Applied Thermal Engineering 178 (2020) 115492

Contents lists available at ScienceDirect

Applied Thermal Engineering

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

Nano-enhanced phase change materials (NePCMs): A review of numerical T

simulations
⁎
Teng Xiong, Long Zheng, Kwok Wei Shah
Department of Building, School of Design and Environment, National University of Singapore, Singapore 117566, Singapore

H I GH L IG H T S

• Numerical methods and prediction models are summarized and discussed.

• Melting and solidification of NePCMs inside different containers are reviewed.
• The effects of nanostructure type, morphology, size, and concentration are analyzed.
• The reasons for the discrepancy between simulation and experiment are identified.
• There is a trade-off between conduction enhancement, convection degradation, and latent heat reduction.

A R T I C LE I N FO A B S T R A C T

Keywords: Dispersing thermally conductive nanostructures is an effective method to improve the thermal performance of
Nano-enhanced phase change materials phase change materials (PCMs). For this purpose, nanocarbons, nanometals, and nano metal oxides have been
Numerical methods used to develop nano-enhanced phase change materials (NePCMs) with unique thermal properties. However,
Prediction models review papers focusing on the numerical simulations of NePCMs are still scarce. The present review provides a
Nanostructures
comprehensive overview of the latest numerical studies on NePCMs for thermal energy storage (TES). These
Melting and solidification
studies are mainly based on single-phase approaches, and the simulation results largely depend on the used
Thermal energy storage
prediction models of effective thermophysical properties. Accordingly, the most common numerical methods
and prediction models are reviewed to address their advantages and limitations. Then, the focus is placed on
melting and solidification of NePCMs inside different containers, including rectangular cavities, tubes, cylinders,
spheres, and annulus. In-depth insights are given into the effects of nanostructure type, morphology, size, and
concentration on heat storage and release performance. The pros and cons of dispersing nanoparticles and other
heat transfer enhancement techniques are also compared, such as mounting fins and using porous foams.
Moreover, a critical discussion is presented to identify the reasons for the discrepancy between simulation and
experiment, as well as the research gaps and future directions. This review aims to update the existing NePCM
studies using different simulation techniques, and to reveal the basic phase change behavior of NePCMs from the
reported results.

T temperature (K) S momentum source term

Ceff effective heat capacity (J/kg·K) Amush mushy zone constant
k thermal conductivity (W/m·K) ui velocity (m/s)
Cp heat capacity (J/kg·K) A intrinsic viscosity (kg/m·s)
L latent heat of fusion (J/kg) d diameter (m)
H total enthalpy (J/kg) M molecular weight (kg/kmol)
m mass (kg) N Avogadro number (mol-1)
t time (s) C’ empirical constant
l length (m) B Boltzmann constant (J/K)
f liquid fraction γ fraction of liquid volume

⁎
Corresponding author.
E-mail address: bdgskw@nus.edu.sg (K.W. Shah).

https://doi.org/10.1016/j.applthermaleng.2020.115492
Received 6 February 2020; Received in revised form 2 May 2020; Accepted 14 May 2020
Available online 26 May 2020
1359-4311/ © 2020 Elsevier Ltd. All rights reserved.
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Re Reynolds number SDBS sodium dodecylbenzene sulfonate

Pr Prandtl number SDS sodium dodecyl sulfate
Lii geometrical factor UV-vis Ultraviolet-visible spectrophotometry
a aspect ratio PIV particle image velocimetry
kii equivalent thermal conductivity (W/m·K) DSC differential scanning calorimetry
R thermal boundary resistance (m2·K/W)
Gr Grashof number 1. Introduction
Ra Rayleigh number
Ha Hartmann number Energy poverty is a major challenge facing the world today due to
Nu Nusselt number the fact that about 850 million people still lack access to electricity.
Gr Grashof number Global energy demand is projected to increase by roughly 30% between
St Stefan number today and 2040, with growing demand for energy services and effi-
subscript ciency improvements [1]. Countries with fast-growing economies,
especially Asian countries, are largely responsible for the growth [2]. So
s solid far, the share of fossil fuels (i.e. oil, coal, and natural gas) in the world’s
l liquid primary energy sources has remained stubbornly high at 85%. Without
0 initial a doubt, the burning of fossil fuels will greatly contribute to greenhouse
np NePCM gas emissions, leading to global warming, extreme weather events, sea
p PCM level rise, and other long-term impacts. According to a new report from
n nanoparticle the International Energy Agency [3], the energy- and process-related
e equivalent CO2 emissions hit another record high of 33 gigatons in 2019, following
ref reference two years of increases. The world must therefore balance the role of
Greek letters energy in social and economic development with the need to dec-
arbonize, and transition from a fossil fuel dominated energy mix to a
ρ density (kg/m3) low-carbon one. For this purpose, many research works have been
ε a small number conducted to tap into secure, affordable and renewable thermal energy
µ dynamic viscosity (kg/m·s) sources (e.g. solar thermal, geothermal, and ocean thermal). The
ϕ volume fraction (vol.%) drawback of the intermittent nature of renewables can be overcome by
ϕmax maximum packing factor installing a thermal energy storage (TES) system between the energy
β expansion coefficient (1/K) supply and demand sectors.
δ thickness (m) TES can be based on sensible heat, latent heat, and thermochemical
List of abbreviations heat. Among these methods, latent heat storage using phase change
materials (PCMs) has received the most attention in the past decade.
PCMs phase change materials PCMs are substances that absorb and release a lot of thermal energy by
NePCMs nano-enhanced phase change materials melting and freezing. The advantages of PCMs come from various as-
TES thermal energy storage pects, including high TES density, narrow operating temperature span,
PV photovoltaic and a small volume change during the phase transition [4,5]. In some
CSP concentrated solar power climate regions, PCMs were found to be effective in improving the
FVM finite volume method thermal performance and energy efficiency of buildings. PCM-in-
FEM finite element method tegrated wallboards, bricks, ceilings, and roofs with high thermal in-
EHCM effective heat capacity method ertia are able to attenuate the room temperature fluctuation, reduce the
EM enthalpy method cooling and heating energy demand, and downsize the HVAC system in
HSTM heat source term method buildings [6]. These are passive cooling and heating technologies. Si-
CFD computational fluid dynamics milarly, PCMs have also been extensively used for thermal management
LBM lattice-Boltzmann method of photovoltaic (PV) cells [7], Li-ion batteries [8], electronic devices
MD molecular dynamic [9], and vehicle components [10]. An actively charged/discharged
DEMT differential effective medium theory PCM system can serve as a buffer to balance the time and spatial mis-
EMT effective medium theory match between renewable energy sources and consumers. For example,
PG propylene glycol installing storage tanks packed with molten salt PCMs (phase change
EG ethylene glycol temperature range of 300–500 °C) has turned out to be a promising TES
MWCNT multi-walled carbon nanotubes method in commercial concentrated solar power (CSP) plants which
GnP graphene nanoplatelets involve interrupted energy conversion cycles [11]. Another idea is to
CNF carbon nanofibers use PCMs with different melting points for waste heat recovery in
SWCNT single-walled carbon nanotubes thermal power plants [12]. The captured waste heat can be reused by
CNT carbon nanotubes district energy systems to provide a cleaner way for heating buildings.
HTF heat transfer fluid Recent advances in PCMs and their applications in different scenarios
ND nanodiamond can be found in the review articles [13–16].
EPM enthalpy porosity method From a material point of view, the main defect of pure PCMs is their
MADM multi-attribute decision making poor thermal conductivity (usually between 0.2 and 0.7 W/m·K), which
DDF double distribution function limits the heat transfer efficiency of TES systems. Enhancing the
VOF volume of fluid thermal performance of PCMs has therefore become critical to their
LTE local thermal equilibrium effectiveness. With the fast development of nanotechnology and con-
LTNE local thermal non-equilibrium trollable synthesis, an easy-to-use method is to disperse thermally
RSM response surface method conductive nanostructures that are smaller than 100 nm in at least one
SGFEM standard Galerkin finite element method dimension. The commonly used ultra-small nanomaterials are carbons
UDF user defined function (e.g. carbon, graphene, graphite), metals (e.g. Cu, Ag), and metal oxides

2
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Table 1
Summary of experimental studies on NePCMs.
Nanostructure Morphology Average size Concentration Base PCM Phase change Thermal enhancement Ref.
temperature

graphene nanoplatelet d of 10 μm, δ of 64 nm 5.0 wt% paraffin wax 51–58 °C 164% thermal conductivity ↑ [19]
graphene nanoplatelet d of 5–10 μm, δ of 4–20 nm 10.0 wt% n-eicosane 35.7 °C 400% thermal conductivity ↑ [20]
graphite nanoplatelet d of 15 μm, δ of 10 nm 7.0 wt% paraffin wax 51–55 °C 207% thermal conductivity ↑ [21]
graphite nanoplatelet d of 15 μm, δ of 35 nm 10.0 wt% paraffin wax 29.7 °C 167% thermal conductivity ↑ [22]
carbon nanotube d of 6–9 nm, l of 5 μm 1.0 wt% n-eicosane 32–40 °C 113% thermal conductivity ↑ [23]
copper nanoparticle d of 10–30 nm 0.5 wt% sodium acetate trihydrate 58–62 °C 25% thermal conductivity ↑ [24]
20% heat transfer rate ↑
copper nanoparticle d of 25 nm 1.0 wt% paraffin wax 55–60 °C 30% melting rate ↑ [25]
28% solidification rate ↑
copper nanowire d of 80–150 nm, l of 10 μm 11.9 vol% tetradecanol 38–40 °C 793% thermal conductivity ↑ [26]
copper nanowire d of 50 nm, l of 10 μm 0.17 wt% calcium chloride 28–30 °C 52% thermal conductivity ↑ [27]
hexahydrate
silver nanoparticle d of 10–18 nm 5.0 wt% organic ester 5.8–7.7 °C 67% thermal conductivity ↑ [28]
silver nanowire d of 50–100 nm, l of 19.3 wt% polyethylene glycol 43–60 °C 1130% thermal conductivity [29]
5–20 μm ↑
copper oxide nanoparticle d of 37–59 nm 0.1 wt% water −0.8–0 °C 35% solidification rate ↑ [30]
alumina nanoparticle d of 10–20 nm 10.0 wt% paraffin wax 61.6 °C 43% thermal conductivity ↑ [31]
27% melting rate ↑
titanium dioxide nanoparticle d of 21 nm 5.0 wt% palmitic acid 60–62 °C 80% thermal conductivity ↑ [32]
titanium dioxide nanoparticle d of 20 nm 1.13 vol% barium chloride hydrate −9.3 °C 13% thermal conductivity ↑ [33]
titanium dioxide nanoparticle d of 50 nm 0.3 wt% paraffin wax 55–58 °C 25% thermal conductivity ↑ [34]
copper oxide nanoparticle d of 40 nm 55–59 °C 29% thermal conductivity ↑
graphene oxide nanosheet l of 5–20 μm, δ of 50 nm 56–57 °C 101% thermal conductivity ↑
magnetite nanoparticle d of 40–75 nm 20.0 wt% paraffin wax 43–50 °C 60% thermal conductivity ↑ [35]
8% latent heat ↑
boron nitride nanosheet l of 0.5–2 μm, δ of 100 nm 10.0 wt% paraffin wax 50–58 °C 60% thermal conductivity ↑ [36]

Note: d, δ, l, and ↑ stand for diameter, thickness, length, and enhancement, respectively.

(e.g. CuO, Al2O3, MgO, TiO2, ZnO) [17]. These highly conductive na-
nomaterials have different morphologies/shapes, including 0D (e.g.
particles, diamonds), 1D (e.g. tubes, rods, fibers, wires), and 2D (e.g.
sheets, platelets, flakes). The colloidal mixtures of nanostructures and
PCMs are called nano-enhanced phase change material (NePCMs),
which can be used in a number of thermal energy-related applications.
Table 1 summarizes several noteworthy studies which have successfully
prepared NePCMs with remarkably enhanced thermal conductivities.
The main factors for the thermal enhancement include the type of base
PCM, as well as the type, morphology, size, and concentration of na-
nostructures [18]. Another important factor is the dispersion stability of
nanostructures in the base PCM, which is discussed in Section 5.1.
Besides the thermal conductivity, nano dispersion could dramati-
cally change the other thermophysical properties of the base PCM, such
as viscosity, density, latent heat of fusion, specific heat, phase change
temperature, and supercooling degree [37]. Some of these changes are
negative and should not be neglected [38]. Numerically simulate the
effects of the changed properties can greatly facilitate the selection of
suitable nanostructures. The simulation results also provide a cost-ef-
fective way to better understand the flow and heat transfer character-
istics of NePCMs in containers [39]. However, there are also challenges
involved. The first difficulty lies in how to properly consider the pre-
sence of nanostructures in numerical parameters and models. Hence,
there is a necessity to elaborate on the difference between the numer-
ical simulation of phase change and that with nano dispersion. The
numerical methods for modeling of NePCMs are scattered across the
literature, which requires a detailed review to address the pros and cons
of each approach. Secondly, the numerical models of NePCMs should be
validated by experiments. However, some experimental studies of
NePCMs [40–44] have reported results that contradicted other simu-
lation results, particularly in the melting process. Hence, it is para-
mount to identify the reasons for these discrepancies, and to use ap-
propriate methods to improve the accuracy of simulation results. Since
numerical models are based on some assumptions to make the calcu-
lation process easier, the existence of nanostructures may require ad-
ditional considerations in the classical phase change formulations.
Furthermore, there is currently no standard way to assess the thermal
performance of NePCM systems, and one may overestimate the real
performance using the same indicators for pure PCMs. Hu et al. [45],
for example, emphasized that a faster melting rate does not always
represent a higher heat storage rate in the cases with nano dispersion. A
deeper insight should be given into the evaluation methods used in the
NePCM literature.
To the best of our knowledge, the previous review papers [46–48]
have not sufficiently discussed the issues mentioned above. Hence, the
novelty of this review is to (1) update the existing NePCM studies using
different numerical techniques, (2) compare the assumptions adopted
in the reported models, (3) address the advantages and limitations of
each model, (4) identify the reasons for the discrepancy between si-
mulation and experiment, and (5) reveal the basic phase change be-
havior of NePCMs. Fig. 1 shows an overview of this work. It starts with
a brief review of the physical models of NePCMs (Section 2.1). Next, the
most common numerical methods that used in macroscale, mesoscale,
and molecular-scale simulations are introduced (Section 2.2). This is
followed by a summary of the prediction models of effective thermo-
physical properties that used in NePCM studies, along with the factors
considered in each model (Section 2.3). Then, we review melting
(Section 3) and solidification (Section 4) processes of NePCMs inside
different containers. The nanostructures are divided into nanocarbons,
nanometals, and nano metal oxides. Particular attention has been given
to the improved thermal performance of NePCM systems. The key
findings are summarized in tables for comparison at the end of each
section. In Section 5, we give a critical discussion on the deviations
between numerical and experimental studies, the basic melting and
solidification characteristics of NePCMs, as well as the pros and cons of
dispersing nanostructures. Based on the literature review, we identify
the research gaps in the past studies, and propose some possible di-
rections for future work.
2. Numerical simulations of NePCMs
2.1. Physical models of NePCMs
When a NePCM is fully melted, it can be seen as a nanofluid. The

