned properties and has a great
The major challenges that may arise while designing the potential to become a good shell material.
encapsulated PCM based thermal system are addressed here as 4. Thermal and structural stability of the microcapsules found to
given below. be substantially improved due to addition of silver nano-
particles. The mechanism for this improvement was attributed
 One of the major obstacles for the commercialization of an to the increased thermal conductivity, toughness and strength
encapsulated PCM based system is the high cost of encapsula- due to distribution of silver nano-particles on the shell surface.
tion. This increases the overall cost of the system. 5. The solidification and melting processes are dominated by
 The correct choice of PCM, shell material, encapsulation prepara- conduction and natural convection, respectively. A high ther-
tion method and its size varies according to the application. mal conductivity, smaller capsule diameter and lower external
 Precise prediction of moving solid–liquid boundary during the surface temperature reduce the total solidification time of the
phase change process is still a major problem to be resolved. encapsulated PCM.
The rate of movement of this boundary is not known a priori. 6. It was observed that the Stefan number, volumetric concen-
 Another important parameter to consider while designing the tration of microcapsule, phase change temperature range and
encapsulated PCM based thermal system is the reduction in capsule diameter have significant influence on the heat trans-
PCM effectiveness over the number of thermal cycles. After fer enhancement of MPCS. Beyond certain limit, the increase in
attaining a certain number of thermal cycles, the thermophy- volumetric concentration of the microcapsule leads to a sub-
sical properties of the PCM deteriorates substantially leading stantial increase in pressure drop and viscosity and decrease in
to a significant reduction in structural and thermal stability of convective heat transfer rate.
the PCM. This results in a decreased system performance.
 For proper functioning of a PCM based TESS, the repetition of Long-term durability while being pumped and being con-
charge and discharge cycles are significantly important. The stantly cooled and heated needs to be experimentally shown for
functioning of the system may disrupt in case the discharged MPCS before a broad industrial adoption.
PCM could not be charged. This is likely to occur for the PCM
based TESS working on natural resources such as solar water
heater, solar space heater etc. Acknowledgment
 For MPCS, the conventional heat transfer correlations cannot
be used due to increased pressure drop and increased viscosity
Authors would like to thank Dr. Andrey Soukhojak and
of the slurry. An in-depth knowledge of heat transfer enhance-
Dr. David Bank (both from The Dow Chemical Company, Midland,
ment mechanism is essential while designing the MPCS based
USA) for their in-depth review and valuable suggestions for the
thermal system.
improvement of this manuscript.
 Manufacture of microencapsulated PCM with a metallic shell
material is still an unresolved problem.
 Other considerable challenges are phase segregation and References
supercooling of the PCM. The inorganic PCMs are observed to
[1] Kyle JA. Material for protecting sheets, &c., in tinning. US Patent 1901; No.
be more prone for these challenges. Although these problems
679,972.
can be alleviated by addition of suitable enhancement materi- [2] Kuznik F, David D, Johannes K, Roux J. A review on phase change materials
als, the impact due to addition of these materials on the latent integrated in building walls. Renewable and Sustainable Energy Reviews
heat storage capacity and phase change temperature of the 2011;15(1):379–91.
[3] Zalba B, Marn JM, Cabeza LF, Mehling H. Free-cooling of buildings with
PCM is evident. phase change materials. International Journal of Refrigeration 2004;27:
839–49.
[4] Pasupathy A, Velraja R, Seeniraj RV. Phase change material-based building
architecture for thermal management in residential and commercial estab-
lishments. Renewable and Sustainable Energy Reviews 2008;12:39–64.
12. Conclusions [5] Antony VAR, Velraj R. Review on free cooling of buildings using phase
change materials. Renewable and Sustainable Energy Reviews
2010;14:2819–29.
This paper presents a thorough survey on the effect of [6] Kandasamy R, Wang XQ, Mujumdar AS. Application of phase change
PCM encapsulation parameters on the flow and heat transfer materials in thermal management of electronics. Applied Thermal Engi-
characteristics as well as structural and thermal stabilities of an neering 2007;27:2822–32.
