Nano Energy (2015) 13, 814826

Available online at www.sciencedirect.com

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

REVIEW

Review on nanoencapsulated phase change

materials: Preparation, characterization
and heat transfer enhancement
Chenzhen Liu, Zhonghao Raon, Jiateng Zhao, Yutao Huo, Yimin Li
School of Electric Power Engineering, China University of Mining and Technology, Xuzhou 221116, China
Received 18 January 2015; received in revised form 10 February 2015; accepted 12 February 2015
Available online 20 February 2015

KEYWORDS

Abstract

Thermal energy storage;

Nanoencapsulated
phase change material;
Nanoencapsulation
method;
Heat transfer
enhancement;
Latent functional
thermal uid

In recent years, phase change materials (PCM) which are recommended as potential thermal
energy storage medium have been receiving signicant attention. The encapsulation technology
of PCM is an effective way to enhance the thermal conductivity and solve the issues of leakage
and corrosion during the melting process. As a good choice of thermal energy storage materials,
the nanoencapsulated phase change materials (NanoPCM) have many advantages, such as small
size, large specic surface and high heat transfer rate. Up to now, there has been no complete
literature review on the preparation, characterization and application of NanoPCM. In this
paper, a comprehensive summary has been presented based on the research of NanoPCM in
recent years. The following four aspects have been reviewed in detail: preparation and
characterization of NanoPCM, application of NanoPCM in latent functional thermal uid,
dynamics simulation study of NanoPCM and heat transfer enhancement of NanoPCM. It is
expected that this review article has certain reference value for the further understanding of
NanoPCM.
& 2015 Elsevier Ltd. All rights reserved.

Contents
Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The preparation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Interfacial polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Emulsion polymerization method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Miniemulsion polymerization method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In situ polymerization method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
n

Corresponding author. Tel.: +86 516 83592000.

E-mail address: raozhonghao@cumt.edu.cn (Z. Rao).

http://dx.doi.org/10.1016/j.nanoen.2015.02.016
2211-2855/& 2015 Elsevier Ltd. All rights reserved.

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Preparation, characterization and heat transfer enhancement

815

Solgel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Applications of NanoPCM in latent functional thermal uid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Heat transfer enhancement of NanoPCM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dynamics simulation study of NanoPCM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Further prospective research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Introduction
Energy shortage is getting worse with the rapid development of economy and industry in the world. After the
energy crisis in the 1970s, the researches on renewable
and sustainable energy have been gaining more and more
attention [1]. The technology of phase change energy
storage realizes the storage, transportation and utilization
of thermal energy when the phase change materials (PCM)
are absorbing and releasing large amounts of latent heat
undergoing phase change. The phase change energy storage
technology, while it is attracting attention gradually, solves
the problem that the energy supply does not match the
demand in time and space [2], increases the energy utilization [3,4] and relieves energy crisis. Therefore, phase
change energy storage technology can be applied to many
elds such as waste heat recovery [5,6], solar energy
storage [710], intelligent building [1115], thermal regulating fabric [1618], electronic devices thermal control
[19,20], battery thermal management system [2123],
and so on.
The performance of phase change energy storage
depends on the properties of PCM. According to the
material properties, the PCM can be divided into organic
and inorganic [4,24]. With strong thermal stability, the
organic PCM are commonly used for energy storage in recent
years [25]. However, some problems of organic PCM will
appear in application such as low thermal conductivity
[26,27] and leakage during phase transition [28,29]. The
leakage causes certain harm to energy storage system and
environment, which limits the further application of PCM
[3032]. In order to solve these problems, the PCM are
encapsulated in a capsule to form the shell-core composite
materials which can be called as encapsulated phase
change materials (EPCM) [3336].

The EPCM are tiny containers which wrap PCM in the

capsule core [37,38]. The EPCM achieve the solidication of
PCM, not only enhancing the stability and heat transfer
efciency of PCM [39], but also facilitating its utilization,
storage and transportation [40]. The EPCM are mainly
composed of two parts [41]: PCM as core and inorganics or
polymer as shell, as shown in Figure 1. The EPCM can be
made in arbitrary shape, either irregular or regular such as
tubular, spherical and oval; and they have single or several
cores within the capsule and multi-walled capsules [4143],
as shown in Figure 2.
According to particle size, EPCM can be divided into the
following three types [1]: Nanocapsulated phase change
materials (NanoPCM) (particle size ranges between 1 and
1000 nm) [44,45], microcapsulated phase change materials
(MicroPCM) (particle size ranges between 1 and 1000 m)
[16,46] and macrocapsulated phase change materials
(MacroPCM) [47,48] (particle size exceeds 1 mm).
MicroPCM technologies are mature after more than 50
years of development. The stability of the PCM capsules is
inuenced by the particle size. In the process of uid ow
the MicroPCM are easily broken and can increase the
viscosity of uid, which limits the application of MicroPCM.
The relationship between stability and particle size of
MicroPCM was studied by Yamagishi et al. [49]. The slurry
which contained the MicroPCM (size distributions ranging

Mononuclear

Matrix
Figure 1

Description of a capsule [41].