3
T. Xiong, et al.
Fig. 1. Overview of the present review.
difference is that the liquid NePCM is usually under buoyancy-driven
laminar flow condition, while the nanofluid can be under both laminar
and turbulent flow conditions [49]. Further, the NePCM also performs
in solid and mushy (semi-solid) states, so it will show different thermal
and rheological behavior as its temperature goes up or down. To con-
sider the dynamics of nanoparticles in the base fluid, the physical
models of liquid NePCMs (nanofluids) can be based on single-phase and
two-phase approaches.
There are two main single-phase models, namely the homogeneous
and thermal dispersion models. The homogeneous model assumes the
ultra-fine nanoparticles are uniformly dispersed in the base fluid. The
nanoparticles can be easily fluidized, so there is no slip between the
base fluid and nanoparticles [50]. Further, the base fluid and nano-
particles are in thermal equilibrium [51]. Under these assumptions, the
nanofluid can be treated as a homogeneous mixture with average
thermophysical properties of components. The homogeneous model is a
“static” model, and it has the benefits of simplicity and high compu-
tational efficiency since all governing equations are given in the general
form. However, the simulation results will largely depend on the ef-
fective thermophysical properties of nanofluid, particularly the thermal
conductivity and viscosity. This is because the influence of dispersing
nanoparticles is only captured in the effective properties. To improve
the homogeneous model, several thermal dispersion models [52–54]
were developed by considering the contribution of thermal dispersion
to heat transfer enhancement of nanofluid. The thermal dispersion ef-
fect results from the random and chaotic motion of nanoparticles in the
base fluid, which produces small perturbations in both velocity and
temperature [55]. Hence, the thermal dispersion model is a “dynamic”
model. For a fully developed nanofluid flow, it can produce a better
result by further considering the nanoparticle migration, which is
mainly due to Brownian motion and thermophoresis [56].
The slip velocity between the base fluid and nanoparticles may not
be zero in the cases with high particle concentrations [57]. Further, the
nanoparticle migration can lead to nonuniform concentration dis-
tributions and thermal properties throughout the flow domain [58].
The above are the solid-liquid flow features of nanofluids. Hence, in the
two-phase methods, the base fluid and nanoparticles are simulated as
two individual phases with different velocities and possible different
temperatures [59]. The most common two-phase mixture models are
Eulerian-Eulerian and Eulerian-Lagrangian. The former is suitable for a
high particle volume fraction, while the latter is suitable for a low
particle volume fraction [60]. The advantages and limitations of each
model have been well explained in the literature [59,61]. Though two-
phase models may provide a realistic result by considering the slip
mechanisms between nanoparticles and base fluid, they are computa-
tionally demanding and time consuming.
Despite numerous studies have focused on the numerical
4
Applied Thermal Engineering 178 (2020) 115492
simulations of nanofluids using two-phase mixture models. The nu-
merical simulations of NePCMs based on two-phase approaches, to the
best our knowledge, have not yet been reported in the literature. One
reason could be that it is much more challenging to couple the physical
states of NePCMs (i.e. solid, mushy, and liquid) with the dynamics of
nanoparticles (i.e. Brownian motion and thermophoresis) in the two-
phase nanofluid models. This means some techniques are needed to
track and control the nanoparticle diffusion in the base PCM upon
phase change. For instance, Brownian motion should be ignored in the
solid NePCM, while it should be individually considered in the mushy
zone and in the liquid NePCM. Further, the reliability of these techni-
ques should be validated against experimental data, which remains
fairly incomplete. In fact, the common two-phase models such as mix-
ture model and Eulerian model are unable to be used in conjunction
with the solidification and melting model in ANSYS Fluent [62]. Con-
sidering these reasons, the vast majority of simulations have been based
on single-phase approaches and classical phase change formulations,
along with the following assumptions [63,64]:
(1) The NePCM is homogeneous and isotropic.
(2) The liquid NePCM is a Newtonian and incompressible fluid.
(3) The liquid NePCM is under laminar flow, and the viscous dissipa-
tion is negligible.
(4) The phase change process is conduction and convection controlled,
and the Boussinesq approximation is used to account for the natural
convection.
(5) The thermophysical properties of NePCM are temperature-in-
dependent, except the thermal conductivity and the density in the
buoyance term.
2.2. Numerical methods used in simulations of NePCMs
Depending on the scale of the problem, the simulations of NePCMs
can be divided into three main types: macroscale, mesoscale, and mo-
lecular-scale. As shown in Fig. 2, each simulation is based on numeri-
cally solving a number of mathematical equations for the concerned
physical phenomena. In the literature, the first two simulations have
been widely adopted to investigate the flow and heat transfer char-
acteristics of NePCMs, while the third one has been used to predict the
effective thermophysical properties of NePCMs. This section introduces
the numerical methods used in each simulation.
2.2.1. Macroscale simulation
Macroscale simulations, such as finite volume method (FVM) and
finite element method (FEM), are based on directly discretizing the
governing equations for fluid flow and heat transfer. The discrete
equations are then numerically solved to obtain velocity and
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Fig. 2. Numerical simulations of NePCMs.

Fig. 3. Flow chart of the macroscale simulation of NePCMs.

temperature fields. Fig. 3 shows a flow chart of the macroscale simu- NePCMs. The correlations can be obtained by prediction models or
lation of NePCMs. Under the assumptions mentioned in Section 2.1, the experimental measurements. As for the phase change (also referred to
basic fundamental is to introduce suitable correlations to capture the as latent heat) models, most simulation studies have used fixed grid
influence of dispersing nanostructures on the material properties of methods which can be divided into three main types: effective heat

5
T. Xiong, et al.
capacity method (EHCM), enthalpy method (EM), and heat source term
method (HSTM). All these methods are straightforward for coding into
FVM or FEM based computational fluid dynamics (CFD) packages (e.g.
COMSOL Multiphysics and ANSYS Fluent).
(1) Effective heat capacity method
In this method, the temperature (T) is the primary dependent
variable in the energy equation Eq. (1).
∂T
ρCeff = ∇ ·(k∇T )
∂t (1)
where k and ρ are the thermal conductivity and density of NePCM,
respectively. Ceff is the effective heat capacity of NePCM which re-
presents both sensible heat (Cp) and latent heat (L).
The EHCM is easy to implement since it only has one unknown
variable T. The energy equation given in the general form also makes
the EHCM suitable for implicit discretization in time [65]. From Eq. (1),
it is clear that the key of this method lies in the specification of Ceff (T)
relationships which can be mainly categorized into two types: empirical
and experimental relationships.
The empirical relationship considers the L as a constant in the Ceff
over the phase change temperature range, within which the NePCM is
treated as a pseudo mushy zone. Thus, the Ceff can be given by [66]:
T < Ts (solid state)
⎧Cp, s
⎪ Cp, s + Cp, l L
Ceff = + Ts ⩽ T < Tl (mushy state)
⎨ 2 Tl − Ts
⎪Cp, l T ⩾ Tl (liquid state)
⎩ (2)
where Cp,s and Cp,l are the specific heat capacities of solid NePCM
and liquid NePCM, respectively.
When dealing with narrow or isothermal phase change problems,
the use of the above relationship may create singularity and con-
vergence issues due to the sharp jump of Ceff in the mushy zone. Hence,
Jin et al. [67] pointed out the accuracy of using the empirical re-
lationship is acceptable when the phase change temperature range is
greater than 2 °C. Further, a small time step is required for accurate
results. This is because when the temperature variation in one time step
is greater than the phase change temperature range, the solver may
underestimate the latent heat contribution in the mushy zone [66].
Hence, this method is less computationally efficient. Some similar Ceff
(T) relationships were compared in a recent study [68].
The experimental relationship can be obtained by differential
scanning calorimetry (DSC), which is more straightforward and accu-
rate than the empirical relationship. Based on the DSC result, the Ceff
can be given by [69,70]:
dH ⎛m · dT ⎞
Ceff =
dt ⎝ dt ⎠ (3)
where H is the total enthalpy of NePCM, m is the mass of the NePCM
sample used in the DSC test. In fact, dH/dt is the heat flow rate through
the NePCM, and dT/dt is the scanning rate of the DSC test (i.e. tem-
perature increase or decrease rate).
Since the obtained Ceff (T) curve by DSC is usually non-linear, it
needs to be processed using piecewise linear interpolation in numerical
simulations. It is worth mentioning that the sample mass and DSC
scanning rate can remarkably influence the obtained results in the dy-
namic mode, in which the sample is heated or cooled at a constant rate.
This is because the sample with a large size may not be in thermal
equilibrium with the ambient environment under a fast heating/cooling
rate [71]. Iten et al. [72] suggested that the DSC scanning rate should
be based on the practical cooling/heating rate of the selected applica-
tion. On the other hand, NePCM samples with a small mass (usually
5–50 mg) may not be entirely homogeneous, so the consistency be-
tween the DSC results using different samples of the same material may
not be guaranteed. To resolve this problem, the isothermal step mode
can be used.
(2) Enthalpy method
6
Applied Thermal Engineering 178 (2020) 115492
In this method, Cp and L are combined into the total enthalpy (H) as
the primary dependent variable in the energy equation Eq. (4):
∂H
ρ = ∇ ·(k∇T )
∂t (4)
Similar to the EHCM, the key of this model is to use a suitable H (T)
relationship, from which the temperature can be derived. The most
common H (T) relationship can be written as [67,73,74]:
T
⎧ ∫T0 Cp, s dT T < Ts (solid state)
⎪ T
s T − Ts
H = ∫T Cp, s dT + L T − T Ts ⩽ T < Tl (mushy state)
⎨ 0 l s
⎪ ∫Ts C dT + L + ∫T C dT T ⩾ Tl (liquid state)
p, s p, l
⎩ T0 Tl (5)
where T0 is the initial temperature at which the H is 0 kJ/kg.
It should be noted that the above relationship is a simplified one
assuming the growth of total enthalpy in each state is linear. The real H
(T) curves should be determined by DSC. As mentioned earlier, the
small mass of sample may influence the DSC results. To characterize the
thermal properties of a bulk material, T-history method was proposed
by Zhang et al. [75]. Owing to its simplicity and accuracy, the T-history
method has been used for thermal characterizations of NePCMs, in-
cluding specific heat, latent heat of fusion, and thermal conductivity
[76–78]. The enthalpy method has gained popularity since it can solve
both smooth and sharp phase transition problems. However, the tem-
perature at a typical grid point may oscillate with time [79]. Further,
the use of linear H (T) curves could produce discrepancies between
simulation and experimental results [80].
(3) Heat source term method
In fact, the HSTM is an alternative discretization for the enthalpy
method. By splitting the H into Cp and L, Eq. (4) can be written as [81]:
∂T ∂f
ρCp = ∇ ·(k∇T ) − ρL
∂t ∂t (6)
where f is the liquid fraction of NePCM, and it can be written as:
⎧0 T < Ts (solid state)
⎪ T − Ts
f= Ts ⩽ T < Tl (mushy state)
⎨ Tl − Ts
⎪1 T ⩾ Tl (liquid state)
⎩ (7)
From Eq. (6), the primary dependent variable in the HSTEM is T.
The HSTM can deal with smooth and sharp phase change problems,
similar to the enthalpy method. The use of the above f (T) relationship
was found to be effective in achieving a faster convergence rate under a
Newton-Raphson procedure [82]. The key of this method is how the f is
updated in each iteration, which usually requires an optimum under-
relaxation factor [66]. A modified HSTEM that does not need any
under-relaxation was proposed by Voller and Swaminathan [83].
Many available phase change models assume that the melting and
solidification processes follow an identical Cp (T) or H (T) relationship,
which may lead to divergence between simulation and experimental
data. This is because the onset temperature of solidification is usually
lower than the end temperature of melting, which is the so called phase
change hysteresis [84]. To consider this phenomenon in a consecutive
charging and discharging process (e.g. PCMs for passive cooling of
building envelopes), two Cp (T) or H (T) relationships should be used:
one for charging and the other one for discharging [85].
Compared to the phase change hysteresis, the supercooling phe-
nomenon is more difficult to be numerically simulated. Most numerical
studies of supercooling were based on the enthalpy method. For ex-
ample, Bony and Citherlet [84] proposed a supercooling model by using
two H (T) curves to separately model the discharging processes of a
PCM water tank with and without supercooling. In the H (T) curve for
describing supercooling, the authors assumed the crystallization pro-
cess of supercooled PCM is instantaneous and isenthalpic. The same
model was used by Huang et al. [74] to consider the supercooling of
T. Xiong, et al.
hydrate salt based PCMs. Based on the EHCM, Jin et al. [86] developed
a supercooling model, which assumes there is an internal heat source in
the PCM to account for the latent heat released from the fast crystal-
lization process. Similarly, Zhou and Han [87] developed a multiphase
model for supercooling by introducing a heat flux source term in the
energy equation. It should be noted, however, that nanoparticles as a
nucleating agent can effectively mitigate the supercooling of PCM. Wu
et al. [88], for instance, decreased the supercooling degree of water by
70.9% by dispersing 0.2 wt% Al2O3 nanoparticles. In a study by Liu
et al. [89], 0.05 wt% graphene oxide nanosheets decreased the super-
cooling degree of water by 69.1% with advancing the onset time of
nucleation by 90.7%. Given these experimental results, most numerical
studies have neglected the supercooling of NePCMs in the solidification
process [90].
In addition to the supercooling degree, many experiments [91,92]
have proved that dispersing nanoparticles can increase the viscosity of
the base PCM, which may weaken the convection heat transfer in the
melting process. Hence, it is important to numerically investigate the
flow behavior of NePCMs. The key for a realistic flow behavior is to
couple the physical states (i.e. solid, mushy, and liquid) with the ve-
locity values of computational cells. Particularly, the velocity should be
vanished in the solid cell. Three solid velocity correction methods are
mainly used:
(1) Switch-off method
It is a straightforward method that directly overwrites the velocity
value to zero in the solid cells. Nevertheless, it may create convergence
issues due to the velocity discontinuity at the mushy zone [79]. To
avoid this, a ramped switch-off method can be used [93].
(2) Variable viscosity method
This method considers that the solid phase has a very large viscosity
value. For example, several numerical studies [94–97] defined the dy-
namic viscosity of the solid NePCM as 106 Pa·s. The ultra-high viscosity
will increase the diffusive term in the momentum equation, thereby
inhibiting all motions in the solid cells. Different viscosity definitions
for the solid phase can be found in [98]. However, this method tends to
produce divergency if the time step does not match with the grid size
[79].
(3) Darcy source term method
This method considers the mushy zone as a porous medium in which
the convection flow is simulated following the Carman-Kozeny equa-
tion. The combination of the enthalpy method and Darcy source term
method is the so called “enthalpy-porosity method [99]” (EPM), which
has been extensively used in the PCM/NePCM literature. In the EPM, a
liquid fraction based Darcy source term S (β) is introduced in the mo-
mentum equation to “switch on/off” the velocity in the case of melting/
freezing, which can be given by:
(1 − β )2
S= Amush ui
(β 3 + ε ) (8)
where ε (usually is 0.001) is a small number to avoid dividing by
zero, and Amush is the mushy zone constant.
The Amush represents the amplitude of the velocity damping; the
larger the Amush, the faster the velocity is damped in the mushy zone.
Though Amush values ranging from 103 to 108 have been recommended
in most phase change studies, the use of different Amush values can exert
significant influence on the simulated results. For example, a higher
Amush vale (107) can lead to a delayed melting rate along with a more
realistic evolution of melting front as compared to a lower one (105)
[100]. Similar results were also obtained for the solidification processes
modeled with using different Amush vales [101]. Given the influence of
nanoparticles on the rheological behavior of the base PCM, the adopted
Amush in the numerical studies of NePCMs should be reported.
2.2.2. Mesoscale simulation
Mesoscale simulations investigate the physical phenomena at a scale
7
Applied Thermal Engineering 178 (2020) 115492
that lies between the macroscale and the microscale. In the literature,
the most common mesoscale simulation technique is lattice-Boltzmann
method (LBM). The LBM follows the discrete movement theory to
consider a set of fictive fluid particles confined to a regular lattice
[102]. The particle streaming and collision are simulated by solving a
special discretized form of the continuous Boltzmann equation for the
single-particle distribution function [103]. Different from the macro-
scale techniques which directly discretize and solve the governing
equations for continuum fluid mechanics (i.e. continuity, momentum,
and energy), the LBM integrates the distribution functions of lattices to
recover the distribution of macroscopic properties of the fluid.
There is a growing trend for using the LBM to solve solid–liquid
phase change problems in recent years, which can be classified into two
main types: phase-field LBM [104] and enthalpy-based LBM [105]. The
phase-field LBM requires extremely small grid spacing for tracking the
solid–liquid interface, and thus it is computationally demanding. Con-
sequently, the phase-field LBM is usually used to study the crystal
growth rather than the flow and heat transfer characteristics of mate-
rials [106]. As for the enthalpy-based LBM, it is actually based on using
classical LB models (e.g. double distribution functions LB model [107]
and multi-relaxation-times LB model [108]) to solve the main part (i.e.
transient, convective and diffusion terms) of Eq. (6). Further, the latent
heat source term in Eq. (6) is introduced as a source term in the tem-
perature distribution function of LB model. The commonly used 2D and
3D discrete velocity models are D2Q9 and D3Q19, respectively. The
simulation of NePCMs using the LBM follows the same assumptions
mentioned in Section 2.1.
The LBM has the benefits of solving linear equations, simple pro-
gramming, and handling complex boundary conditions. More im-
portantly, the LBM is very suitable and stable for parallel computing
owing to its explicit scheme, local interactions, and consequently a very
low communication-to-computation ratio [109]. However, there are
also some issues to be resolved. For example, a deviation term can be
produced in most LBM-based phase change models when recovering the
corresponding macroscopic equations [110,111]. In addition, most of
the NePCM models based on the LBM were not validated against a wide
range of experimental data, so there should be more investigations fo-
cused on this area.
2.2.3. Molecular-scale simulation
When the problem is investigated at the molecular-scale, the con-
tinuum assumption is no more valid. Molecular dynamic (MD) simu-
lation considers the interactions between a set of atoms and molecules
(system components) over a fixed period of time until the system
reaches a dynamic evolution [102]. Since the time period is extremely
short, typical MD time steps are usually in the order of 1 fs (10−15 s).
The MD simulation solves Newton’s equations of motion to obtain the
trajectories of atoms and molecules, from which the physical quantity
of interest can be derived. Further, molecular mechanics force fields or
interatomic potentials are used to calculate forces between the particles
and their potential energies, which is the key for an accurate MD si-
mulation of the studied physical quantity [112].
As mentioned in Section 2.2.1, the thermal characterizations of
NePCMs can be influenced by many factors, and the obtained results
may have uncertainties. The MD simulation can be used to investigate
the thermophysical properties of NePCMs. Yu et al. [113] adopted an
optimized MD method (Fig. 4) to simulate the influence of SiO2 nano-
particles on the thermophysical properties of NaCl molten salt PCM.
Their results showed that dispersing 2.4 vol% of SiO2 nanoparticles
significantly improved the thermal conductivity of NaCl by up to
44.2%. The shear viscosity of molten NaCl was also decreased by up to
23.6%. Further, the melting point of NaCl increased with the volume
fraction of SiO2 nanoparticles. Zhang et al. [114] performed a non-
equilibrium MD to simulate ethylene–vinyl acetate paraffin PCMs dis-
persed with different concentrations of graphene. The simulated results
showed that the case with dispersing 0.7 wt% of graphene reached a
T. Xiong, et al.
Fig. 4. Flow chart of the optimized MD simulation of NaCl-SiO2 molten salt NePCMs [113].
better thermal conductivity enhancement than those with dispersing
higher concentrations (1.5 wt%, 3.6 wt%, and 7.0 wt%). This trend may
be due to the complex interactions between ethylene–vinyl acetate and
graphene. Similar MD simulations of nanocarbons enhanced PCMs were
also conducted by Tafrishi et al. [115] and Babaei et al. [116]. Despite
the thermal conductivity enhancement, the latent heat reduction
caused by nanoparticles should also be investigated. Zhao et al. [117],
for instance, indicated that dispersing 19.72 wt% CuO nanoparticles
reduced the melting enthalpy of paraffin wax by as much as 51.5%. The
significant latent heat reduction is due to the dense phase which results
from the interactions between nanoparticles and PCM.
Table 2 summarizes the above mentioned numerical methods along
with their advantages and limitations.
2.3. Prediction models and factors
As mentioned in Section 2.1, the effective thermal conductivity (knp)
and viscosity (µnp) of NePCMs are very important for accurate simula-
tion results. Though the underlying mechanisms for the thermal and
rheological properties of nanofluids are still not well understood with
some remain controversial [119]. Several prediction models have been
extensively used in numerical studies of NePCMs to obtain the knp and
µnp. This section focusses on these models with their limitations and
applicable ranges.
2.3.1. Effective dynamic viscosity
(1) Brinkman model
μp
μnp =
(1 − ϕ)2.5 (9)
8
Applied Thermal Engineering 178 (2020) 115492
By extending the Einstein’s equation [120], Brinkman [121] pro-
posed this model to predict the viscosity of particle suspensions with
moderate loadings. The Brinkman model considers the dispersion of
one solute-molecule to a continuous solution. Several experiments
[122–124] have verified that the Brinkman model underestimated the
viscosity of nanofluids, except in the case of low particle volume frac-
tions (ϕ < 3%).
(2) Krieger-Dougherty (K-D) model
−Aϕmax
ϕ ⎞
μnp = μp ⎜⎛1 − ⎟
⎝ ϕmax ⎠ (10)
where ϕmax is the maximum packing factor, and A is the intrinsic
viscosity.
Krieger and Dougherty [125] derived this semi-empirical equation
based on the differential effective medium theory (DEMT). The values
of ϕmax and A for particles in the shapes of spheres, ellipsoids, cylinders,
rods, and dumbbells can be found in [125,126]. However, comparisons
have shown that the K-D model can underestimate the viscosity of TiO2
and Al2O3 nanofluids [127]. Chen et al. [128] pointed out that the best
prediction results can be achieved using the concentration of nano-
particle aggregates. For nanospheres, the aggregate size is about 3 times
of the primary nanoparticles size. Given these results, the K-D model
may not be very suitable for predicting the viscosity of nanoparticle
suspensions.
Three empirical correlations Eqs. (11)–(13) were proposed based on
experimental data, and they have been frequently adopted in the
NePCM studies.
(3) Vajjha’s model
μnp = 0.983e (12.959ϕ) μp , 0.01 ⩽ ϕ ⩽ 0.1 for Al2 O3 nanofluid (11)
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