[7] Tan FL, Tso CP. Cooling of mobile electronic devices using phase change
encapsulated PCM. The major findings of this survey are listed as materials. Applied Thermal Engineering 2004;24:159–69.
given below. [8] Lu TJ. Thermal management of high power electronics with phase change
cooling. International Journal of Heat and Mass Transfer 2000;43:2245–56.
[9] Yagi J, Akiyama T. Storage of thermal energy for effective use of waste heat
1. The core-to-coating ratio found to be a critical parameter that from industries. Journal of Materials Processing Technology 1995;48:
decides the mechanical and thermal stability of the encapsu- 793–804.
lated PCM. A higher core-to-coating ratio results in a weak [10] Nomura T, Okinaka N, Akiyama T. Waste heat transportation system, using
phase change material (PCM) from steelworks to chemical plant. Resources,
shell, whereas, lower core-to-coating ratio reduces the amount
Conservation and Recycling 2010;54:1000–6.
of PCM contained, hence, decreases the heat storage and [11] Mondal S. Phase change materials for smart textiles—an overview. Applied
release capacity. Thermal Engineering 2008;28:1536–50.
2. Thermal conductivity of shell material plays an important role [12] Gin B, Farid MM. The use of PCM panels to improve storage condition of
frozen food. Journal of Food Engineering 2010;100:372–6.
in the heat exchange between the PCM and the HTF. For higher [13] Martin V, He B, Setterwall F. Direct contact PCM–water cold storage.
heat transfer rates, a metallic shell material like copper, Applied Energy 2010;87:2652–9.
5614 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

[14] Fath HES. Technical assessment of solar thermal energy storage technologies. [46] Biswas DR. Thermal energy storage using sodium sulfate decahydrate and
Renewable Energy 1998;14(1–4):35–40. water. Technical note. Solar Energy 1977;19:99–100.
[15] Shukla A, Buddhi D, Sawhney RL. Solar water heaters with phase change [47] Fang G, Li H, Yang F, Liu X, Wu S. Preparation and characterization of nano-
material thermal energy storage medium: a review. Renewable and encapsulated n-tetradecane as phase change material for thermal energy
Sustainable Energy Reviews 2009;13:2119–25. storage. Chemical Engineering Journal 2009;153:217–21.
[16] Mettawee EBS. Assassa GMR. Experimental study of a compact PCM solar [48] Fang Y, Kuang S, Gao X, Zhang Z. Preparation and characterization of novel
collector. Energy 2006;31:2958–68. nano-encapsulated phase change materials. Energy Conversion and Man-
[17] Sokolov M, Keizman Y. Performance indicators for solar pipes with phase agement 2008;49:3704–7.
change storage. Solar Energy 1991;47(5):339–46. [49] Khodadadi JM, Hosseinizadeh SF. Nanoparticle-enhanced phase change
[18] Sarier N, Onder E. The manufacture of microencapsulated phase change materials (NEPCM) with great potential for improved thermal energy
materials suitable for the design of thermally enhanced fabrics. Thermo- storage. International Communications in Heat and Mass Transfer
chimica Acta 2007;452:149–60. 2007;34:534–43.
[19] Agyenim F, Hewitt N, Eames P, Smyth M. A review of materials, heat [50] Sukhorukov G, Fery A, Mohwald H. Intelligent micro- and nanocapsules.
transfer and phase change problem formulation for latent heat thermal Progress in Polymer Science 2005;30:885–97.
energy storage systems (LHTESS). Renewable and Sustainable Energy [51] /www.teappcm.comS.
Reviews 2010;14:615–28. [52] /www.pcmproducts.netS.
[20] Sharma A, Tyagi VV, Chen CR, Buddhi D. Review on thermal energy storage [53] /www.microteklabs.comS.
with phase change materials and applications. Renewable and Sustainable [54] /www.basf.comS.
Energy Reviews 2009;13:318–45. [55] /www.energain.dupont.comS.