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822
823
823
823
824
824
824

Figure 2

Polynuclear

Multi-wall
Morphology of a capsule [41].

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Table 1

C. Liu et al.

Core and shell of NanoPCM.

Core

Shell

Method

Capsule mean
size

n-Tetradecane
[74]
Palmitic acid
[87]
n-Dodecanol
[80]
n-Dodecanol
[73]
n-Heptadecane
[66]
n-Octadecane
[77]
n-Octadecane
[81]
n-Octadecane
[81]
n-Octadecane
[83]
n-Octadecane
[63]
n-Nonadecane
[67]
nDotriacontane
[76]
n-Tetradecane
[84]
Parafn [65]
Parafn [82]

Polystyrene

Miniemulsion in situ polymerization

132 nm

SiO2

Solgel method

183.7 nm

Polymethyl methacrylate (PMMA)

Miniemulsion polymerization

150 nm

Styrene-butyl acrylate copolymer

Miniemulsion polymerization

Polystyrene

Emulsion polymerization

St(styrene) MMA (methylmethacrylate)

copolymer
Methyl methacrylate(PMMA)

Miniemulsion in situ polymerization

90100 nm
(range)
10 nm60 m
(range)
102 nm

Direct miniemulsion method

119 nm

Poly(ethyl methacrylate) (PEMA)

Direct miniemulsion method

140 nm

Methyl methacrylate-co-allyl methacrylate

(MMA-co-AMA)
Polystyrene

577693 nm

Poly(methyl methacrylate) (PMMA)

Free radical emulsion polymerization and

in situ polymerization
Ultrasonic-assistant miniemulsion in-situ
polymerization
Via emulsion polymerization

Polystyrene(PS)

Miniemulsion polymerization method

100350 nm
(range)
168.2 nm

Urea formaldehyde

In situ polymerization

100 nm

Polyurea
Carboxymethyl cellulose (CMC)

Interfacial polycondensation reaction

in situ polymerization

498.2 nm
50 nm

from 5 to 1000 m) particles (20 vol%) in water was circulated by a pump - circulating system. It was observed that
the MicroPCM with particle size of 10001500 m were
rapidly broken during the pump circulation. The breakage
rate of the MicroPCM with particle size of 75300 m was
40% after 500 times of pump circulation. The breakage rate
of the MicroPCM with particle size of 20100 m was less
than 10% after 4000 times of pump circulation. But the
MicroPCM with particle size of 510 m were almost not
broken during the pump circulation more than 7000 times.
The results demonstrated that the breakage rates
decreased as the MicroPCM particle sizes decreased, and
smaller sized MicroPCM were more durable and withstood
stress from the pump circulation.
Adding MicroPCM to function thermal uid can increase
the viscosity of uid [5052], and MicroPCM easily fracture in
the process of uid or pump circulation, which is the obstacle
of long-term circulation. For the small particle size, large
specic surface area, suspension stability and low breakage
rate during pumping compared with MicroPCM, NanoPCM are
gaining attention gradually [53]. Sukhorukov et al. [54]
observed that when the same force is applied the deformation of 10 nm size capsules is smaller than that of 10 m size
capsules. Besides, the NanoPCM have some unique properties, such as volume effect, surface effect, macroscopic

124 nm

quantum tunneling effect and so on [55], that make them

steadily disperse in the thermal uid, and ensure the
application in energy storage and thermal management
[56]. Therefore, nanocapsule of PCM has good growth
prospects.
Currently, there are many researchers who have summarized and reported research progress, preparation methods
and application status of MicroPCM [41,5759]. But comprehensive summary for NanoPCM has not been reported yet. In
this paper, research progress on preparation method, application in latent functional uid, and heat transfer enhancement of NanoPCM in recent years will be summarized.

The preparation methods

The chemical method, physical method and physic chemical
method are usually adopted for microcapsule preparation
[60]. Inorganic and polymer are commonly used as shell
[61], and most of the particle sizes range from 5 to 400 m.
The particle diameter of NanoPCM is smaller than that of
MicroPCM, therefore, the traditional preparation technologies of MicroPCM are not suitable for NanoPCM. Currently,
the main methods for preparation of nanocapsule are listed
as follows.