is influenced by many factors, such as sample

A linear H (T) relationship may produce discrepancies between numerical

μnp = 0.919e (22.853ϕ) μp , 0.01 ⩽ ϕ ⩽ 0.06 for CuO nanofluid

demanding, which is related to the number of particles.

and isothermal phase change problem problems.
(12)

deviation term can be produced when recovering the corresponding

variable thermophysical properties is not straightforward
Vajjha [129] developed the equations based on the empirical cor-
relations by Sahoo et al. [130] and Namburu et al. [131]. Vajjha et al.
[132] suggested that Eqs. (11) and (12) are practical within 20–90 °C.
The authors used ethylene glycol/water (EG/W, 60:40) as the base

• Difficult to decide the most suitable force fields [113].

optimum under-relaxation factor is required [83].
fluid, but the average nanoparticle size was not reported.
(4) Corcione’s model
time step is needed for accuracy [66].

μp

viscosity is not a direct input [102].

μnp =

models for NePCMs are scare.

oscillation problems [79].

1 − 34.87(dn dp, e )−0.3ϕ1.03 (13)

efficiency [66].

computational efficiency [66].

equations [110,111].
• mass and DSC scanning rate [72].

where dn is the nanoparticle diameter, and dp,e is the equivalent

experimental results [80].

diameter of the base fluid molecule given by:

• A suitable C (T) relationship

1
• Difficult to solve sharp

3
⎛ 6M ⎞
dp, e = 0.1 ⎜
• ALowsmallcomputational

Nπρp,0 ⎟
(14)
• Computationally
⎝ ⎠
p

• Temperature

• Amacroscopic
where M is the molecular weight of the base fluid, N is the Avogadro
• Validated
• Modeling

number, and ρp,0 is the density of the base fluid at 20 °C.

Limitations

[102].

The above model was developed by fitting a large number of ex-

• Bulk
• Low
• and
• An

perimental data of nanofluids with a standard deviation of 1.84%, in-

cluding water, ethanol, EG, and propylene glycol (PG) dispersed with
TiO2, Al2O3, SiO2, and Cu nanoparticles [122]. The applicable ranges of
faster convergence rate under a Newton-Raphson procedure [82].
for both isothermal and smooth phase change problems.

for both isothermal and smooth phase change problems.

for non-equilibrium processes at the atomic level [118].

dn and ϕ were reported to be 25–200 nm and 0.0001–0.071, respec-

complex geometries and porous medium [103].

tively. Further, the correlation was independent of temperature within

• molecules [102]. for considering the interactions between
for smooth phase change problems (phase change

20–60 °C.
Table 3 summarizes the above prediction models of effective dy-
namic viscosity. Based on the reported models, there are several issues
simple for in-house programming.
equation is given in the general form.

to be resolved:
temperature range is greater than 2 °C [67]).

• Simulate dynamic properties of the system.

and simple programming

First, the base fluids studied in the above models are water, ethanol,
for simulating complex fluids.
parallel computing [109].

PG, and EG, whereas their rheological properties, molecular structures,

and intermolecular interactions are different from those of PCMs (e.g.
for complex geometries.
computational efficiency.

paraffin wax and eutectic salts). Using these nanofluid prediction

one unknown variable.

to reach convergence.

models to evaluate the viscosity of NePCMs may produce uncertainties.

Second, surfactants have been frequently used to improve the sus-
pension stability of nanoparticles, which was also found to increase the
• Mesoscopicfor nature
• Suitableequations

viscosity of nanofluids [133]. However, none of the above models

• Conceptually

considered this effect.

• Suitable for

Third, the morphology of nanoadditives has an important influence

• Suitable
• Suitable
• Suitable

• Suitable
• Suitable
• Suitable
Advantages

• Energy

• ALinear
• High
• Only

on the viscosity of nanofluids, but most of the above models are only
• Easy

applicable for microspheres or nanospheres. For example, a recent

study [134] have shown that nano-Al2O3 in the shapes of nanoparticles
and nanorods increased the viscosity of eutectic salt by 25% and 37%,
LAMMPS [115–117]; Materials Studio
COMSOL Multiphysics (FEM); ANSYS

COMSOL Multiphysics (FEM); ANSYS

COMSOL Multiphysics (FEM); ANSYS

respectively, However, dispersing multi-walled carbon nanotubes

(MWCNT) [135] and graphene [136] could reduce the viscosity of
nanofluids, which was attributed to the self-lubrication effect of
MWCNT and graphene. Hence, using the above models may produce
uncertainties for the NePCMs dispersed with non-spherical nano-
Common CFD codes
Summary of the main techniques for simulations of NePCMs.

OpenLB; Palabos

particles.
Fluent (FVM)

Fluent (FVM)

Fluent (FVM)

[113,114]

2.3.2. Effective thermal conductivity

The Maxwell model [137] based on the effective medium theory
(EMT) assumes there is no slip between the base fluid and particles, so it
is a “static” model. Hamilton and Crosser [138] further extended the
Maxwell model to non-spherical particles. However, the Hamilton-
Enthalpy-based
Phase change

Crosser (HC) model not only underestimated the thermal conductivity

enhancement by dispersing nanosized particles, but also failed to ad-
EHCM
model

HSTM

dress the influence of nanoparticle size and temperature dependency.

LBM

N.A.
EM

On the other hand, factors such as thermal dispersion, thermal interface

resistance, Brownian motion, and nanoparticle morphology also have
Simulation technique

significant impacts. Accordingly, several extensions were developed by

adding a “dynamic” part into the Maxwell-HC model [139].
(1) Thermal dispersion model
FVM/FEM
Table 2

kn + 2kp − 2ϕ (kp − kn )
kp + C′ (ρCp )np |u| ϕdn
LBM

knp =
MD

kn + 2kp + ϕ (kp − kn ) (15)

9
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Table 3
Summary of prediction models of effective dynamic viscosity used in NePCM studies. Note: the values without a citation are summarized based on the reviewed
studies in Section 3 and 4.
Prediction model Factors Applicability

Morphology Particle size Temperature (°C) Concentration (vol.%)

Brinkman model ϕ, µp microsphere > 1000 nm [121] 0–170 °C 1–8%

K-D model ϕ, µp, ϕmax, A sphere, ellipsoid, cylinder, rod, dumbbell > 1000 nm [125] 20–40 °C 1–2%
Vajjha’s model ϕ, µp nanoparticle 10–100 nm 20–90 °C [129] 1–10% for Al2O3 [129]
1–6% for CuO [129]
Corcione’s model ϕ, µp, dn, dp,e nanoparticle 25–200 nm [122] 20–60 °C [122] 0.01–7.1% [122]

where u is the fluid velocity, and C’ is an empirical constant which is (4) Nan’s model
usually evaluated following the work by Wakao and Kaguei [140].
3 + ϕ [2β11 (1 − L11) + β33 (1 − L33 )]
It should be note, however, that the values of C’ were not explicitly knp = kp
3 − ϕ (2β11 L11 + β33 L33 ) (22)
stated in any NePCM studies except the studies [141,142]. The second
part of Eq. (15) represents the contribution of thermal dispersion effect, where
which is the so called dispersion thermal conductivity. The form of the
k11 − kp k33 − kp
dispersion thermal conductivity was proposed by Xuan and Roetzel β11 = , β33 =
[54], and it was adopted by Khanafer et al. [143] for modeling Cu kp + L11 (k11 − kp ) kp + L33 (k33 − kp ) (23)
nanofluids. However, the temperature dependency is not considered in where L11 and L33 are the geometrical factors of nanostructures, and
this model, which may produce deviations for simulation results. they can be expressed as:
(2) Vajjha’s model
a2 a
kn + 2kp − 2ϕ (kp − kn ) BT L11 = − cosh−1 a, for a > 1 and L33 = 1 − 2L11
knp = kp + 5 × 10 4γϕ (ρCp )p f (T , ϕ ) 2(a2 − 1) 2(a2 − 1)3 2
kn + 2kp + ϕ (kp − kn ) ρn dn
(24)
(16)
a2 a
where B is the Boltzmann constant (B = 1.3807 × 10−23 J/K), γ is L11 = + cos−1 a, for a < 1 and L33 = 1 − 2L11
2(a2 − 1) 2(1 − a2)3 2
the fraction of the liquid volume traveling with a nanoparticle and can
(25)
be defined as:
1
γ = 8.4407(100ϕ)−1.07304, 0.01 ⩽ ϕ ⩽ 0.1 for Al2 O3 nanofluid (17) L11 = L33 = , for a = 1
3 (26)
γ= 9.881(100ϕ)−0.9446, 0.01 ⩽ ϕ ⩽ 0.06 for CuO nanofluid (18) where a is the aspect ratio of nanostructures, k11 and k33 and are the
The empirical function f (T, ϕ) can be given by: equivalent thermal conductivities along different cell directions, and
they can be expressed as:
f (T , ϕ)
kn
T k ii = θLii kn
, i = 1, 3
= (2.8217 × 10−2ϕ + 3.917 × 10−3) + ( −3.0669 × 10−2ϕ 1+
Tref kp (27)
− 3.9112 × 10−3) (19) where
The second part of Eq. (16) captures the improved thermal con- Rkp