[21] Zhu N, Ma Z, Wang S. Dynamic characteristics and energy performance of [56] /www.aegisbt.comS.
buildings using phase change materials: a review. Energy Conversion and [57] Rady M. Granular phase change materials for thermal energy storage:
Management 2009;50:3169–81. experiments and numerical simulations. Applied Thermal Engineering
[22] Khudhair AM, Farid MM. A review on energy conservation in building 2009;29:3149–59.
applications with thermal storage by latent heat using phase change [58] Velraj R, Seeniraj RV, Hafner B, Faber C, Schwarzer K. Heat transfer
materials. Energy Conversion and Management 2004;45:263–75. enhancement in a latent heat storage system. Solar Energy 1999;65(3):
[23] Xi L, Zhang P, Wang RZ. Preparation and thermal characterization of 171–80.
expanded graphite/paraffin composite phase change material. Carbon [59] Fan L, Khodadadi JM. Thermal conductivity enhancement of phase change
2010;48:2538–48. materials for thermal energy storage: a review. Renewable and Sustainable
[24] Song G, Ma S, Tang G, Yin Z, Wang X. Preparation and characterization of Energy Reviews 2011;15(1):24–46.
flame retardant form-stable phase change materials composed by EPDM, [60] Jegadheeswaran S, Pohekar SD. Performance enhancement in latent heat
paraffin and nano magnesium hydroxide. Energy 2010;35:2179–83. thermal storage system: a review. Renewable and Sustainable Energy
[25] Xi P, Gu X, Cheng B, Wang Y. Preparation and characterization of a novel Reviews 2009;13:2225–44.
polymeric based solid–solid phase change heat storage material. Energy [61] Ettouney HM, Alatiqi I, Al-Sahali M, Al-Ali SA. Heat transfer enhancement
Conversion and Management 2009;50:1522–8. by metal screens and metal spheres in phase change energy storage
[26] Garcia LB, Ventol L, Cordobilla R, Benages R, Calvet T, Cuevas-Diarte MA. systems. Renewable Energy 2004;29:841–60.
Phase change materials (PCM) microcapsules with different shell composi- [62] Sari A. Form-stable paraffin/high density polyethylene composites as
tions: preparation, characterization and thermal stability. Solar Energy solid–liquid phase change material for thermal energy storage: preparation
Materials & Solar Cells 2010;94:1235–40. and thermal properties. Energy Conversion and Management 2004;45:
[27] Li W, Zhang XX, Wang XC, Niu JJ. Preparation and characterization of 2033–42.
microencapsulated phase change material with low remnant formaldehyde [63] Bellemare JV. Thermally reflective encapsulated phase change pigment. US
content. Materials Chemistry and Physics 2007;106:437–42. Patent 2007;No. 0031652 A1.
[28] Sari A, Alkan C, Karaipekli A, Onal A. Preparation, characterization and [64] Regin AF, Solanki SC, Saini JS. Heat transfer characteristics of thermal energy
thermal properties of styrene maleic anhydride copolymer (SMA)/fatty acid storage system using PCM capsules: a review. Renewable and Sustainable
composites as form stable phase change materials. Energy Conversion and Energy Reviews 2008;12:2438–58.
Management 2008;49:373–80. [65] Farid MM, Khudhair AM, Razack SAK, Al-Hallaj S. A review on phase change
[29] Alkan C, Sari A, Karaipekli A, Uzun O. Preparation, characterization, and energy storage: materials and applications. Energy Conversion and Manage-
thermal properties of microencapsulated phase change material for thermal ment 2004;45:1597–615.
energy storage. Solar Energy Materials & Solar Cells 2009;93:143–7. [66] Zhao CY, Zhang GH. Review on microencapsulated phase change materials
[30] Green KB. Carbonless paper production. Ohio: NCR Corporation; 1953. (MEPCMs): fabrication, characterization and applications. Renewable and
[31] Hawlader MNA, Uddin MS, Khin MM. Microencapsulated PCM thermal- Sustainable Energy Reviews 2011;15:3813–32.
energy storage system. Applied Energy 2003;74:195–202. [67] Dutil Y, Rousse DR, Salah NB, Lassue S, Zalewski L. A review on phase-
[32] Jahns E. Microencapsulated phase change material. Technical report, BASF, change materials: mathematical modeling and simulations. Renewable and
Germany. Sustainable Energy Reviews 2011;15:112–30.