Preparation, characterization and heat transfer enhancement

817

Figure 4 (a) POM images of PS/heptadecane Micro/NanoPCM

and (b) SEM images of PS/heptadecane Micro/NanoPCM [66].

Figure 3 SEM and TEM images of NanoPCM (a) with and

(b) without Fe3O4 nanoparticle [65].

(i).
(ii).
(iii).
(iv).
(v).

Interfacial polymerization method.

Emulsion polymerization method [62,63].
Miniemulsion polymerization method [64].
In situ polymerization method.
Solgel method.

Table 1 summarizes several NanoPCM prepared by the

following methods.

Interfacial polymerization
In the process of preparing phase change capsules through
interfacial polymerization method, the core material is
emulsied rstly after the formation of the oil/water or
water/oil emulsion by using appropriate emulsier. Then
the polymer as capsule is formed on the surface of the core
by polymerization of the monomers. Finally the capsule is
separated from oil phase or water phase. When the method
for preparing NanoPCM is used, the core must be added to
the syringe with a capillary tube. It requires the setting of
high voltage and direct current. Besides, and the distance

between the needle of the syringe and liquid level of

monomer solution needs to be as near as possible.
Interfacial polymerization method is suitable for the
NanoPCM employing water soluble and oil soluble of PCM
core. Up to now, NanoPCM have been prepared by interfacial polymerization method using parafn as core and
polyurea as shell.
Park et al. [65] synthesized the NanoPCM via interfacial
polycondensation method, whose core and shell were
parafn and polyurea, respectively. The results of differential scanning calorimeter (DSC) analysis showed that the
melting temperature and latent heat of the NanoPCM were
measured to be 56.54 1C and 101.1 J/g, freezing temperature and latent heat were measured to be 47.82 1C and
105.6 J/g. Figure 3 shows the scanning electron microscope
(SEM) and transmission electron microscope (TEM) images of
the NanoPCM. It is clear that the NanoPCM have a spherical
structure. Besides, the particles size is mainly in the range
of 400600 nm.

Emulsion polymerization method

Emulsion polymerization method, one of common methods to
produce organic NanoPCM, mainly consists of the following
steps. First of all, the insoluble monomer in the solvent
dispersed uniformly in the reaction medium under the
function of the emulsier, the surfactant and the mechanical

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C. Liu et al.

Figure 5 TEM micrographs of SBA/n-dodecanol NanoPCM synthesized with different amounts of emulsier LAS: (a) 2%, (b) 3%,
(c) 4%, and (d) 5% [73].

stirring. Then the polymer membrane is generated on the

surface of the core through adding the initiator to initiate
polymerization reaction. Eventually the NanoPCM come
into being.
Emulsion polymerization method is often used for polymer polymerization which is suitable for preparation of
NanoPCM using liquid PCM as core material. So far, NanoPCM
have been prepared via emulsion polymerization method
which commonly uses alkane as core and polystyrene or poly
(methyl methacrylate) as shell.
Sari et al. [66] synthesized Micro/Nanoencapsulated
phase change materials (Micro/NanoPCM) with the nheptadecane as core and the polystyrene (PS) as shell
through emulsion polymerization method. The DSC results
demonstrated that the melting temperature and latent heat
of PS/heptadecane (1:2) Micro/NanoPCM were 21.48 1C and
136.89 J/g, respectively. The freezing temperature and
latent heat were 21.37 1C and 134.67 J/g, separately. The
latent heat of melting decreased from 136.89 J/g to
128.27 J/g due to the damage of several capsules after
5000 thermal cycles. The results of thermal gravimetric
analysis (TGA) showed that the Micro/NanoPCM represents
good thermal stability in the preparation process. The
polarized optical microscopy (POM) and SEM images are
presented in Figure 4(a) and (b), respectively. The PS/
heptadecane (1:2) Micro/NanoPCM is in incomplete spherical which can be clearly seen from micrographs. The
particle sizes tested by the particle size distribution (PSD)

distributed in the range of 10 nm40 m. And later Sari

et al. [67] fabricated Micro/NanoPCM using n-nonadecane as
core and poly (methyl methacrylate) (PMMA) as shell by
means of the emulsion polymerization. The PSD results
exhibited that the particle sizes were in the range of
10 nm40 m. The melting temperature and latent heat
were measured to be 31.23 1C and 139.20 J/g by DSC. The
Micro/NanoPCM have good thermal stability after 5000
thermal cycles. All of the results indicated that the
preparation of PS/n-heptadecane and PMMA/n-nonadecane
Micro/NanoPCM had promising potential in different thermal energy storage applications such as solar thermal
controlling of building envelopes, thermoregulation textiles, thermal protecting of vehicle battery systems, thermal regulating application, and so on.
Back et al. [68] and Alkan et al. [69] also successfully
synthesized and characterized the NanoPCM through emulsion polymerization method.