ductivity induced by Brownian motion of nanoparticles with con- θ=

⎧ 2+( 1
a ) ln
, for a ⩾ 1
⎨ (2 + 2a) Rkp
sidering the influence of temperature. The authors [144] suggested that , for a ⩽ 1
⎩ dn (28)
the applicable ranges of dn and T are 29–77 nm and 25–90 °C, respec-
tively. where R is the thermal boundary resistance between the nanos-
(3) Corcione’s model tructures and base fluid.
10 0.03 The main feature of this EMT based model is that the interfacial
⎡ T k ⎤
knp = kp ⎢1 + 4.4Re0.4Pr 0.66 ⎛⎜ ⎞⎟ ⎛⎜ n ⎞⎟ ϕ0.66⎥ thermal resistance and nanostructure morphology are considered
⎝ Tfr ⎠ ⎝ kp ⎠ (20) [146]. Hence, the Nan’s model is practical for nanostructures in the
⎣ ⎦
shapes of aligned continuous fibers, laminated flat plates, spheres, and
where Pr is the Prandtl number of the base fluid, and Tfr is the misoriented ellipsoidal particles. However, its accuracy is greatly af-
freezing point of the base fluid. Re is the nanoparticle Reynolds number fected by the assumption of R. For instance, the predicted thermal
which is defined as: conductivity of graphene nanoplatelets (GnP)/eicosane at 10 °C showed
2ρp BT the best agreement with experimental data for R of 9 × 10−9 m2·K/W
Re = [20]. At 20 °C, Harish et al. [147] validated the Nan’s model for GnP
πμp2 dn (21)
enhanced lauric acid with assuming the R to be 10−8 m2·K/W. On the
Corcione [122] developed this semi-empirical model by regression other hand, the Nan’s model has not been validated against the ex-
analysis. The model considers the nanoparticle size, fluid temperature, perimental data of liquid NePCMs, which requires further investiga-
and base fluid properties. It showed a standard deviation of 1.86% tions. Xu and Kleinstreuer [148] proposed a similar model which con-
against the experimental data of water, EG, and PG dispersed with Cu, siders the influence of nanoparticle aggregates.
Al2O3, CuO, and TiO2 nanoparticles. The applicable ranges of dn, ϕ, and Table 4 summarizes the above prediction models of effective
T were 10–150 nm, 0.002–0.09, and 21–51 °C, respectively. Chon et al. thermal conductivity. It is worth mentioning that in Eqs. (15) and (16),
[145] also developed a similar equation for Al2O3 nanofluids, which has the nanofluid velocity and temperature are used as correlation factors
a different definition of nanoparticle Reynolds number as compared to to control the dynamic terms. This is because the nanoparticle move-
Eq. (21). ment and its influence should be weakened in the solid. Some studies

10
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Table 4
Summary of prediction models of effective thermal conductivity used in NePCM studies.
Prediction model Factors Applicability

Morphology Particle Size Temperature (°C) Concentration (vol.%)

Thermal dispersion model kn, kp, ϕ, C’, ρnp, Cp,np, u, dn nanoparticle 10–100 nm 0–80 °C 1–10%
Vajjha’s model kn, kp, ϕ, ρp, Cp, p, ρn, dn, T nanoparticle 29–77 nm [144] 25–90 °C [144] 1–10% [144]
Corcione’s model kn, kp, ϕ, ρp, Cp, p, µp, dn, T nanoparticle 10–150 nm [122] 21–51 °C [122] 0.2–9% [122]
Nan’s model kn, kp, ϕ, a, R, dn, ln fibers, plates, spheres, ellipsoidal particles Aspect ratio < 1000 20–70 °C 1–3%

Note: the values without a citation are summarized based on the reviewed studies in Section 3 and 4.

also introduced the liquid fraction as a correlation factor in the dynamic
terms, which ensures these dynamic models can be smoothly reduced to
the Maxwell model in the solid cells. On the other hand, using the above
thermal conductivity models may produce the same issues facing the
viscosity models mentioned in Section 2.3.1.
2.3.3. Other thermophysical properties
Eq. (29)-(32) gives the prediction models of other effective ther-
mophysical properties used in the NePCM studies, including density (ρ),
specific heat (Cp), thermal expansion coefficient (β), and latent heat of
fusion (L) [149]:
ρnp = (1 − ϕ) ρp + ϕρn
(ρCp )np = (1 − ϕ)(ρCp )p + ϕ (ρCp )n
(ρβ )np = (1 − ϕ)(ρβ )p + ϕ (ρβ )n
(ρL)np = (1 − ϕ)(ρL)p
Among the above properties, the most important one for the thermal
performance of NePCMs is L. Since the nanoparticles do not change
phase, Eq. (32) considers the increase of nanoparticle volume fraction
will reduce the latent heat of NePCMs. Nevertheless, this might not
always be true in experimental results. For example, Shaikh et al. [150]
found that dispersing 1 vol% of carbon nanofibers (CNF), single-walled
carbon nanotubes (SWCNT), and MWCNT increased the latent heat of
paraffin wax by 6.8%, 10.1%, and 13.0%, respectively. Zeng et al.
[151] and Wang et al. [152] also reported a minor increase in latent
heat by adding MWCNT into pure PCMs. As for the nano metal oxides,
dispersing 0.3 wt% of TiO2 nanoparticles and CuO nanoparticles were
found to enhance the latent heat of paraffin wax by as much as 15.7%
and 64.7%, reservedly [34]. Similar results were also obtained by dis-
persing 2 wt% of α-Al2O3 nanoparticles into paraffin wax [153]. The
reason for these results is related to the interactions between the mo-
lecules of base PCM and nanoparticles. If the potential of nanoparticle/
PCM molecular interaction is greater than that of PCM intermolecular
interaction, the latent heat may increase [150].
Despite the latent heat of PCMs can be increased by nanoparticles,
the vast majority of studies have observed degraded latent heat in both
experiments [18,37,38] and MD simulations [117,154]. The incon-
sistent variations of latent heat may be one reason for the discrepancy
between simulation and experimental results, since the numerical
models based on Eq. (32) always assume that the latent heat is reduced
by nanoparticles. Hence, more efforts should be devoted to an improved
understanding of the underlying mechanisms for the variation of latent
heat with nanoadditives.
3. Melting studies of NePCMs
3.1. Nanocarbon enhanced PCMs
Carbon nanomaterials, including graphite, carbon nanotubes (CNT),
and GnP, have been positively used to enhance pure PCMs due to their
excellent thermal conductivity (2000–3500 W/m·K). Das et al. [155]
simulated the melting of n-eicosane/GnP in a vertically oriented shell-
and-tube system based on the EPM. The K-D models showed that dis-
persing 3 vol% of GnP increased the effective viscosity of NePCM by
36.1% and reduced the latent heat by 8.5%. The increased viscosity was
found to suppress the convection heat transfer, thereby greatly off-
setting the benefit of the enhanced thermal conductivity of 205.8%.
Hence, the authors suggested to keep the GnP loading below 3 vol%. At
a heat transfer fluid (HTF) temperature of 60 °C, dispersing 2 vol% of
GnP significantly reduced the melting time by 41%. Following the same
method, the authors [156,157] further compared the effects of different
nanocarbon morphologies and system orientations on the melting rate
of n-octadecane. 0D carbon nanodiamond (ND), 1D SWCNT, and 2D
GnP were used to enhance the PCM. A low particle loading of 1 vol%
(29) was adopted in each case to maintain a moderate increase in the visc-
(30) osity of NePCM. As shown in Fig. 5, the melting time is shortened by
1%, 15%, and 25% for ND, SWCNT, and GnP in the vertical shell-and-
(31) tube system, respectively [156]. As for the horizontal system, the
melting time is reduced by 2%, 27%, and 40% for ND, SWCNT, and
(32) GnP, respectively [157]. Hence, the horizontal system is more efficient
in improving the effectiveness of carbon nanostructures.
Kant et al. [158] investigated the melting of NePCMs in a square
cavity. Their numerical method was based on the EHCM and Darcy
source term method. Three kinds of PCMs (capric acid, CaCl2·6H2O, and
n-octadecane) were enhanced by 1 vol%, 3 vol%, and 5 vol% graphene
nanoparticles. The nanoparticles increased the heat conduction but
considerably degraded the natural convection. The melting rate was
improved in all cases, indicating the contribution of the enhanced
conduction heat transfer is large enough to make up the degraded
convection heat transfer. It should be noted that the reduced latent heat
is another important reason for the accelerated melting rate, particu-
larly in the case of a high particle loading. However, the authors did not
address this in both cases. A similar study was recently performed by
Iachachene et al. [159], in which a trapezoidal cavity was used to store
graphene nanoparticles enhanced paraffin wax. The thermal con-
ductivity of paraffin wax was assumed to be enhanced by 20–100%. The
simulation results showed that the increase of thermal conductivity
should be higher than 80% to achieve an improved heat transfer per-
formance.
For GnP which is non-spherical, the prediction models discussed in
Section 2.3.2 may not be able to give results with acceptable accuracy.
Accordingly, Singh et al. [160] used Chu’s model [161] to evaluate the
effective thermal conductivity of sugar alcohol/GnP with considering
the GNP aspect ratio, interfacial thermal resistance, anisotropy, non-
linearity effects, and GnP loading. Based on the EPM, a 2-D shell-and-
tube model was established to compare the effects of varying the fin
height and GnP loading on the melting rate. Fig. 6 shows that 5 vol% of
GnP can reduce the melting time by 54.8% which is higher than the
optimized fin by 48.4%. Using both heat transfer enhancement tech-
niques, the melting time is notably shortened by 67.7%. As a follow-up
to the study [160], Singh et al. [162] further demonstrated that the
degraded convection efficiency can be overcome using an optimized fin
with dispersing 5 vol% GnP in a conical shell-and-tube container
(Fig. 7). The charging time was considerably reduced by 57%. Further,
a multi-attribute decision making (MADM) analysis was used to eval-
uate the material attributes of NePCMs. The results showed the thermal