[33] Mehling H, Cabeza LF. Heat and cold storage with PCM—an up to date [68] Prakash J, Garg HP, Datta G. A solar water heater with a built-in latent heat
introduction into basics and applications. Springer; 978-3-540-68556-2. storage. Energy Conversion and Management 1985;25(1):51–6.
[34] Fang G, Chen Z, Li H. Synthesis and properties of microencapsulated paraffin [69] Bony J, Citherlet S. Numerical model and experimental validation of
composites with SiO2 shell as thermal energy storage materials. Chemical heat storage with phase change materials. Energy and Buildings
Engineering Journal 2010;163(1-2):154–9. 2007;39:1065–72.
[35] Hart RL, Work DE Flame resistant microencapsulated phase change materi- [70] Talmatsky E, Kribus A. PCM storage for solar DHW: an unfulfilled promise?
als. US Patent 1995;No. 5,435,376. Solar Energy 2008;82:861–9.
[36] /www.cristopia.comS. [71] Ibanez M, Cabeza LF, Sole C, Roca J, Nogues M. Modelization of a water tank
[37] Jin Z, Wang Y, Liu J, Yang Z. Synthesis and properties of paraffin capsules as including a PCM module. Applied Thermal Engineering 2006;26:1328–33.
phase change materials. Polymer 2008;49:2903–10. [72] Cabeza LF, Ibanez M, Sole C, Roca J, Nogues M. Experimentation with a
[38] Zhang H, Wang X, Wu D. Silica encapsulation of n-octadecane via sol–gel water tank including a PCM module. Solar Energy Materials & Solar Cells
process: a novel microencapsulated phase-change material with enhanced 2006;90:1273–82.
thermal conductivity and performance. Journal of Colloid and Interface [73] Mehling H, Cabeza LF, Hippeli S, Hiebler S. PCM-module to improve hot
Science 2010;343:246–55. water heat stores with stratification. Renewable Energy 2003;28:699–711.
[39] Sari A, Alkan C, Karaipekli A, Uzun O. Microencapsulated n-octacosane as [74] Tyagi VV, Kaushik SC, Tyagi SK, Akiyama T. Development of phase change
phase change material for thermal energy storage. Solar Energy materials based microencapsulated technology for buildings: a review.
2009;83:1757–63. Renewable and Sustainable Energy Reviews 2011;15:1373–91.
[40] Zhang H, Wang X. Synthesis and properties of microencapsulated n- [75] Schossig P, Henning HM, Gschwander S, Haussmann T. Micro-encapsulated
octadecane with polyurea shells containing different soft segments for heat phase-change materials integrated into construction materials. Solar
energy storage and thermal regulation. Solar Energy Materials & Solar Cells Energy Materials & Solar Cells 2005;89:297–306.
2009;93:1366–76. [76] Castellon C, Medrano M, Roca J, Nogues M, Castell A, Cabeza LF. Use of
[41] /www.climator.comS. microencapsulated phase change materials in building applications. ASH-
[42] /www.rubitherm.comS. RAE 2007.
[43] Cabeza LF, Castellon C, Nogues M, Medrano M. Use of microencapsulated [77] Douglas CH. Phase change materials in floor tiles for thermal energy
PCM in concrete walls for energy savings. Energy and Buildings storage. Topical report 2002; Colorado State University, USA.
2007;39:113–9. [78] Castellon C, Medrano M, Roca J, Cabeza LF, Navarro ME, Fernandez AI,
[44] Ryu HW, Woo SW, Shin BC, Kim SD. Prevention of supercooling and Lazaro A, Zalba B. Effect of microencapsulated phase change material in
stabilization of inorganic salt hydrates as latent heat storage materials. sandwich panels. Renewable Energy 2010;35:2370–4.
Solar Energy Materials and Solar Cells 1992;27:161–72. [79] Li J, Xue P, Ding W, Han J, Sun G. Micro-encapsulated paraffin/high-density
[45] Fan YF, Zhang XX, Wang XC, Li J, Zhu QB. Super-cooling prevention of polyethylene/wood flour composite as form-stable phase change material
microencapsulated phase change material. Thermochimica Acta 2004; for thermal energy storage. Solar Energy Materials & Solar Cells
413(1–2):1–6. 2009;93:1761–7.