Miniemulsion polymerization method

Miniemulsion polymerization method is the most common
method for preparing NanoPCM at present. In this method,
polymerization reaction is carried out within tiny droplets,
which are stable, decentralized, size at nanometer
level under the effect of high shear force, and contain
water, monomer, emulsier and initiator, etc. During the

Preparation, characterization and heat transfer enhancement

819

Figure 6 SEM micrographs of NanoPCM with various amounts of polyaniline (a) 0 g, (b) 0.5 g, (c) 1.0 g, (d) 1.5 g and (e) 2.0 g [83].

miniemulsion polymerization reaction, the monomer determines the chemical composition of product and the properties of latex [70], and the size and morphology of the
polymer emulsion formed nally are same as those of the
original droplets [71,72].
Compared with emulsion polymerization, the miniemulsion polymerization method in preparation of NanoPCM has
the advantages of less energy input and high stability. This
method is suitable for the combination of alkane as PCM
core and polystyrene, polyurea, styrene-butyl acrylate
(SBA), styrene (St)-methylmethacrylate (MMA) copolymer
and poly (methyl methacrylate) as shell.
The NanoPCM containing n-dodecanol as core and
styrene-butyl acrylate (SBA) copolymer as shell were
synthesized through miniemulsion polymerization method

by Chen et al. [73]. The particle size, morphology and

thermal performances of the NanoPCM were measured by
PSD, TEM and DSC, respectively. The results showed that the
encapsulation efciency of NanoPCM has reached 98.4%.
The spherical structure of the NanoPCM can be seen clearly
from Figure 5. When the mass ratio of monomers/n-dodecanol reached 1:1, the average particle size got 100 nm, the
thermal decomposition was about 195 1C, and the phase
change temperature and phase change enthalpy were
18.4 1C and 109.2 J/g, respectively.
Fang et al. synthesized the NanoPCM, whose shell is
polystyrene and core is n-tetradecane [74], n-octadecane
[63,75] or n-dotriacontane [76] via miniemulsion polymerization method. The synthesized NanoPCM were spherical
and the z-average particle size was 132 nm, 124 nm and

820

C. Liu et al.

168.2 nm, respectively. The results of DSC analysis represented that the melting temperature and latent heat of the
n-tetradecane/polystyrene nanocapsules were 4.04 1C and
98.71 J/g, and the freezing temperature and latent heat
were 3.43 1C and 91.27 J/g, respectively. The latent heat of
the n-octadecane/polystyrene nanocapsules reached up to
124.4 J/g. The melting temperature and latent heat of the
n-dotriacontane/polystyrene nanocapsules were measured
to be 70.9 1C and 174.8 J/g, and the freezing temperature
and latent heat were measured to be 63.3 1C and 177.1 J/g,
respectively.
Tumirah et al. [77] fabricated the NanoPCM with noctadecane as core and styrene (St)-methylmethacrylate
(MMA) copolymer as shell using miniemulsion in-situ polymerization method. The morphology, particle size and
thermal properties of the NanoPCM were characterized by
SEM, dynamic light scattering (DLS) and DSC. When the
shell/core mass ratio was 3:1, the mean diameter, melting
temperature and freezing temperature of the spherical
NanoPCM were 102 nm, 29.5 1C and 24.6 1C, respectively.
The melting and freezing latent heat reached 107.9 J/g and
104.9 J/g, separately. After 360 heating/cooling cycles, the
fabricated NanoPCM still had good chemical stability and
thermal reliability.
The NanoPCM with the average size below 200 nm were
also synthesized using miniemulsion polymerization method
by Luo et al. [78], Fuensanta et al. [79], Chen et al. [80] and
Zhang et al. [81].