11
T. Xiong, et al.
Fig. 5. (a) 3D numerical model of the shell-and-tube system [156] and (b) total melting time for pure PCM and NePCMs with 1 vol% of nanocarbons in vertical and
horizontal systems [157].
conductivity has the highest normalized weight of 51%, followed by the
latent heat of 26%. The authors indicated that GnP is the best thermal
conductivity enhancer for PCMs, since it exhibits the highest thermal
conductivity enhancement along with the lowest latent heat reduction
as compared to the nano metals and nano metal oxides.
Empirical viscosity models of eutectic PCMs (LiNO3-KCl) with dif-
ferent GnP loadings were obtained by rotational rheometer [163].
Fig. 8 shows that most prediction models, including the Brinkman
model, have largely underestimated the real viscosity of GnP enhanced
PCM. Using these prediction models may lead to a large under-
estimation of the degraded natural convection heat transfer in simu-
lated results. Their results showed that when using the measured
viscosity, dispersing 1 vol% of GnP can even prolong the melting time
by 6%, and dispersing 5 vol% of GnP only shortened the melting time
by 17%. In the light of these results, it is necessary to use the measured
thermophysical properties to obtain credible numerical results.
Fig. 6. Total melting time for different sets of heat transfer enhancement techniques [160].
12
Applied Thermal Engineering 178 (2020) 115492
3.2. Nanometal enhanced PCMs
Nanometals are also well known for their remarkable thermal
conductivity. Cu nanoparticles, with average thermal conductivity of
400 W/m·K and diameter of 100 nm, has been widely used to enhance
pure PCMs [164]. Darzi et al. [165] compared the benefits of dispersing
Cu nanoparticles (diameter of 80 nm) and changing the shapes of tube
heat exchanger (Fig. 9) for enhancing the melting rate of n-eicosane in a
horizontally oriented cylindrical annulus. The inclusion of 2 vol% and
4 vol% of nanocopper shortened the charging time by 25% and 46%,
respectively. Under the same operating condition, dispersing 4 vol% of
nanocopper outweighed mounting 4 fins in terms of the charging rate.
However, dispersing nanoparticles did not eliminate the stable melting
pattern at the bottom region of the annulus, as shown in Fig. 10. This
can be addressed from two aspects. On one hand, the solid PCM next to
the heat exchanger will first melt to liquid phase at the beginning of
melting. The liquid PCM with a low thermal conductivity will wrap the
T. Xiong, et al.
Fig. 7. Schematic of a conical shell-and-tube NePCM system with fins [160].
heat transfer tube, acting as a “thermal insulation” layer. The thickness
of the insulation layer will grow with time, further inhibiting the heat
from transferring to the outer region with solid PCM. This is the so
called “self-insulating” effect of PCM [166]. On the other hand, the heat
transfer rate at the top region can be compensated by the convection
heat transfer, while the bottom region is usually dominated by the
conduction heat transfer. Dispersing nanoparticles only increased the
PCM thermal conductivity, so it is unable to effectively mitigate the
imbalance of heat transfer mechanisms along the container height. To
achieve a more uniform melting process, mounting fins at the bottom
region of the container with dispersing nanoparticles can be explored.
A similar study of annulus system was conducted by Jourabian et al.
[167] to discuss the combinations of changing the position of tube heat
exchanger and Cu nanoparticle loading. The effective thermal con-
ductivity of water/nanocopper PCM was determined by a semi-
Fig. 8. Comparison between prediction models and experimental data [163].
13
Applied Thermal Engineering 178 (2020) 115492
empirical equation [168] considering the nanoparticle diameter, water
molecular size, and Brownian motion velocity. The enthalpy-based LBM
with a double distribution function (DDF) model was used to solve the
temperature and velocity fields. Mounting the heat exchanger at the
bottom section of the container with dispersing 4 vol% of nanocopper
was found to be the best heat transfer enhancement scheme. The en-
hancement is due to the shrinkage of the heat conduction dominated
region, so more regions benefit from the convection melting. However,
the increased viscosity of NePCM weakened the convection heat
transfer which is worthy of further attention. Using the same method,
similar conclusions were drawn in another two melting studies of
square cavity containers [169,170].
Feng et al. [107] developed a novel DDF-LBM involving density
evolution equation and temperature evolution equation. Their model
treated the latent heat source term with an implicit scheme, thereby
avoiding iteration steps in solving the temperature field. Results
showed that the Cu nanoparticle enhanced ice performed a higher heat
transfer rate in a square cavity heated from below. The time for
reaching a melting fraction of 0.7 was reduced by up to 17.2%. In-
creasing the volume fraction of Cu nanoparticles from 0 to 0.05 and
0.10, the energy storage rate was increased by 3.33% and 4.73% at a
Grashof number (Gr) of 5.0 × 104, and 1.5% and 5.33% at a Gr of
2.5 × 105, respectively. Interestingly, in the case at high nanoparticle
loading and Gr, an asymmetric solid–liquid interface was formed
(Fig. 11). This has been ascribed to the asymmetric distribution of the
convection cells.
Hosseinizadeh et al. [171] simulated the unconstrained melting of
nanocopper/paraffin in a spherical container. The moving interface
between the air and molten NePCM was tracked by the volume of fluid
(VOF) model. The phase change rate under different Stefan numbers
(St, 0.05, 0.1 and 0.15) and nanoparticle loadings (0%, 2% and 4%)
were examined. Since the mushy NePCM occupied most of the con-
tainer, its thermal conductivity should be carefully considered by ex-
perimental measurements. Recently, Boukani et al. [172] further in-
vestigated the influence of adding nanocopper and changing the aspect
ratio of elliptical container on the unconstrained melting of n-octade-
cane. The authors adopted the same numerical methods used in [171].
For a given aspect ratio, adding nanocopper was reported to promote
the melting rate and suppress the volume expansion of NePCM. The best
combination scheme was using an aspect ratio of 0.5 along with a
T. Xiong, et al.
Fig. 9. Cylindrical annulus with (a) circular tube, (b) vertical-oriented elliptical tube, (c) horizontal-oriented elliptical tube, and (d) finned circular tube [165].
Fig. 10. Stable and unstable melting patterns at the bottom and top region of
annulus [165].
nanoparticle loading of 3 vol%, reducing the melting time by 4.9%.
A magnetic field can produce a volume force on the nanoparticles,
thereby affecting the phase change process. Kohyani et al. [173] si-
mulated the melting process of cyclohexane/nanocopper in a square
porous cavity with horizontal magnetic field. The effects of porosity,
nanoparticle loading, Hartmann number (Ha, stands for the magnetic
field intensity), and Rayleigh number (Ra) on the melting behavior
were considered individually. An implicit CFD code based on the EHCM
was developed to solve the dimensionless governing equations. The
strong magnetic field weakened the action of natural convection,
transforming the solid–liquid interface from a curvature to a straight
line. It was reported that changing the porosities of Al-porous medium
was more effective in improving the melting rate than changing the
nanoparticle loadings. However, the authors draw this conclusion
without considering the latent heat reduction. For example, changing
the porosity from 0.6 to 0.1 can at least reduce the total latent heat by
50% since the porous foam does not change phase. This is an important
reason for the greatly improved melting rate. This issue has been con-
sidered in a recent study by Li et al. [174], in which the porosity of
metal foam was 0.95 to keep a similar PCM mass as dispersing 5 vol% of
Cu nanoparticles.
3.3. Nano metal oxide enhanced PCMs
Nano metal oxides such as Al2O3 and CuO nanoparticles has been
another option to enhance pure PCMs. Most nano metal oxides have
relatively low thermal conductivity (about 40 W/m·K), so the loadings
of Al2O3 and CuO nanoparticles are usually higher than those of na-
nocarbons and nanometals. However, it would produce undesirable
viscosity augmentation and convection degradation. For example,
Parsazadeh and Duan [175] numerically investigated the melting rate
of paraffin wax dispersed with Al2O3 nanoparticles in a finned shell-
and-tube system. The results indicated that 4 vol% of Al2O3 nano-
particles deteriorate the overall melting heat transfer, leading to longer
14
Applied Thermal Engineering 178 (2020) 115492
charging time in all cases investigated. This is because the small
thermal conductivity enhancement by Al2O3 nanoparticles may not be
able to compensate the convection degradation. To resolve this down-
side, an idea is to prepare hybrid NePCMs by dispersing both metal and
metal oxide nanoparticles, which combines the thermal properties of
each nanoparticles.
Instead of using the prediction models which have great un-
certainties, Ghalambaz et al. [176] used experimental data to obtain the
evolution of NePCM thermophysical properties at different loadings of
Ag-MgO nanoparticles. The variation of solid–liquid interface in the
cases of four different dimensionless variables (k, µ) = (0,0), (5,18),
(18,18), (18,5) was particularly analyzed to find out the best compo-
sition scheme of the hybrid nanoparticles. The fastest melting rate was
achieved when the ratio of dimensionless k to µ was 18:5. The result
demonstrated that the melting rate can be improved only when the
thermal conductivity enhancement is much higher than the viscosity
augmentation. The same authors also simulated the melting of Ag-
MgO/water in a square cavity heated by an inner tube heat exchanger
[177]. The variation of solid–liquid interface was greatly affected by
the changed thermal conductivity rather than the changed viscosity.
In recent years, high porosity metal and carbon foams with an ex-
cellent thermal conductivity have also been widely used to enhance the
melting heat transfer of PCMs. However, using porous foams will in-
hibit the convection flow of liquid PCM more than mounting fins and
dispersing nanoparticles [178]. In 2015, Hossain et al. [179] firstly
reported on the melting of nano-CuO enhanced cyclohexane in an
aluminium foam. Their model (Fig. 12) considered the local thermal
equilibrium (LTE) assumption with ruling out the convection motion in
the foam. Later, a hybrid nano-Al2O3/metal foam combination was
examined by Mahdi and Nsofor [180], which considerably enhanced
the melting rate of paraffin RT82 in a triplex shell-and-tube system. The
authors modified the EPM formulations based on the local thermal non-
equilibrium (LTNE) assumption to describe the heat and mass transfer
of NePCM in a copper foam. The convection effect, non-Darcy effect,
Brownian motion, and temperature-dependent thermophysical proper-
ties were considered. By dispersing nano-Al2O3 at loadings of 1 vol%,
3 vol%, and 5 vol%, the melting time was shortened by 16.7%, 17.9%,
and 19.7%, respectively. The melting in a foam with porosity of 0.95 is
much faster than that with porosity of 0.98 (18 min vs 120 min). The
authors explained this is because the total volume occupied by the
porous metal foam increased at a lower porosity, as well as the total
heat transfer area. Hence, the melting rate was notably improved with
only losing a small amount of latent heat.
Optimizing the geometric structure to further improve the NePCM
system was performed by Huo and Rao [108], in which a separate plate
was mounted to mitigate the undesirable heat accumulation in the
upper region of a square cavity. The nonuniform melting process results
from the imbalance of heat transfer mechanisms along the container
height as analyzed before. For all Ra and nanoparticle loadings, a
middle-located plate showed the fastest melting rate. Particularly, the
melting time was shortened by 10% for dimensionless plate height of
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

Fig. 11. Streamlines, temperature fields, and locations of solid–liquid interface at different dimensionless times (Gr = 2.5 × 105) [107].

Fig. 12. (a) Schematic of NePCM filled with a porous metal foam, (b) a magnified view of a representative control volume [179].

15
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

0.5 with dispersing 3 vol% of Al2O3 nanoparticles. The temperature

standard deviation was diminished by the separate plate, indicating a
mitigation of the heat accumulation in the upper region. However,
when the dimensionless plate height was less than 0.3, the heat accu-
mulation will slow down the overall melting rate. Similarly, Elbahjaoui
and El Qarnia [141] optimized the combinations of different para-
meters such as nano-Al2O3 loading, Re, Ra, and the aspect ratio of
NePCM slab. They reported that the melting rate was mainly affected by
Re and Ra rather than the nanoparticle loadings.
Among different PCM containers, shell-and-tube systems have been
extensively studied due to the ease of manufacture and modeling.
Varying The system inclination angle from 0 to 90°, a comparative
study by Pahamli et al. [181] showed that a vertically oriented shell-
and-tube system filled with paraffin RT50 and 4 vol% of CuO nano-
particles can achieve the fastest melting rate. Alomair et al. [94] ex-
perimentally and numerically investigated the influence of CuO nano-
particle loading and container height on the melting characteristics of
coconut oil. The NePCM dispersed with 0.25 vol% of CuO nanoparticles
was prepared by magnetic stirring and sonication, showing good sta-
bility without sedimentation. Both simulation and experimental results
showed an improved melting rate, but a small portion of gradually
diminished solid PCM/NePCM remained at the bottom region for a
prolonged period of time. This has been ascribed to the imbalance of
heat transfer mechanisms along the height of containers, particularly
the ones with a high aspect ratio. Similar results were also obtained in
the studies [182,183]. To achieve a uniform melting process, other heat
transfer enhancement techniques are needed to support the NePCM.
Using the same methodology, the melting behavior of nano-CuO/n-
octadecane in a horizontal cylinder and a square cavity were in-
vestigated by Dhaidan et al. [95,96]. Parsazadeh and Duan [184] per-
formed a statistical numerical study on both dispersing CuO nano-
particles in PCM and in HTF. The authors adopted the response surface
method (RSM) to analyze the effects of three parameters on the system
response, including the particle loading in PCM, particle loading in
HTF, and the HTF temperature. As shown in Fig. 13, two 3D plots were
used to elaborate the correlations between the above parameters. It is
clear that there is an optimum value for the nanoparticle loading in Fig. 13. 3D liquid fraction plots for (a) nanoparticle loading in PCM and HTF
PCM, which lies between 0.02 and 0.04. This is because dispersing temperature (b) nanoparticle loading in PCM and in HTF [184].
3.5 vol% of CuO nanoparticles has less negative impact on the natural
convection as compared to dispersing 7.0 vol% of CuO nanoparticles.
4. Solidification studies of NePCMs
The convection degradation is an important adverse effect induced
by nano metal oxides, particularly in the case of a high particle loading.
4.1. Nanocarbon enhanced PCMs
Arasu and Mujumdar [185] simulated the melting of nano-Al2O3 en-
hanced paraffin in a 25 mm × 25 mm cavity heated from different or-
Different from the melting process, the solidification of PCMs is
ientations. In all cases studied, dispersing 2 vol% nano-Al2O3 showed
predominated by conduction heat transfer throughout the entire pro-
better heat transfer performance than dispersing 5 vol% nano-Al2O3.
cess [187–189]. Hence, the negative effect viscosity augmentation and
Similar conclusions were also drawn by Arıcı et al. [186]. Given these
convection degradation may be eliminated in the solidification process
results, it is important to consider the coupling effects of the enhanced
of NePCMs. Another benefit is that nanoparticles can effectively miti-
conduction and the reduced convection. Dimensionless numbers such
gate the supercooling of NePCMs [190]. In 2015, Fan et al. [191] firstly
as the Nusselt number (Nu) and the Grashof number (Gr) can be used to
simulated the unidirectional solidification of GnP enhanced dodecanol.
evaluate the ratio of conduction to convection. As previously discussed,
Rather than using the prediction models, the authors experimentally
the viscosity augmentation is not likely to offset the melting enhance-
measured the effective thermophysical properties of NePCMs at dif-
ment in the case of a moderate nanoparticle loading. However, when
ferent GnP loadings. The HSTM was used to model the 1D phase change
the loading exceeds a certain value, the melting enhancement could be
(Stefan) problem. The relative solidification rates were quantitatively
outweighed. Numerical and experimental studies by Dhaidan et al. [97]
compared, showing an improvement of 34% by dispersing 1.0 wt% of
have verified that the melting rate of nano-CuO/n-octadecane was
GnP. The authors pointed out that the simulation is based on the EMT,
notably improved when increasing the nanoparticle loading from 0 to
so the migration of GnP nanoparticles and their interactions with the
1 wt%, whereas the enhancement ratio decreased when increasing the
moving solid–liquid interface, such as particle segregation and mor-
loading from 1 to 3 wt% and from 3 to 5 wt%. From a material point of
phological instability are not considered.
view, a high nanoparticle loading tends to cause particle agglomeration
Later, Singh et al. [192] numerically analyzed the solidification of
and segregation issues. Hence, further numerical and experimental
GnP/eutectic salt in a finned shell-and-tube system. The fin aspect ratio
studies are needed to investigate the optimum thermal properties of
has been optimized in the melting study [160]. The thermophysical
NePCMs.
properties of NePCM were treated as temperature-dependent poly-
Table 5 summarizes the above reviewed studies to which the readers
nomials in the EPM equations. The solidification time was reduced to
can refer.
7.6 h in the case of finned PCM, and it was further reduced to 5.3 h by

16
 Table 5
Summary of numerical studies on the melting process of NePCMs.
Base PCM Nanostructure Concentration Melting Container Prediction model CFD code and method Amush Results and findings Ref.
T. Xiong, et al.

point

n-eicosane GnP with l of 1 μm and δ of 2 vol% 36 °C vertical shell-and- K-D model for µ Fluent based on EPM 105 41% melting time ↓ [155]
10 nm tube Nan’s model for k convection heat transfer was degraded due to the
increased µ
n-eicosane carbon ND with d of 10 nm 1 vol% 36 °C vertical shell-and- K-D model for µ Fluent based on EPM 105 1% melting time ↓ [156]
SWCNT with l of 1 μm and d tube Nan’s model for k 15% melting time ↓
of 1 nm 26% melting time ↓
GnP with l of 1 μm and δ of
10 nm
n-eicosane carbon ND with d of 10 nm 1 vol% 36 °C horizontal shell-and- K-D model for µ Fluent based on EPM 105 2% melting time ↓ [157]
SWCNT with l of μm and d of tube Nan’s model for k 27% melting time ↓
1 nm 40% melting time ↓
GnP with l of 1 μm and δ of
10 nm
capric acid graphene nanoparticles 1 vol% 32 °C square cavity Brinkman model for µ COMSOL based on EHCM 106 dispersing graphene increased the melting rate but [158]
CaCl2·6H2O 3 vol% 29 °C Vajjha’s model for k and Darth source term also degraded the convection heat transfer within
n-octadecane 5 vol% 28.2 °C method large cavities
paraffin wax graphene nanoparticles 0.5–2.0 vol% 46 °C trapezoidal cavity Brinkman model for µ Fluent based on EPM N.A. the enhancement of k should be higher than 80% to [159]
k was assumed to be achieve improved performance
enhanced by 20–100%
sugar alcohol GnP with l of 10 μm and δ of 1 vol% 166.3 °C vertical shell-and- Vajjha’s model for µ Fluent based on EPM 105 5% GnP outperformed optimized fin [160]
10 nm 3 vol% tube Chu’s model [161] for 67.7% melting time ↓ by 5% GnP + optimized fin
5 vol% k convection heat transfer was weakened due to the
increased µ and fin height
eutectic salt LiNO3- GnP with l of 10 μm and δ of 1 vol% 166 °C vertical conical Brinkman model for µ Fluent based on EPM 105 57% melting time ↓ by 5% GnP + optimized fin [162]

17
KCl 10 nm 3 vol% shell-and-tube Chu’s model [161] for
5 vol% k
eutectic salt LiNO3- GnP with l of 10 μm and δ of 1 vol% 166 °C vertical shell-and- Experimental data for µ Fluent based on EPM 105 the prediction models largely underestimated the µ [163]
KCl 10 nm 3 vol% tube Chu’s model [161] for of NePCM
5 vol% k 6% melting time ↑ by 1% GnP
43% melting time ↓ by 5% GnP + optimized fin
n-eicosane Cu nanoparticles with d of 2 vol% 36 °C horizontal shell-and- Brinkman model for µ Fluent based on EPM N.A. 25% melting time ↓ [165]
80 nm 4 vol% tube thermal dispersion 46% melting time ↓
model for k 4% GnP outperformed mounting 4 fins
convection heat transfer was weakened due to the
increased µ and fin height
water Cu nanoparticles with d of 2 vol% 0 °C horizontal shell-and- Brinkman model for µ enthalpy-based DDF-LBM N.A. 4% Cu nanoparticles + heat exchanger mounted at [167]
100 nm 4 vol% tube Patel’s model [168] for with D2Q9 lattice model the bottom achieved the best heat transfer
k enhancement
water Cu nanoparticles with d of 1 vol% 0 °C square cavity Brinkman model for µ enthalpy-based DDF-LBM N.A. 33% melting time ↓ by 2% Cu nanoparticles + heat [169]
100 nm 2 vol% Patel’s model [168] for with D2Q9 lattice model exchanger mounted at the bottom
k
water Cu nanoparticles with d of 1 vol% 0 °C square cavity Brinkman model for µ enthalpy-based DDF-LBM N.A. 50% melting time ↓ by 2% Cu [170]
100 nm 2 vol% Patel’s model [168] for with D2Q9 lattice model nanoparticles + optimized tube heat exchanger
k arrays
water Cu nanoparticles with d of 5 vol% 0 °C square cavity Brinkman model for µ enthalpy-based DDF LBM N.A. 17.9% melting time ↓ [107]
100 nm 10 vol% thermal dispersion with D2G9 and D2Q9 5.33% energy storage rate ↑
model for k lattice models
paraffin wax Cu nanoparticles 2 vol% 29 °C sphere Brinkman model for µ Fluent based on EPM with 105 12% melting time ↓ [171]
4 vol% thermal dispersion VOF model 25% melting time ↓
model for k
n-octadecane Cu nanoparticles with d of 1 vol% 28 °C elliptical capsule Brinkman model for µ Fluent based on EPM with 105 1.8% melting time ↓4.9% melting time ↓ [172]
80 nm 3 vol% Vajjha’s model for k VOF model
(continued on next page)
Applied Thermal Engineering 178 (2020) 115492
 Table 5 (continued)