 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616 5615

[80] Kenisarin MM, Kenisarina KM. Form-stable phase change materials for inside cylindrical encapsulation. International Journal of Thermal Sciences
thermal energy storage. Renewable and Sustainable Energy Reviews 2008;47:858–74.
2012;16:1999–2040. [112] Stritih U. An experimental study of enhanced heat transfer in rectangular
[81] Nallusamy N, Sampath S, Velraj R. Experimental investigation on a com- PCM thermal storage. International Journal of Heat and Mass Transfer
bined sensible and latent heat storage system integrated with constant/ 2004;47:2841–7.
varying (solar) heat sources. Renewable Energy 2007;32:1206–27. [113] Tan FL, Hosseinizadeh SF, Khodadadi JM, Fan L. Experimental and computa-
[82] Esen M, Durmus A, Durmus A. Geometric design of solar-aided latent heat tional study of constrained melting of phase change materials (PCM) inside
store depending on various parameters and phase change materials. Solar a spherical capsule. International Journal of Heat and Mass Transfer
Energy 1998;62(1):19–28. 2009;52:3464–72.
[83] Kousksou T, Bruel P. Encapsulated phase change material under cyclic pulsed [114] Ettouney H, El-Dessouky H, Al-Kandari E. Heat transfer characteristics
heat load. International Journal of Refrigeration 2010;33(8):1648–56. during melting and solidification of phase change energy storage process.
[84] Song Q, Li Y, Xing J, Hu JY, Marcus Y. Thermal stability of composite phase Industrial and Engineering Chemistry Research 2004;43:5350–7.
change material microcapsules incorporated with silver nano-particles. [115] Cho K, Choi SH. Thermal characteristics of paraffin in a spherical capsule
Polymer 2007;48:3317–23. during freezing and melting processes. International Journal of Heat and
[85] Davis DA, Hart RL, Work DE, Virgallito DR. Macrocapsules containing Mass Transfer 2000;43:3183–96.
microencapsulated phase change materials. US Patent 2004;No. 6835334. [116] Zukowski M. Experimental study of short term thermal energy storage unit
[86] Ma S, Song G, Li W, Fan P, Tang G. UV irradiation-initiated MMA based on enclosed phase change material in polyethylene film bag. Energy
polymerization to prepare microcapsules containing phase change paraffin. Conversion and Management 2007;48:166–73.
Solar Energy Materials & Solar Cells 2010;94:1643–7. [117] Ismail KAR, Henrıquez JR. Solidification of PCM inside a spherical capsule.
[87] Zhang XX, Tao XM, Yick KL, Wang XC. Structure and thermal stability of Energy Conversion & Management 2000;41:173–87.
microencapsulated phase-change materials. Colloid and Polymer Science [118] Ismail KAR, Henrıquez JR. Numerical and experimental study of spherical
2004;282:330–6. capsules packed bed latent heat storage system. Applied Thermal Engineer-
[88] Salaun F, Devaux E, Bourbigot S, Rumeau P. Material containing micro- ing 2002;22:1705–16.
capsules, in particular phase-changing material. US Patent 2009;No. [119] Ismail KAR. Moraes RIR. A numerical and experimental investigation of
0291309 A1. different containers and PCM options for cold storage modular units for
[89] Su J, Ren L, Wang L. Preparation and mechanical properties of thermal energy domestic applications. International Journal of Heat and Mass Transfer
storage microcapsules. Colloid and Polymer Science 2005;284:224–8. 2009;52:4195–202.
[90] Ohtsubo T, Tsuda S, Tsuji K. A study of the physical strength of fenitrothion [120] Akgun M, Aydın O, Kaygusuz K. Experimental study on melting/solidifica-
microcapsules. Polymer 1991;32(13):2395–9. tion characteristics of a paraffin as PCM. Energy Conversion and Manage-
[91] Roy SK, Sengupta S. An evaluation of phase change microcapsules for use in ment 2007;48:669–78.
enhanced heat transfer fluids. International Communications in Heat [121] Regin AF, Solanki SC, Saini JS. An analysis of a packed bed latent heat
Transfer 1991;18:495–507. thermal energy storage system using PCM capsules: numerical investiga-
[92] Wei J, Kawaguchi Y, Hirano S, Takeuchi H. Study on a PCM heat storage system tion. Renewable Energy 2009;34:1765–73.