In situ polymerization method

In the process of preparing phase change capsules through
in situ polymerization method, the reaction monomer and
catalyst are all located outside the core. The monomer is
soluble in the continuous phase, but the polymer is immiscible with the continuous phase. Therefore, the polymerization reaction occurs on the surface of the core. With the
development of the polymerization, the prepolymer is
generated gradually on the surface of the core, and nally
the capsule shell is formed [57].
Up to now, in the in situ polymerization method, the organics,
which are commonly polymers such as urea-formaldehyde resin,
melamine-formaldehyde, carboxymethyl cellulose, poly (methyl
methacrylate) and poly (allyl methacrylate), have been mainly
coated as shell material.
Hu et al. [82] synthesized the NanoPCM (parafn as core
and carboxymethyl cellulose (CMC)-modied MF as shell) via
in situ polymerization method. The obtained CMC-modied
nanocapsules were spherical in shape with an average
diameter of 50 nm. When the mass content of parafn in
the nanocapsules were 31.6%, 49.1% and 63.1%, the corresponding phase change enthalpy were 41.79 J/g, 64.85 J/g
and 83.46 J/g, respectively, and the corresponding cracking
ratio of the nanocapsules was 17.5%, 10.6% and 11.0% when
the nanocapsules suspension was sheared mechanically at
5000 rpm for 10 min.
Wang et al. [83] synthesized the NanoPCM through free
radical emulsion polymerization method and in situ polymerization method, using poly (methyl methacrylate-co-allyl
methacrylate) as a shell and n-octadecane as core. Figure 6
shows the SEM micrographs of NanoPCM with various amounts

Figure 7 SEM micrographs of PA/SiO2 NanoPCM prepared at

different PH of the solvent:(a) 11, (b) 11.5 and (c) 12 [87].

of polyaniline (PANI). The inuences of different contents of

polyaniline as nucleating agent on the surface morphology, the
crystallization property and the thermal stability of NanoPCM
were investigated. The results reected that the shape of
capsule is spherical, the particle size distributes between 100
1000 nm and the average size is in the range of 577693 nm.
There is a little effect of additive amount of the polyaniline on
the morphology, the particle size and the encapsulation
efciency of capsule, but increasing the amount of polyaniline
would decrease the degree of supercooling. When the adding
amount of polyaniline were 0 g, 0.5 g, 1.0 g, 1.5 g, and 2.0 g,
the corresponding supercooling degree of the capsule were
2.3 1C, 0.8 1C, 0.4 1C, 1.1 1C and 0.5 1C, respectively.

Preparation, characterization and heat transfer enhancement

821

Figure 8 Effect of mass concentration of slurry on temperature distribution [104].

The NanoPCM, containing n-tetradecane as the core,

were fabricated via in situ polymerization method by Fang
et al. [84]. The shell is the polymerization product of urea
and formaldehyde. The results of SEM analysis showed that
the NanoPCM had mean size of about 100 nm and ntetradecane was well encapsulated. The mass content of
n-tetradecane exceeded 60%, and the phase change
enthalpy reached up to 134.16 J/g.

Solgel method
Solgel method requires relative mild condition in the
preparation. The main processes are as follows: rstly,
metal alkoxide as precursor mixes uniformly with the
solvent, catalyst and complexing agent, etc. Secondly, a
stable and transparent colloidal solution comes into being
after hydrolysis and condensation chemical reaction. Then
the gel with three-dimensional network structure was
formed after aging of the sol. Finally, MacroPCM or NanoPCM

can be prepared after drying, sintering and curing

[41,85,86]. Solgel method is suitable for NanoPCM with
alkane, palmitic acid and indium as core material and
silicon dioxide as shell material.
Latibari et al. [87] successfully synthesized the NanoPCM
which contains palmitic acid (PA) as core and SiO2 as shell
through solgel method. Three samples (S1, S2 and S3) of
PA/SiO2 nanocapsules were prepared at three different PH
values (11, 11.5 and 12), respectively. The micrographs of
PA/SiO2 NanoPCM can be seen from Figure 7, and it is clear
that the NanoPCM has a spherical structure. The results of
Fourier transform infrared spectroscope (FTIR), X-ray diffractometer (XRD) and Energy dispersive X-ray Spectrometry (EDS) indicated that the NanoPCM were synthesized
successfully, and they had compact and smooth surface. SEM
and TEM tests indicated that the mean diameters of S1, S2
and S3 were 183.7 nm, 466.4 nm and 722.5 nm, respectively. The encapsulation ration of PA for S1, S2 and S3 were
82.53%, 84.28% and 88.32%, respectively. The thermal
conductivity of the NanoPCM was improved compared to