Base PCM Nanostructure Concentration Melting Container Prediction model CFD code and method Amush Results and findings Ref.
point
T. Xiong, et al.

cyclohexane Cu nanoparticles 1 vol% 7 °C square cavity Brinkman model for µ in-house CFD code based N.A. changing porosity outperformed changing [173]
5 vol% static Maxwell model on EHCM nanoparticle loading
for k a strong magnetic field lead to an increased melting
rate and a straight solid–liquid interface
paraffin wax Cu nanoparticles with d of 1 vol% 35 °C vertical shell-and- Vajjha’s models for µ Fluent based on EPM 105 25.9% melting time ↓ [174]
15 nm, 50 nm and 100 nm 5 vol% tube and k nanoparticles with small diameter showed a better
heat transfer enhancement than the ones with big
diameter
porous foam showed much better melting
enhancement than nanoparticles
paraffin wax Al2O3 nanoparticles with d of 4 vol% 47 °C Vertical shell-and- Vajjha’s models for µ Fluent based on EPM with 105 dispersing Al2O3 decreased the overall heat [175]
59 nm tube and k VOF model transfer rate, leading to longer charging time in all
cases
water Ag nanoparticles with d of 2 vol% 0 °C square cavity experimental data for µ MATLAB based on EPM 1.6 × 106 the best heat transfer enhancement was obtained [176]
25 nm and MgO nanoparticles and k when the ratio of dimensionless k to µ was 18:5
with d of 40 nm
water Ag nanoparticles with d of 5 vol% 0 °C square cavity experimental data for µ MATLAB based on EPM 1.6 × 106 the solid–liquid interface was greatly affected by [177]
25 nm and MgO nanoparticles and k the changed k rather than the changed µ.
with d of 40 nm
cyclohexane CuO nanoparticles 5–20 vol% 7 °C square cavity Brinkman model for µ NATURE based on EHCM N.A. porous foam showed much better melting [179]
static Maxwell model enhancement than nanoparticles
for k
paraffin wax Al2O3 nanoparticles 1 vol% 82 °C horizontal shell-and- Vajjha’s models for µ Fluent based on EPM with N.A. 19.7% melting time ↓ by 5% Al2O3 nanoparticles [180]
3 vol% tube and k considering local thermal porous foam showed much better melting
5 vol% equilibrium enhancement than nanoparticles

18
paraffin wax Al2O3 nanoparticles 3 vol% N.A. square cavity Vajjha’s models for µ enthalpy-based MRT-LBM N.A. 10% melting time ↓ [108]
5 vol% static Maxwell model with D2Q9 lattice model the separate plate should be mounted at a certain
for k height for a uniform melting process
paraffin wax Al2O3 nanoparticles 2–8 vol% 47 °C rectangle cavity Brinkman model for µ in-house CFD code based 1.6 × 106 by up to 14.25% melting time ↓ [141]
thermal dispersion on EHCM the Re and Ra showed higher influence than
model for k nanoparticle loadings
paraffin wax CuO nanoparticles 2 wt% 50 °C shell-and-tube with experimental data for µ in-house CFD code based 106 4.56% melting time ↓ [181]
4 wt% different and k on EPM 11.16% melting time ↓
orientations the vertical shell-and-tube system showed the
highest melting rate
coconut oil CuO nanoparticles 3 vol% 24 °C vertical shell-and- Brinkman model for µ COMSOL based on EHCM N.A. 11.1% melting time ↓ [94]
5 vol% tube static Maxwell model 13.8% melting time ↓
for k both simulation and experiment showed
accelerated melting rate
coconut oil CuO nanoparticles 3 vol% 24 °C vertical cylinder Brinkman model for µ COMSOL based on EHCM 105 the use of prediction models caused discrepancies [183]
5 vol% static Maxwell model and Darth source term between simulation and experiment
for k method
n-octadecane CuO nanoparticles 1 wt% 28 °C horizontal cylinder Brinkman model for µ COMSOL based on EHCM N.A. 4.5% melting time ↓ [95]
3 wt% thermal dispersion 10.1% melting time ↓
5 wt% model for k 12.8% melting time ↓
n-octadecane CuO nanoparticles 1 wt% 28 °C square cavity Brinkman model for µ COMSOL based on EHCM N.A. 5.5% melting time ↓ [96]
3 wt% thermal dispersion 8.9% melting time ↓
5 wt% model for k 11.7% melting time ↓
paraffin wax CuO nanoparticles with d of 2–4 vol% for HTF 55 °C vertical shell-and- Brinkman model for µ Fluent based on EPM 105 adding 3.5% CuO nanoparticles in PCM [184]
10 nm 3.5–7 vol% for tube Vajjha’s models for k outperformed adding 7% CuO in PCM
PCM
paraffin wax Al2O3 nanoparticles 2 vol% 47 °C square cavity Vajjha’s models for µ Fluent based on EPM N.A. adding 2% Al2O3 nanoparticles in PCM [185]
5 vol% and k outperformed adding 5% Al2O3 in PCM
(continued on next page)
Applied Thermal Engineering 178 (2020) 115492
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

[186]

[97]
Ref.

the melting enhancement rate was decreased with

outperformed adding 3% and 5% Al2O3 in PCM
adding 1% Al2O3 nanoparticles in PCM
Results and findings

the particle loading

Fig. 14. Schematic of the triplex shell-and-tube TES system with fins [160].

adding 5 vol% of GnP. Further, decreasing the St (HTF temperature)

and increasing the Re (HTF flow rate) also improved the solidification
Amush

N.A.
108

rate. Nevertheless, reducing the St is more efficient than increasing the

Re in enhancing the heat transfer of TES.
More recently, Alizadeh et al. [193] developed a novel triplex shell-
CFD code and method

Fluent based on EPM

Fluent based on EPM

and-tube system (Fig. 14) and expedited the freezing of water using V-
shaped fins and SWCNT. Their model was based on the HSTM and
solved by the standard Galerkin finite element method (SGFEM). The
fin design was optimized by the RSM with considering the angle be-
tween fin branches, the fin length, and the fin thickness. The fin length
and branch angle greatly affected the solidification rate, while the in-
fluence of the fin thickness was insignificant. The freezing time was
Brinkman model for µ
Vajjha’s models for µ

shortened by 33.1% by adding 5 vol% of SWCNT and 46.4% by

thermal dispersion
Prediction model

mounting fins, respectively. It should be noted that a part of the con-

tainer space is occupied by the fins, which will lead to a reduced latent
model for k

heat. This is also a reason for the faster freezing rate by mounting fins
and k

over adding SWCNT. However, this issue was not considered by the
authors.
Note: d, δ, l, ↓ and ↑ stand for diameter, thickness, length, reduction, and enhancement, respectively.
horizontal shell-and-
square cavity

4.2. Nanometal enhanced PCMs

Container

In 2007, Khodadadi and Hosseinizadeh [194] firstly reported on the

tube

accelerated freezing process of water enhanced by Cu nanoparticles

with an average diameter of 10 nm. Their method based on the EMT
and single-phase assumption was later used in a body of NePCM studies.
Melting
point

47 °C

28 °C

Results showed that the freezing time of water was shortened from
3000 s to 1400 s by dispersing 20 vol% of nanocopper. However, the
authors did not consider the particle sedimentation and dispersion
stability under such a high particle loading. Both experimental and
Concentration

numerical investigations are needed to ascertain the optimal particle

1–3 vol%

loading ranges, within which the NePCM can be considered as a single-

1 wt%
3 wt%
5 wt%

phase mixture. In addition, the largely reduced latent heat should also
be considered.
Al2O3 nanoparticles with d of

CuO nanoparticles with d of

Recently, more and more simulation-based studies have compared

different heat transfer enhancement techniques for promoting the so-
lidification rate of PCMs. For example, the freezing process of water in a
wavy cavity (Fig. 15) was studied by Abdollahzadeh and Esmaeilpour
Nanostructure

[195] to quantify the contributions of adjusting container surface wa-

viness and dispersing Cu nanoparticles. The authors maintained the
59 nm

same container volume for each case studied. Dispersing nanoparticles

9 nm

showed the best enhancement in Case II with a waviness of 0.2 m and a

Gr of 106, reducing the freezing time by up to 8.5%. Increasing the
Table 5 (continued)

surface waviness prolonged the freezing time whereas at a high Gr,

increasing the waviness could reduce the freezing time. The authors
n-octadecane
paraffin wax

stated that adjusting the surface waviness does not reduce the latent
Base PCM

heat, which is the advantage over dispersing nanoparticles. A similar

study can be found in [90].
Modularized PCM slab is another good option to increase the

19
T. Xiong, et al.
Fig. 15. Schematic of the vertical wavy cavity filled with NePCM [195].
Fig. 16. (a) TES system consists of NePCM slabs and (b) computational domain [196].
contact surface area between PCM and HTF. Elbahjaoui and Qarnia
[196] numerically studied the solidification of nano-copper/n-octade-
cane filled in a vertical slab with considering natural convection, as
shown in Fig. 16. The effects of varying the particle loading, slab aspect
ratio, and the dimensionless HTF temperature were examined. The
solidification rate was improved with increasing the particle loading
and slab aspect ratio, and decreased with increasing the HTF tem-
perature. The best heat transfer enhancement scheme was by dispersing
8 vol% of nanocopper under a slab aspect ratio of 6 and a dimensionless
HTF temperature of 1.1, reducing the solidification time by as much as
26.9%.
The advantages of nanoparticles over other heat transfer enhance-
ment techniques may be lost in the solidification process. For example,
the discharging time of a horizontal shell-and-tube system was reduced
by 9% and 16% by dispersing 2 vol% and 4 vol% of Cu nanoparticles
into n-eicosane [165]. Whereas mounting four fins shortened the dis-
charging time by 28%, which outperformed the enhancement by Cu
nanoparticles. Since dispersing 4 vol% of Cu nanoparticles out-
performed mounting four fins in the melting process, it can be con-
cluded that extending the heat transfer area is more efficient than
dispersing nanoparticles in the solidification process. In the melting
process, the nanoparticles can better accommodate the convection flow,
while mounting fins can greatly suppress the convection flow. Hence,
20
Applied Thermal Engineering 178 (2020) 115492
dispersing nanoparticles is more efficient than mounting fins in the
melting process rather than in the solidification process. Similar con-
clusions were also emphasized in the comparison between using porous
medium and dispersing nanoparticles [174].
It has been verified by numerical comparison that the influence of
natural convection heat transfer can be ruled out in the solidification
process [197]. This assumption makes the simulation process simpler,
which has been widely adopted in recent studies. For example, a series
of numerical studies were performed by Lohrasbi et al. [198–201] to
model the freezing process of nanocopper/water in different finned
shell-and-tube tanks, as shown in Fig. 17. In a typical analysis, the re-
search group firstly used the RSM to optimize the fin design, and then
compared the effectiveness of mounting fins and dispersing nano-
particles. In the study [44], dispersing 2.5 vol% and 5.0 vol% of Cu
nanoparticles improved the discharging rate by 1.099 and 1.208 time,
respectively. Whereas mounting fins improved the discharging rate by
as much as 5.749 time. Given the expedition of discharging rate and the
reduction in latent heat, the authors concluded that mounting fins
showed much better heat transfer enhancement than dispersing nano-
particles.
T. Xiong, et al.
Fig. 17. Finned PCM tanks studied in (a) [198], (b) [199,200], and (c) [201].
4.3. Nano metal oxide enhanced PCMs
An interest study was recently carried out by Sheikholeslami and
Mahian [202], in which CuO nanoparticles and external magnetic field
were firstly used to improve the freezing process of water in a porous
annulus. The Koo-Kleinstreuer-Li (KKL) prediction model [203] was
used for calculating the effective thermal conductivity and viscosity of
the NePCM. The RSM was used to analyze the effects of three factors,
including the nanoparticle loading, Ha (magnetic force), and Ra. The
complete freezing time of water was found to linearly decrease with the
nano-CuO loading and the Ha, and non-linearly increase with the Ra.
The freezing time was shortened by 14% for a nano-CuO loading of
4 vol% and 23.5% for a Ha of 10, respectively.
Triplex shell-and-tube systems have been frequently used to extend
the contact surface area between HTF and PCM, so they will show
better heat transfer rates than the normal shell-and-tube systems.
Recently, a triplex shell-and-tube tank filled with nano Al2O3/paraffin
RT82 was studied by Mahdi and Nsofor [204]. User defined function
(UDF) codes were used to input the temperature-dependent thermo-
physical properties of NePCM. The solidification process of NePCM at
two HTF temperatures (65 °C and 70 °C) were investigated, respec-
tively. Dispersing nano Al2O3 did not show much difference at the in-
itial stage, but the solidification rate increased with the particle loading
and elapse of time as heat conduction dominated the heat transfer re-
gime. A total solidification time reduction of 20% was achieved by
adding 8 vol% of Al2O3 nanoparticles.
Later on, Mahdi and Nsofor [205] used open-celled porous copper
foam to further improve the discharging performance of the same
NePCM system studied in [180,204]. Three cases were simulated,
Fig. 18. 2D triplex shell-and-tube systems with: (a) NePCM [204], (b) fins with NePCM [206] and (c) porous foam with NePCM [180,205].
21
Applied Thermal Engineering 178 (2020) 115492
including adding nano-Al2O3 alone, using metal foam alone, and using
both metal foam and nano-Al2O3. The authors compared the LTE model
used in [179] with the LTNE model used in [180], and they verified that
the simpler LTE model can obtain results with acceptable accuracy. This
has been ascribed to the small temperature difference between the
NePCM and metal foam during the heat conduction dominated solidi-
fication process. Based on an LTE-modified EPM, the complete solidi-
fication time was shortened by 19.6% (8 vol% nanoparticle loading),
77.7% (0.98 porosity with 8 vol% nanoparticle loading), and 96.5%
(0.95 porosity with 8 vol% nanoparticle loading), respectively.
More recently, Mahdi and Nsofor [206] improved the solidification
of paraffin RT82 by means of a hybrid strategy, including mounting fins
and adding nano-Al2O3. The combinations of using different fin arrays
mounted on the inner and outer tubes and dispersing nanoparticles with
different loadings were analyzed, with considering the volume usage
(i.e. the ratio of occupied volume by nanostructures or fins to total PCM
volume) in each technique. Results indicated that the solidification
process was significantly shortened using the hybrid strategy, by as
much as 33.4%. However, for the same volume usage, a much better
heat transfer efficiency can be achieved by mounting fins alone. The 2D
models established in [180,204–206] are shown in Fig. 18. These stu-
dies have given a benchmark of using CFD techniques to compare dif-
ferent heat transfer enhancement techniques and evaluate their in-
dividual contributions to PCM systems.
Table 6 summarizes the above reviewed studies to which the readers
can refer.
 Table 6
Summary of numerical studies on the solidification process of NePCMs.
Base PCM Nanostructure Concentration Solidification point Container Prediction model CFD code and Amush Results and findings Ref.
T. Xiong, et al.