for rapid heat supply. Applied Thermal Engineering 2005;25:2903–20. [122] Wu S, Fang G. Dynamic performances of solar heat storage system with
[93] Ettouney H, Alatiqi I, Al-Sahali M, Al-Hajirie K. Heat transfer enhancement packed bed using myristic acid as phase change material. Energy and
in energy storage in spherical capsules filled with paraffin wax and metal Buildings 2011;43(5):1091–6.
beads. Energy Conversion and Management 2006;47:211–28. [123] Royon L, Guiffant G. Investigation on heat transfer properties of slurry of
[94] Castellon C, Nogues M, Roca J, Cabeza LF. Design of a plastic encapsulation stabilized paraffin during a melting process. Energy Conversion and Man-
for phase change materials (PCM) in buildings. Advanced thermal energy agement 2011;52(2):1073–6.
storage through phase change materials and chemical reactions feasibility [124] Gschwander S, Schossig P, Henning HM. Micro-encapsulated paraffin in
studies and demonstration projects. Eighth workshop, 18–20 April 2005 , phase-change slurries. Solar Energy Materials & Solar Cells 2005;89:307–15.
Kizkalesi, Turkey. [125] Royon L, Guiffant G, Perrot P. Forced convection heat transfer in a slurry of
[95] Werner R. Compatibility of organic latent heat storage materials and plastic phase change material in an agitated tank. International Communications in
container materials. Heat Recovery Systems and CHP 1987;7(4):383–8. Heat and Mass Transfer 2000;27(8):1057–65.
[96] Sun G, Zhang Z. Mechanical strength of microcapsules made of different [126] Zhang S, Niu J. Experimental investigation of effects of supercooling on
wall materials. International Journal of Pharmaceutics 2002;242:307–11. microencapsulated phase-change material (MPCM) slurry thermal storage
[97] Hatfield JC. Encapsulation of phase change materials. US Patent capacities. Solar Energy Materials & Solar Cells 2010;94:1038–48.
1987;No.4,708,812. [127] Diaconu BM, Varga S, Oliveira AC. Experimental study of natural convection
[98] Zhang X, Chao N, Zhang X, Xu J. Natural microtubule encapsulated phase- heat transfer in a microencapsulated phase change material slurry. Energy
change materials and preparation thereof. US Patent 2010; No. 0071882A1. 2010;35:2688–93.
[99] Darkwa J, Su O. Thermal simulation of composite high conductivity [128] Choi E, Cho YI, Lorsch HG. Forced convection heat transfer with phase-
laminated microencapsulated phase change material (MEPCM) board. change-material slurries: turbulent flow in a circular tube. International
Applied Energy 2012;95:246–52. Journal of Heat and Mass Transfer 1994;37(2):207–15.
[100] Majumdar P, Saidbakhsh A. A heat transfer model for phase change thermal [129] Zeng R, Wang X, Chen B, Zhang Y, Niu J, Wang X, Di H. Heat transfer
energy storage. Heat Recovery Systems and CHP 1990;10(5/6):457–68. characteristics of microencapsulated phase change material slurry in
[101] Teng YM, Akin JE. An effective capacity approach to Stefan problems using laminar flow under constant heat flux. Applied Energy 2009;86:2661–70.
simple isoparametric elements. International Communications in Heat and [130] Charunyakorn P, Sengupta S, Roy SK. Forced convective heat transfer in
Mass Transfer 1994;21(2):179–88. microencapsulated phase change material slurries: flow in circular ducts.
[102] Qarnia HE. Numerical analysis of a coupled solar collector latent heat International Journal of Heat and Mass Transfer 1991;34(3):819–33.
storage unit using various phase change materials for heating the water. [131] Cabeza L, Heinz A, Streicher W. Inventory of phase change materials (PCM).
Energy Conversion and Management 2009;50:247–54. Technical report 2007; Graz University of Technology Austria.