822

C. Liu et al.

that of pure PA. A test of 2500 thermal cycling for S3

indicated that the melting and freezing temperatures of the
NanoPCM were changed from 61.6 1C to 60.1 1C and from
57.08 1C to 56.85 1C, respectively. The latent heats of
melting and freezing were changed from 180.91 J/g to
177.3 J/g and from 181.22 J/g to 178.6 J/g, respectively.
These results indicated that the NanoPCM have good
thermal properties and reliability and chemical stability.
Hong et al. [88] synthesized the NanoPCM through solgel
method, which used silica as shell and indium as core. Two
types of silica obtained from tetraethylorthosilicate (TEOS) and
sodium silicate have been used in the NanoPCM. The particle
size and the degree of super-cooling of the two kinds of
NanoPCM were analyzed and compared. The research results
showed that the core diameter and shell thickness of NanoPCM
using TEOS-derived silica as shell were 200 nm and 100 nm and
those of the other NanoPCM were 200 mm and 50 nm, respectively. When the change rate of the temperature were 1 1C/
min, 5 1C/min, 10 1C/min, 20 1C/min and 40 1C/min, the supercooling were 32 1C, 33 1C, 34 1C, 36 1C and 41 1C, respectively.
And the corresponding super-cooling of the other NanoPCM are
3.9 1C, 6.1 1C, 8.3 1C, 10.2 1C and 14 1C at the same temperature change rate, respectively.
Among the methods introduced above, interfacial polymerization method is widely used in encapsule of dye and
pesticides, which has the advantages of simple process and
wide commercial application. However, less researches
focus on the interfacial polymerization and the choice of
shell material is relatively fewer for the synthesis of
NanoPCM. The preparation of NanoPCM using in situ polymerization has good capsule morphology and thermal properties. Further research should be committed to not only
simplify the process, but also reduce the cost of industrial
scale production. The miniemulsion polymerization method
is a great way to prepare core/shell polymers [89]. There
have been many studies that using this method successfully
synthesized NanoPCM which have good thermal performance and stability. In the preparation process of NanoPCM
using miniemulsion polymerization method, the demands of
higher stability of system and polymerization rate moderate
can be easily met [90]. Besides, the size of the capsule can

be adjusted by controlling the stabilizer dosage. The

advantages of miniemulsion polymerization indicate that
the process of preparation NanoPCM is easy to control and
conducive to the implementation of industrial production.

Applications of NanoPCM in latent functional

thermal uid
The latent functional thermal uid, composed of thermal
uid as continuous phase and PCM particle additives as
dispersion, is a kind of solidliquid two phase liquid [91,92].
Due to the fact that the latent functional thermal uid has
higher heat storage capacity and heat transfer coefcient
than traditional single phase uid, researchers have paid
more and more attention to it in recent years. The EPCM
slurry is a kind of latent functional thermal uid which is
composed of encapsulated PCM and single phase heat
transfer uid [93]. EPCM slurry, as efcient heat transfer
medium in the heat storage, not only improves the heat
storage capacity and heat transfer rate, but also reduces
the heat exchanger size, uid conveying pipeline size and
transport energy consumption. EPCM slurry can be widely
used in various energy storage systems to achieve the
storage and transportation of energy.
Currently MicroPCM slurry, as latent functional thermal
uid, has been studied by many researchers [9498]. Heat
transfer coefcients of MicroPCM slurry were measured by
Wang et al. [99]. The MicroPCM slurry consisted of microencapsulated 1-bromohexadecane and water, with the mass
fraction of MicroPCM varying from 5% to 27.6%. The results
showed that the thermal storage capacity and heat transfer
coefcients were both improved after adding MicroPCM. The
same results can also be found in the work of Delgado [100]
and Rao [101]. Although EPCM slurry has more advantages in
heat storage capacity and heat transfer performance compared
with traditional heat transfer uid, it has some disadvantages,
such as easily fracturing in the process of ow during pumping,
increasing the uid's viscosity, making the pipe easy to wear
and jam [102,103] and so on. NanoPCM has the advantages of
small size and larger specic surface area. It was more stable

Figure 9 The typical structures of NanoPCM [107].