method

dodecanol GnP 0.5 wt% 24 °C heat transfer slab experimental data for in-house CFD N.A. 26% solidification time ↓ [191]
1.0 wt% k code based on 34% solidification time ↓
HSTM
eutectic salt LiNO3- GnP with l of 10 μm and δ of 1 vol% 166 °C vertical shell-and- Vajjha’s model for µ Fluent based on 105 29.1% solidification time ↓ [192]
KCl 10 nm 3 vol% tube Chu’s model [161] for EPM 39.8% solidification time ↓
5 vol% k 48.5% solidification time ↓
water SWCNT 2.5 vol% 0 °C vertical triple shell- static Maxwell model SGFEM based on N.A. 13.9% solidification time ↓ [193]
5.0 vol% and-tube for k HSTM 33.1% solidification time ↓
46.4% solidification time ↓ by mounting fins
water Cu nanoparticles with d of 10 vol% 0 °C square cavity Brinkman model for µ Fluent based on 105 33.3% solidification time ↓ [194]
10 nm 20 vol% thermal dispersion EPM 53.3% solidification time ↓
model for k
water Cu nanoparticles with d of 2.5 vol% 0 °C wavy cavity Brinkman model for µ in-house CFD N.A. by up to 8.5% solidification time ↓ [195]
1 nm 5.0 vol% thermal dispersion code based on
model for k EPM
water Cu nanoparticles with d of 5 vol% 0 °C wavy cavity Brinkman model for µ in-house CFD N.A. by up to 18.4% solidification time ↓ [90]
1 nm 10 vol% thermal dispersion code based on
model for k EPM
n-octadecane Cu nanoparticles 2 vol% 28 °C rectangle cavity Brinkman model for µ in-house CFD 1.6 × 106 by up to 26.9% solidification time ↓ [196]
8 vol% static Maxwell model code based on
for k EHCM
n-eicosane Cu nanoparticles with d of 2 vol% 36 °C horizontal shell- Brinkman model for µ Fluent based on N.A. 9% solidification time ↓ [165]
80 nm 4 vol% and-tube thermal dispersion EPM 16% solidification time ↓
model for k mounting fins outperformed dispersing nanoparticles in

22
all cases
water Cu nanoparticles 2.5 vol% 0 °C vertical shell-and- static Maxwell model SGFEM based on N.A. optimized fins showed much better solidification [201]
5.0 vol% tube for k HSTM enhancement than dispersing nanoparticles
paraffin wax Cu nanoparticles with d of 1 vol% 35 °C vertical shell-and- Vajjha’s models for µ Fluent based on 105 by up to 28.2% solidification time ↓ [174]
15 nm, 50 nm and 100 nm 5 vol% tube and k EPM nanoparticles with small diameter achieved a better
heat transfer enhancement than the ones with big
diameter
porous foam showed much better solidification
enhancement than dispersing nanoparticles
water Cu nanoparticles 2.5 vol% 0 °C vertical shell-and- static Maxwell model SGFEM based on N.A. 9.9% solidification time ↓ [200]
5.0 vol% tube for k HSTM 20.8% solidification time ↓
optimized fins showed much better solidification
enhancement than dispersing nanoparticles
water Cu nanoparticles 2.5 vol% 0 °C vertical shell-and- static Maxwell model SGFEM based on N.A. 8.8% solidification time ↓ [199]
5.0 vol% tube for k HSTM 16.9% solidification time ↓
optimized fins showed much better solidification
enhancement than dispersing nanoparticles
water Cu nanoparticles 2.5 vol% 0 °C vertical shell-and- static Maxwell model SGFEM based on N.A. optimized fins showed much better solidification [198]
5.0 vol% tube for k HSTM enhancement than dispersing nanoparticles
water CuO nanoparticles 4 vol% 0 °C porous annulus KKL model [203] for µ SGFEM based on N.A. 14% solidification time ↓ by 4% nano-CuO [202]
cavity and k HSTM 23.5% solidification time ↓ by a magnetic field with Ha
of 10
paraffin wax Al2O3 nanoparticles 3 vol% 82 °C horizontal triplex Vajjha’s models for µ Fluent based on 106 9.7% solidification time ↓ [204]
5 vol% shell-and-tube and k EPM 14% solidification time ↓
8 vol% 19.8% solidification time ↓
the solidification reduction percentage was almost
independent of the HTF temperature
(continued on next page)
Applied Thermal Engineering 178 (2020) 115492
T. Xiong, et al. Applied Thermal Engineering 178 (2020) 115492

5. Discussions

[205]

[206]
Ref.

5.1. Potential reasons for discrepancies

much better solidification enhancement than dispersing

77.7% solidification time ↓ by 8% nano-Al2O3 + 0.98

96.5% solidification time ↓ by 8% nano-Al2O3 + 0.95

under the same volume usage, mounting fins showed

Significant thermal enhancements by dispersing various nanos-

porous foam showed much better solidification

19.6% solidification time ↓ by 8% nano-Al2O3

tructures in PCMs have been simulated by most of the numerical studies

enhancement than dispersing nanoparticles

summarized in Table 5 and 6. Nevertheless, some experimental works
have reported that dispersing nanoparticles actually degraded the
overall heat transfer performance, particularly in the cases with strong
natural convection. For example, Ho and Gao [40] found the melting of
n-octadecane doped with 5 wt% and 10 wt% of nano Al2O3 was strongly
deteriorated in a square cavity. Zeng et al. [41] also demonstrated that
Results and findings

porous copper foam

porous copper foam

dispersing 1 wt% and 2 wt% of CNT greatly improved the melting rate
of dodeconal in a vertical cylinder at the initial stage. But as the melting
nanoparticles

proceeded the trend was reversed, and the dodeconal temperature

showed a much faster increase than the ones dispersed with CNT. As for
the solidification process, Fan and Khodadadi [42] reported that the
solidification time of nano-CuO/cyclohexane was linearly shortened
with the particle loading in the simulated results. However, the soli-
dification time was non-linearly shortened with the nanoparticle
Amush

106

106

loading in the experimental results. The potential reasons for these

discrepancies can be explained from three aspects:
(1) Unstable dispersion of the nanoparticles
Fluent based on

Fluent based on
CFD code and

All the experimental works [40–42] have observed particle sedi-

mentation issues at the end of the experiment, so it is difficult to prove
method

their repeatability. Since the flow velocity of the liquid NePCM is very
EPM

EPM

small in the natural convection, the velocity of nanoparticle sedi-

mentation should not be neglected in the cases without using stabilizers
Vajjha’s models for µ

Vajjha’s models for µ

or surfactants. This is an important reason for the discrepancy between

Prediction model

simulation and experimental results since any of the reported NePCM

models have not considered the particle sedimentation. On the other
hand, Alomair et al. [94] experimentally demonstrated that a NePCM
and k

and k

with very small particle sedimentation can achieve a faster melting rate
than the pure PCM. A better dispersion stability of nanoparticles also
results in stronger nanoparticle/PCM molecular interactions, thereby
horizontal triplex

horizontal triplex

improving the thermal properties of NePCM [150]. Hence, as long as

shell-and-tube

shell-and-tube

the dispersion stability of nanoparticles in the base PCM is satisfied, the

Container

NePCM can be considered as a homogeneous mixture and modeled

using single-phase approaches.
Several techniques can be used to improve the dispersion stability of
Note: d, δ, l, and ↓ stand for diameter, thickness, length, and reduction, respectively.
Solidification point

nanoparticles in the base PCM, including chemical treatment and

physical treatment. In the former technique, surfactants have been ex-
tensively used to stabilize the dispersed nanoparticles, either by elec-
trostatic approach [207] or surface modification approach [208]. In the
82 °C

82 °C

later technique, ultrasonication [209] and ball milling [210] have been
used to stabilize water-based and oil-based nanofluids. The colloidal
Concentration

stability of liquid NePCMs (nanofluids) can be mainly evaluated by

visual inspection [211], UV–vis spectrophotometer [212], and ζ-po-
3 vol%
5 vol%
8 vol%

1 vol%
2 vol%
3 vol%

tential method [213,214]. For example, Wensel et al. [211] improved

the suspension stability of SWCNT/Fe2O3/MgO in the water by adding
sodium dodecylbenzene sulfonate (SDBS) as the surfactant. The nano-
fluids were prepared using ultrasonication. As shown in Fig. 19, the
nanofluid with using surfactant (c) has a very uniform color distribution
Al2O3 nanoparticles

Al2O3 nanoparticles

than the one without using surfactant (b). Hwang et al. [212] used
UV–vis method to test the relationship between the absorbance of
Nanostructure

MWCNT, Fullerene, CuO/oil nanofluids and particle concentration. The

nanofluids were improved by adding sodium dodecyl sulfate (SDS) as
the surfactant. From the obtained relationship, the nano dispersion
stability can be estimated. As for the ζ potential method, it has been
used by Wang et al. [213] and Li et al. [214] to evaluate the dispersion
Table 6 (continued)

behavior of nanofluids improved by surfactants. The ζ-potential is

highly related to the absorbance of nanofluids, and a higher ζ-potential
paraffin wax

paraffin wax

represents a better dispersion stability of the system. On the other hand,

Base PCM

the dispersion stability of nanoparticles can influence the thermal sta-

bility of NePCMs. Hence, the NePCM thermal conductivity and latent
heat after many thermal cycles can also be used to evaluate the