[103] Costa M, Buddhi D, Oliva A. Numerical simulation of a latent heat thermal [132] Chen Z, Fang G. Preparation and heat transfer characteristics of micro-
energy storage system with enhanced heat conduction. Energy Conversion encapsulated phase change material slurry: a review. Renewable and
and Management 1998;39(3/4):319–30. Sustainable Energy Reviews 2011;15:4624–32.
[104] Dwarka K, Kim JS. Thermal analysis of composite phase change [133] Zhang P, Ma ZW, Wang RZ. An overview of phase change material slurries:
drywall systems. Trans ASME Journal of Solar Energy Engineering MPCS and CHS. Renewable and Sustainable Energy Reviews 2010;14:
2005;127:352–6. 598–614.
[105] Long JY. Numerical and experimental investigation for heat transfer in [134] Eames PC, Griffiths PW. Thermal behavior of integrated solar collector/
triplex concentric tube with phase change material for thermal energy storage unit with 65 1C phase change material. Energy Conversion and
storage. Solar Energy 2008;82:977–85. Management 2006;47:3611–8.
[106] Veerappan M, Kalaiselvam S, Iniyan S, Goic R. Phase change characteristic study [135] Alvarado JL, Marsh C, Sohn C, Phetteplace G, Newell T. Thermal performance
of spherical PCMs in solar energy storage. Solar Energy 2009;83:1245–52. of microencapsulated phase change material slurry in turbulent flow under
[107] Wu S, Fang G, Liu X. Thermal performance simulations of a packed bed cool constant heat flux. International Journal of Heat and Mass Transfer
thermal energy storage system using n-tetradecane as phase change 2007;50:1938–52.
material. International Journal of Thermal Sciences 2010;49:1752–62. [136] Yang R, Xu H, Zhang Y. Preparation, physical property and thermal physical
[108] Arkar C, Medved S. Influence of accuracy of thermal property data of a phase property of phase change microcapsule slurry and phase change emulsion.
change material on the result of a numerical model of a packed bed latent Solar Energy Materials & Solar Cells 2003;80:405–16.
heat storage with spheres. Thermochimica Acta 2005;438:192–201. [137] Wang X, Niu J, Li Y, Wang X, Chen B, Zeng R, Song Q, Zhang Y. Flow and heat
[109] Zukowski M. Mathematical modeling and numerical simulation of a short transfer behaviors of phase change material slurries in a horizontal circular
term thermal energy storage system using phase change material for tube. International Journal of Heat and Mass Transfer 2007;50:2480–91.
heating applications. Energy Conversion and Management 2007;48:155–65. [138] Chen B, Wang X, Zeng R, Zhang Y, Wang X, Niu X, Li Y, Di H. An experimental
[110] Zivkovic B, Fujii I. An analysis of isothermal phase change of phase change study of convective heat transfer with microencapsulated phase change
material within rectangular and cylindrical containers. Solar Energy material suspension: laminar flow in a circular tube under constant heat
2001;70(1):51–61. flux. Experimental Thermal and Fluid Science 2008;32:1638–46.
[111] Kalaiselvam S, Veerappan M, Aaron AA, Iniyan S. Experimental and analy- [139] Zhang Y, Rao Z, Wang S, Zhang Z, Li X. Experimental evaluation on natural
tical investigation of solidification and melting characteristics of PCMs convection heat transfer of microencapsulated phase change materials
5616 P.B. Salunkhe, P.S. Shembekar / Renewable and Sustainable Energy Reviews 16 (2012) 5603–5616

slurry in a rectangular heat storage tank. Energy Conversion and Manage- [141] Sabbah R, Farid MM, Al-Hallaj S. Micro-channel heat sink with slurry of
ment 2012;59:33–9. water with micro-encapsulated phase change material: 3D-numerical
[140] Hu X, Zhang Y. Novel insight and numerical analysis of convective heat study. Applied Thermal Engineering 2008;29:445–54.
transfer enhancement with microencapsulated phase change material [142] Zhang Y, Wang S, Rao Z, Xie J. Experiment on heat storage characteristic of
slurries: laminar flow in a circular tube with constant heat flux. Interna- microencapsulated phase change material slurry. Solar Energy Materials
tional Journal of Heat and Mass Transfer 2002;45:3163–72. and Solar Cells 2011;95:2726–33.