Preparation, characterization and heat transfer enhancement

than MicroPCM in structure. The fracture rate, the effect of
increasing the uid's viscosity and wearing the pipeline are all
smaller than those of MicroPCM [39,54]. NanoPCM slurry as
latent functional thermal uid has broad application prospects
in the eld of intelligent building, thermal regulating fabric
and electronic devices thermal control, etc. Therefore, the
development of NanoPCM slurry is inevitable.
Fang et al. [74] synthesized polystyrene/n-tetradecane
NanoPCM using ultrasonic assistant miniemulsion in situ polymerization, and added the NanoPCM to water as latent
functional thermal uid which was utilized in cold thermal
energy storage. The research results showed that the thermal
conductivity of the water was improved from 0.6226 W/(m K)
to 0.63806 W/(m K) and from 0.7296 W/(m K) to 0.84676 W/
(m K) at the temperature of 5 1C and 25 1C after adding
NanoPCM with the mass fraction of 15%, respectively. When
the temperature is 5 1C and the mass concentration of the
NanoPCM are 15%, 7.5%, 3.75% and 0%, the viscosities are
16.16 mPa s, 12.18 mPa s, 8.56 mPa s, and 4.68 mPa s, respectively. It is visible that the NanoPCM slurry in the low viscosities
range is suitable for using as latent functional thermal uid.
Seyf et al. [104] studied the thermal characteristic of a
microtube (NanoPCM slurry as coolant) heat sink with tangential impingement through three dimensional numerical simulation. The NanoPCM slurry consists of polyalphaolen (PAO) as
base uid and octadecane as nanoparticle. As shown in
Figure 8, when the Reynolds number (Re) is 400, the
temperature boundary layer growth for NanoPCM slurry coolant is slower than that of pure PAO, and increasing the mass
concentration of slurry can reduce the wall temperature and
uniform the temperature distribution in solid and liquid
phases. And later Seyf et al. [105] analyzed the effects of
mass concentration and Reynolds number of NanoPCM slurry
on convection heat transfer of steady laminar owing past an
isothermal square cylinder by means of numerical solution.
The NanoPCM slurry consists of water and n-octadecane
NanoPCM with an mean diameter of 100 nm. The results
showed that the NanoPCM has signicant effect on enhancing
the heat transfer ability and the increases in volume fraction
and Reynolds number lead to enhancement of heat transfer
and shear stress over the cylinder.
Wu et al. [103] synthesized the polymer/parafn NanoPCM
using miniemulsion polymerization method. The NanoPCM
were added in water to form NanoPCM slurry which could
enhance the heat transfer coefcient of jet impingement and
spray cooling. The results showed that the volume fraction of
the NanoPCM has a great effect on heat transfer coefcient.
Compared to water, slurry with 28% volume fraction of
NanoPCM enhances heat transfer coefcient by 50% and 70%,
for jet impingement and spray cooling, respectively.

Heat transfer enhancement of NanoPCM

Although NanoPCM slurry as latent functional thermal uid
has higher heat storage capacity and heat transfer coefcient than traditional single phase uid, the heat transfer
coefcient is still low. And PCM has a larger degree of
supercooling in phase change, so its application is limited
[106]. Therefore, the heat transfer of NanoPCM must be
enhanced in order to reduce the degree of supercooling and
improve the heat transfer efciency.

823
Park et al. [65] synthesized the magnetic Fe3O4 nanoparticles (NPs)-embedded PCM nanocapsules (Mag-PCM) based
on a parafn core and polyurea shell via interfacial polycondensation method. Three weight percentages of Fe3O4
were added to PCM nanocapsules, respectively. The weight
percentages of Fe3O4 nanoparticles in Mag-PCM were measured to be 3.1%, 5.7% and 6.6% by TGA. The Fe3O4
nanoparticles were embedded in the polyurea shell. When
the amount of Fe3O4 NPs is added, the thermal conductivity
of the nanocapsules increased and the supercooling degree
of parafn decreased.

Dynamics simulation study of NanoPCM

With the unceasing development of computer technology,
the computer simulation has been widely used in studies of
PCM. Some researchers studied thermal properties, self
diffusion, mesoscopic morphology and evolution mechanism
of the NanoPCM by dynamics simulation.
Rao et al. [107] studied the self diffusion of the NanoPCM by
molecular dynamic simulation. In this study two NanoPCM
models were fabricated by using n-octadecane as core material and SiO2 as shell materials: one with constrained shell and
another with free shell. Figure 9 shows the typical structures
of NanoPCM. The molecular dynamic simulation results
showed that thickness and hardness of NanoPCM shell has
impact on the self diffusion properties of NanoPCM. The
NanoPCM with constrained shell will restrain the torsion and
stretch strength of molecular chain outside the core materials,
and the diffusion coefcient of NanoPCM will decreased. The
NanoPCM with free shell will increase the uidity of core
material, reduce the thermal contact resistance between
capsules and enhance the heat transfer of the whole capsule.
Later, Rao et al. [108] studied the evolution mechanisms
and mesoscopic morphologies of the NanoPCM by dissipative
particle dynamics simulation method. The simulation results
showed that the two types of NanoPCM can be synthesized
using n-docosane as a core materials and ethyl acrylate
(EA), styrene (St) or allyloxy nonyl-phenoxy propanol polyoxyethylene ether ammonium sulfate (DNS-86) as shell
materials, respectively. A typical coreshell structure of
the NanoPCM can be synthesized when the proportion of the
components is suitable. The NanoPCM failed to be synthesized when the surfactant and shell materials is excess. And
the optimal encapsulation rate of n-docosane is 54.51%
analyzed by dissipative particle dynamics simulation. The
results of particle dynamics simulation research could be
useful in the design and experiment of the NanoPCM.

Further prospective research

MicroPCM has been studied for many years, but the
researches on NanoPCM start in recent years. Many
researchers studied the preparation and characterization
of the NanoPCM, but there are still many aspects worth our
further investigation. Suggestions for the future works can
be summarized into the following several aspects:
(1) Raise the efciency of preparation of NanoPCM: since
the production efciency of NanoPCM is quite low, it is
difcult to meet the needs of industrial applications.

824
Therefore, increasing the productivity of the NanoPCM
is inevitable.
(2) Molten salt and hydrated salt encapsulation: molten salt
and hydrated salt have high latent when they occurred
in phase transition, so they are very suitable as energy
storage materials. But at present the research of the
core of NanoPCM mainly focuses on organic material.
Therefore, molten salt and hydrated salt as core of
NanoPCM need further research.
(3) Applications of NanoPCM: up to now, there has been
little research work of NanoPCM applied in waste heat
recovery, solar energy storage, intelligent building,
thermal regulating fabric, electronic devices thermal
control and battery thermal management system, etc.
Therefore further studies of NanoPCM application are
needed.
(4) Further researches on preparation of NanoPCM with higher
encapsulation efciency, better stability, better thermal
performance and more uniform particle size distribution
need to be conducted. The diversity in choice of core and
shell material, the optimal process conditions and the
reduction of production cost can not be neglected.

Conclusions
This paper mainly reviewed the research progress of
NanoPCM in recent years. This review consists of four parts:
preparation and characterization of NanoPCM, application
of NanoPCM in latent functional thermal uid, heat transfer
enhancement of NanoPCM and dynamics simulation study of
NanoPCM. Five kinds of available preparation methods on
NanoPCM have been introduced, that is, interfacial polymerization method, emulsion polymerization method, miniemulsion polymerization method, in situ polymerization
method and solgel method. The characterizations of
NanoPCM preparation using the above methods were
described. Applications of NanoPCM in latent functional
thermal uid were summarized. Not only the thermal
storage capacity of the thermal transfer uid can be
increased, but also the performance of thermal conductivity
of the uid can be enhanced by adding the NanoPCM. And
then, this paper introduced the self diffusion, evolution
mechanisms and mesoscopic morphologies of the NanoPCM
by dynamics simulation. Finally, the limitations of current
research of NanoPCM were explained, and the further
prospective research of NanoPCM were discussed.

Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Nos. 51406223 and U1407125) and the
National Natural Science Foundation of Jiangsu Province
(No. BK20140190).

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Chenzhen Liu received his Bachelor degree
in Thermal Energy and Power Engineering
from Hebei University of Engineering in
2010, and Master degree in Power Engineering from Guangdong University of Technology in 2014. He is currently pursuing his
Ph.D. under the supervision of Prof. Zhonghao Rao and Prof. Yimin Li at China University of Mining and Technology. His
research mainly focuses on nano uid.
Zhonghao Rao received his Bachelor degree
in Thermal and Power Engineering and
Master degree in Thermal Engineering from
Guangdong University of Technology in 2008
and 2010, and Ph.D. in Chemical Process
Equipment from South China University of
Technology in 2013. He is currently a professor working at China University of Mining
and Technology. His research mainly focuses
on thermal energy conversion and storage
especially by using phase change materials.

Jiateng Zhao received his Bachelor degree

in Thermal Energy and Power Engineering
from China University of Mining and Technology in 2013. He is currently pursuing his
Master degree under the supervision of Prof.
Zhonghao Rao and Prof. Yimin Li at China
University of Mining and Technology. His
research mainly focuses on thermal physical
properties of nano uid.

Yutao Huo received his Bachelor degree in

Thermal Energy and Power Engineering from
China University of Mining and Technology in
2014. He is currently pursuing his Master
degree under the supervision of Prof. Zhonghao Rao at China University of Mining and
Technology. His research mainly focuses on
heat and mass transfer and nano uid.

Yimin Li received his Ph.D. in Engineering

Mechanics from China University of Mining
and Technology in 1998. He worked at
School of Electric Power Engineering, China
University of Mining and Technology. Currently he is Professor and Dean of School of
Electric Power Engineering, China University of Mining and Technology. His research
mainly focuses on the theory of uid.