23
T. Xiong, et al.
Fig. 19. Color distributions of (a) water, (b) nanofluid without using surfactant,
and (c) nanofluid with using surfactant [211].
dispersion stability of nanoparticles [215].
(2) Uncertainties of the prediction models
Most of the currently used prediction models of effective viscosity
and thermal conductivity have uncertainties for NePCMs. This can also
produce uncertainties to the simulations involving conduction and
convection heat transfer. Particularly, the Brinkman model has been
reported to largely underestimate the real increase in the effective
viscosity of PCM dispersed with non-spherical GnP [163] and CNT [41].
It has also been pointed out that simulated results using different pre-
diction models can show a deviation, which is because some models did
not consider the influence of nanoparticle diameter [216]. Based on
these results, it is suggested to use the measured viscosity and thermal
conductivity in the numerical simulation.
(3) Limitations of the numerical assumptions
The vast majority of NePCM studies are based on single-phase ap-
proaches assuming the NePCM is a stable and homogeneous mixture,
and thus some physical phenomenon were not considered in any of the
reported studies. For example, the prediction models mentioned in
Section 2.3.2 did not consider the influence of nanoparticle migration
induced by Brownian motion and thermophoresis. Nanoparticles in the
liquid PCM may aggregate at a high particle loading, which is due to the
large surface area to volume ratio and high surface energy [217]. This
may lead to heterogeneous distribution of thermophysical properties
throughout the control volume. Further, the dynamic diffusion of na-
noparticles and their interactions with the moving solid–liquid interface
can cause engulfment and/or rejection of nanoparticles [142]. Given
the above issues, the single-phase assumption may break down. Ac-
cordingly, additional considerations are necessary in the classical phase
change formulations. For instance, a recent numerical study by Hasadi
[218] considered the mass transport of Cu nanoparticles in the melting
process of water, showing a concentration field induced by the nano-
particle rejection at the solid–liquid interface.
5.2. Basic phase change behavior of NePCM
5.2.1. Melting process of NePCM
Based on the reported simulation results [158–160], conduction and
convection are two main heat transfer mechanisms, and the convection
is more efficient in improving the melting process. Hence, a majority of
numerical studies have investigated the impact of nanoparticles on the
melting rate. There is a clear trend that the melting rate accelerates
with the particle loading, which is due to the enhanced thermal
24
Applied Thermal Engineering 178 (2020) 115492
conductivity. But when the particle loading exceeds a threshold, the
increased viscosity will strongly degrade the convection efficiency and
in turn slow down or even counteract the contribution of the improved
conduction. Hence, it is important to numerically analyze the optimum
ranges of particle loading for different PCM systems. In addition, the
nanostructures with high surface area to volume ratio and small dia-
meter show better heat transfer enhancements. Owning to the ad-
vantages of high thermal conductivity, high aspect ratio, large interface
contact area, and the minor side effects on latent heat reduction and
viscosity augmentation, GnP shows the best heat transfer enhancement
for PCM systems. It can be also found that most simulation-based stu-
dies have adopted the EPM due to its simplicity and efficiency in
modeling the convection melting of NePCMs. However, the mushy zone
constant should be carefully decided in the EPM, which requires further
attention.
The container geometries and orientations can also influence the
effectiveness of nanoparticles. For example, GnP enhanced n-eicosane
showed a faster melting rate in the horizontal shell-and-tube system
than the vertical one [156,157]. This is because the influence of natural
convection is not strong in the container with a low aspect ratio, so
dispersing nanoparticles is more effective in this case. However, a re-
verse finding was obtained in [181], showing that NePCM in the ver-
tical shell-and-tube system melted faster than that in the horizontal one.
By comparing the two studies, it was found that the HTF tube used in
[181] is much smaller than the one used in [156,157], so the melting in
[181] is more affected by natural convection which is more efficient
than adding nanoparticles in enhancing the melting process.
In comparison with mounting fins and using porous metal foams,
dispersing nanostructures can better accommodate the convection flow
of the liquid NePCM. But the overall enhancement by nanoparticles is
still moderate as compared to the fins and metal foams. Another pro-
blem is that nanoparticles can only enhance the overall conduction heat
transfer, so it is less efficient in mitigating the heat accumulation pro-
blem induced by the strong natural convection in the upper region of
containers with a high aspect ratio [94,108,165]. To further improve
the system performance, hybrid strategies by means of dispersing na-
noparticles and extending heat transfer area are suggested.
5.2.2. Solidification process of NePCM
Based on the reported simulation results [155–157,174,191,192],
nanoparticles was found to be more efficient in the solidification pro-
cess than the melting process. This is because nanoparticles will cause
viscosity augmentation and consequently offset or even degrade the
improved conduction heat transfer in the melting process. However, the
solidification process is predominated by conduction heat transfer, so
the side effect of viscosity augmentation can be eliminated. A clear
trend can be also identified that the solidification rate always increases
with the nanoparticle loading. But at high particle loadings, the single-
phase assumption may break down due to the nanoparticle sedi-
mentation and migration issues. Accordingly, experimental works are
needed to ascertain the nanoparticle loading ranges within which the
single-phase assumption is reasonable to be used. Likewise, dispersing
GnP with high aspect ratio and excellent thermal conductivity shows
the best solidification enhancement as compared to the nanometals and
nano metal oxides.
As for the solidification process, the effectiveness of dispersing na-
noparticles is clearly inferior to that of using fins and metal foams. This
is decided by the material properties and limitations of nanostructures,
as well as the main heat transfer mechanism in the solidification pro-
cess. Hence, dispersing nanoparticles is actually more suitable for the
scenarios which only need a complete melting/freezing cycle rather
than a very fast melting/freezing rate. For example, for PCM integrated
walls and roofs which have a strict U-value requirement, nanoparticles
can improve the effective utilization of latent heat without increasing
the system weight and cost.
T. Xiong, et al.
5.3. Research gaps and future outlook
Several research gaps and outlook for further work have been
identified from the reported studies:
(1) Since the current prediction models have large uncertainties which
can lead to discrepancy between simulation and experiment
[163,183], there is an urgent need to develop new empirical models
for NePCMs. For this purpose, experimental studies using different
characterization methods are strongly encouraged. It is also im-
portant to understand the diffusion of nanostructures and its in-
fluence on the thermophysical properties of solid, mushy, and li-
quid NePCMs. Potential approaches include MD simulation
[113–117] and particle image velocimetry (PIV) [219].
(2) Most of the current prediction models have not considered the
temperature dependency of effective viscosity, which also has not
been considered in most of the reported simulations. In fact, the
viscosity of NePCM was found to decrease with temperature in
some experiments [92,220]. Hence, the degraded convection heat
transfer may be recovered with the increase of temperature. It is
suggested to consider the viscosity-temperature dependency in the
numerical model.
(3) Most of the reported studies have used the melting/solidification
rates to evaluate the TES performance of NePCM systems. However,
nanoparticles will usually reduce the latent heat as discussed in
Section 2.3.3. This is also a reason for the accelerated phase change
process. From another point of view, the increased melting/solidi-
fication rate may not represent an improved heat storage/release
rate [45]. Most studies did not consider this issue except [174] and
[206]. Hence, trade-off studies should be made to consider the in-
fluence of conduction enhancement, convection degradation, and
latent heat reduction. The impact of dispersing nanoparticles on the
energy storage/release rate and exergy efficiency of system is worth
further study.
(4) Though the simulations based on single-phase approaches remain
dominant in NePCM studies, they are unable to consider the in-
fluence of microscopic transport of nanoparticles such as the par-
ticle agglomeration and sedimentation issues. In this regard, new
two-phase and multi-phase models should be developed for
NePCMs with considering the influence of nanoparticle diffusion.
For example, the LBM models with mesoscopic nature can be used
in this area. But as discussed in Section 2.1, it is always difficult to
couple the physical states of the base PCM with the dynamics of
nanoparticles.
(5) To our knowledge, there are only a few studies [95,96,185,186]
available in which the numerical models have been validated
against the experimental data of phase change behavior of NePCMs.
The majority of the reported models have only been validated
against the previous experimental data of pure PCMs. This may not
be a proper validation method. In the future, more experimental
studies of NePCMs are needed to validate the newly proposed nu-
merical methods and models.
(6) Most of the reported studies (Table 5 and 6) have used 105 and 106
as the mushy zone constant in their NePCM models. However, these
Amush values also have not been validated by experiments. Since the
liquid NePCM can become mudlike at a high nanoparticle loading
[211], the Amush of NePCM and its influence should be reconsidered.
Apparently, more investigations should be focused on this topic.
6. Conclusions
Dispersing thermally conductive nanostructures offer an approach
to remarkably enhance the thermal performance of pure PCMs, thereby
improving their effectiveness in TES applications. Here, we provide a
comprehensive review on the simulation-based studies of NePCMs.
Important conclusions are as follows:
25
Applied Thermal Engineering 178 (2020) 115492
(1) The melting rate of NePCMs can be improved by nanoparticles
within a certain range of loading. The nanoparticles will also cause
viscosity augmentation and consequently offset or even degrade the
improved conduction heat transfer. Numerically investigate the
optimal nanoparticle properties and loadings for given systems is
significant to improve the phase change process and heat storage
rate.
(2) The solidification rate of NePCMs always increases with the nano-
particle loading. Under high particle loadings, the particle ag-
gregation and sedimentation issues should be considered in the si-
mulation since the single-phase assumption may not be valid. The
reduced latent heat by nanoparticles also improves the heat release
rate.
(3) The effectiveness of nanoparticles is more prominent in the solidi-
fication process than in the melting process. The effectiveness can
also be influenced by the container structures, geometries and or-
ientations, which is related to the material properties and main heat
transfer mechanisms.
(4) The selection of suitable nanostructures should be based on the
thermal conductivity, aspect ratio, interface contact area, and the
side effects on latent heat reduction and viscosity augmentation.
Nanocarbons, particularly GnP and CNT, showed the best heat
transfer enhancement for PCM systems.
(5) There is an urgent need to develop new empirical models for the
thermophysical properties of NePCMs, particularly thermal con-
ductivity and viscosity models. The uncertainties of the current
prediction models is the main reason for the discrepancy between
simulation and experiment. Hence, it is suggested to use the mea-
sured thermal properties with considering the temperature de-
pendency in simulations.
(6) For NePCMs, trade-off studies must be conducted to consider the
influence of conduction enhancement, convection degradation, and
latent heat reduction.
Declaration of Competing Interest
None.
Acknowledgements
This work has been supported by City Developments Limited (CDL)
project R-296-000-174-720 and NUS-AGC Inc. project R-296-000-183-
597. Acknowledgement is also given to Department of Building,
National University of Singapore.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.applthermaleng.2020.115492.
References
[1] I.E. Agency, World Energy Outlook (2019) 2019.
[2] L.H.J. Raijmakers, D.L. Danilov, R.A. Eichel, P.H.L. Notten, A review on various
temperature-indication methods for Li-ion batteries, Appl. Energy 240 (2019)
918–945.
[3] I.E. Agency, Global CO2 emissions in 2019, in, 2020.
[4] Y. Wang, X. Yang, T. Xiong, W. Li, K.W. Shah, Performance evaluation approach
for solar heat storage systems using phase change material, Energy Build. 155
(2017) 115–127.
[5] X. Yang, T. Xiong, J.L. Dong, W.X. Li, Y. Wang, Investigation of the Dynamic
Melting Process in a Thermal Energy Storage Unit Using a Helical Coil Heat
Exchanger, Energies 10 (2017) 1129.
[6] H. Akeiber, P. Nejat, M.Z.A. Majid, M.A. Wahid, F. Jomehzadeh, I. Zeynali
Famileh, J.K. Calautit, B.R. Hughes, S.A. Zaki, A review on phase change material
(PCM) for sustainable passive cooling in building envelopes, Renew. Sustain.
Energy Rev. 60 (2016) 1470–1497.
[7] P. Singh, S. Khanna, V. Becerra, S. Newar, V. Sharma, T.K. Mallick, D. Hutchinson,
J. Radulovic, R. Khusainov, Power improvement of finned solar photovoltaic
T. Xiong, et al.
phase change material system, Energy 193 (2020) 116735.
[8] S. Hekmat, G.R. Molaeimanesh, Hybrid thermal management of a Li-ion battery
module with phase change material and cooling water pipes: An experimental
investigation, Appl. Therm. Eng. 166 (2020) 114759.
[9] Z. Huang, N. Xie, X. Zheng, X. Gao, X. Fang, Y. Fang, Z. Zhang, Experimental and
numerical study on thermal performance of Wood's alloy/expanded graphite
composite phase change material for temperature control of electronic devices,
Int. J. Therm. Sci. 135 (2019) 375–385.
[10] N.R. Jankowski, F.P. McCluskey, A review of phase change materials for vehicle
component thermal buffering, Appl. Energy 113 (2014) 1525–1561.
[11] C. Prieto, L.F. Cabeza, Thermal energy storage (TES) with phase change materials
(PCM) in solar power plants (CSP). Concept and plant performance, Appl. Energy
254 (2019) 113646.
[12] W. Kostowski, K. Pajączek, A. Pociecha, J. Kalina, P. Niedzielski, A. Przybył,
Methods of waste heat recovery – A compressor station case study, Energy
Convers. Manage. 197 (2019) 111837.
[13] S.-F. Li, Z.-H. Liu, X.-J. Wang, A comprehensive review on positive cold energy
storage technologies and applications in air conditioning with phase change ma-
terials, Appl. Energy 255 (2019) 113667.
[14] J. Jaguemont, N. Omar, P. Van den Bossche, J. Mierlo, Phase-change materials
(PCM) for automotive applications: A review, Appl. Therm. Eng. 132 (2018)
308–320.
[15] J. Pereira da Cunha, P. Eames, Thermal energy storage for low and medium
temperature applications using phase change materials – A review, Appl. Energy
177 (2016) 227–238.
[16] J. Chen, S. Kang, J.E, Z. Huang, K. Wei, B. Zhang, H. Zhu, Y. Deng, F. Zhang, G.
Liao, Effects of different phase change material thermal management strategies on
the cooling performance of the power lithium ion batteries: A review, Journal of
Power Sources, 442 (2019) 227228.
[17] K.W. Shah, A review on enhancement of phase change materials - A nanomaterials
perspective, Energy Build. 175 (2018) 57–68.
[18] M.A. Kibria, M.R. Anisur, M.H. Mahfuz, R. Saidur, I.H.S.C. Metselaar, A review on
thermophysical properties of nanoparticle dispersed phase change materials,
Energy Convers. Manage. 95 (2015) 69–89.
[19] L.-W. Fan, X. Fang, X. Wang, Y. Zeng, Y.-Q. Xiao, Z.-T. Yu, X. Xu, Y.-C. Hu, K.-
F. Cen, Effects of various carbon nanofillers on the thermal conductivity and en-
ergy storage properties of paraffin-based nanocomposite phase change materials,
Appl. Energy 110 (2013) 163–172.
[20] X. Fang, L.-W. Fan, Q. Ding, X. Wang, X.-L. Yao, J.-F. Hou, Z.-T. Yu, G.-H. Cheng,
Y.-C. Hu, K.-F. Cen, Increased thermal conductivity of eicosane-based composite
phase change materials in the presence of graphene nanoplatelets, Energy Fuels 27
(2013) 4041–4047.
[21] S. Kim, L.T. Drzal, High latent heat storage and high thermal conductive phase
change materials using exfoliated graphite nanoplatelets, Sol. Energy Mater. Sol.
Cells 93 (2009) 136–142.
[22] M. Li, A nano-graphite/paraffin phase change material with high thermal con-
ductivity, Appl. Energy 106 (2013) 25–30.
[23] A. Karaipekli, A. Biçer, A. Sarı, V.V. Tyagi, Thermal characteristics of expanded
perlite/paraffin composite phase change material with enhanced thermal con-
ductivity using carbon nanotubes, Energy Convers. Manage. 134 (2017) 373–381.
[24] W. Cui, Y. Yuan, L. Sun, X. Cao, X. Yang, Experimental studies on the supercooling
and melting/freezing characteristics of nano-copper/sodium acetate trihydrate
composite phase change materials, Renew. Energy 99 (2016) 1029–1037.
[25] J.L. Zeng, Z. Cao, D.W. Yang, L.X. Sun, L. Zhang, Thermal conductivity en-
hancement of Ag nanowires on an organic phase change material, J. Therm. Anal.
Calorim. 101 (2009) 385–389.
[26] J.-L. Zeng, F.-R. Zhu, S.-B. Yu, L. Zhu, Z. Cao, L.-X. Sun, G.-R. Deng, W.-P. Yan,
L. Zhang, Effects of copper nanowires on the properties of an organic phase change
material, Sol. Energy Mater. Sol. Cells 105 (2012) 174–178.
[27] T. Sreethawong, K.W. Shah, S.-Y. Zhang, E. Ye, S.H. Lim, U. Maheswaran,
W.Y. Mao, M.-Y. Han, Optimized production of copper nanostructures with high
yields for efficient use as thermal conductivity-enhancing PCM dopant, J. Mater.
Chem. A 2 (2014).
[28] R. Parameshwaran, R. Jayavel, S. Kalaiselvam, Study on thermal properties of
organic ester phase-change material embedded with silver nanoparticles, J.
Therm. Anal. Calorim. 114 (2013) 845–858.
[29] Y. Deng, J. Li, T. Qian, W. Guan, Y. Li, X. Yin, Thermal conductivity enhancement
of polyethylene glycol/expanded vermiculite shape-stabilized composite phase
change materials with silver nanowire for thermal energy storage, Chem. Eng. J.
295 (2016) 427–435.
[30] P. Chandrasekaran, M. Cheralathan, V. Kumaresan, R. Velraj, Enhanced heat
transfer characteristics of water based copper oxide nanofluid PCM (phase change
material) in a spherical capsule during solidification for energy efficient cool
thermal storage system, Energy 72 (2014) 636–642.
[31] M. Nourani, N. Hamdami, J. Keramat, A. Moheb, M. Shahedi, Thermal behavior of
paraffin-nano-Al2O3 stabilized by sodium stearoyl lactylate as a stable phase
change material with high thermal conductivity, Renew. Energy 88 (2016)
474–482.
[32] R.K. Sharma, P. Ganesan, V.V. Tyagi, H.S.C. Metselaar, S.C. Sandaran, Thermal
properties and heat storage analysis of palmitic acid-TiO2 composite as nano-en-
hanced organic phase change material (NEOPCM), Appl. Therm. Eng. 99 (2016)
1254–1262.
[33] Q. He, S. Wang, M. Tong, Y. Liu, Experimental study on thermophysical properties
of nanofluids as phase-change material (PCM) in low temperature cool storage,
Energy Convers. Manage. 64 (2012) 199–205.
[34] D. Dsilva Winfred Rufuss, L. Suganthi, S. Iniyan, P.A. Davies, Effects of
26
Applied Thermal Engineering 178 (2020) 115492
nanoparticle-enhanced phase change material (NPCM) on solar still productivity,
J. Clean. Prod., 192 (2018) 9-29.
[35] N. Şahan, M. Fois, H. Paksoy, Improving thermal conductivity phase change
materials—A study of paraffin nanomagnetite composites, Sol. Energy Mater. Sol.
Cells 137 (2015) 61–67.
[36] X. Fang, L.-W. Fan, Q. Ding, X.-L. Yao, Y.-Y. Wu, J.-F. Hou, X. Wang, Z.-T. Yu, G.-
H. Cheng, Y.-C. Hu, Thermal energy storage performance of paraffin-based com-
posite phase change materials filled with hexagonal boron nitride nanosheets,
Energy Convers. Manage. 80 (2014) 103–109.
[37] J.M. Munyalo, X. Zhang, Particle size effect on thermophysical properties of na-
nofluid and nanofluid based phase change materials: A review, J. Mol. Liq. 265
(2018) 77–87.
[38] K.Y. Leong, M.R. Abdul Rahman, B.A. Gurunathan, Nano-enhanced phase change
materials: A review of thermo-physical properties, applications and challenges, J.
Storage Mater. 21 (2019) 18–31.
[39] R. Du, W. Li, T. Xiong, X. Yang, Y. Wang, K.W. Shah, Numerical investigation on
the melting of nanoparticle-enhanced PCM in latent heat energy storage unit with
spiral coil heat exchanger, Build. Simul. 12 (2019) 869–879.
[40] C.J. Ho, J.Y. Gao, An experimental study on melting heat transfer of paraffin
dispersed with Al2O3 nanoparticles in a vertical enclosure, Int. J. Heat Mass
Transf. 62 (2013) 2–8.
[41] Y. Zeng, L.-W. Fan, Y.-Q. Xiao, Z.-T. Yu, K.-F. Cen, An experimental investigation
of melting of nanoparticle-enhanced phase change materials (NePCMs) in a
bottom-heated vertical cylindrical cavity, Int. J. Heat Mass Transf. 66 (2013)
111–117.
[42] L. Fan, J.M. Khodadadi, A theoretical and experimental investigation of uni-
directional freezing of nanoparticle-enhanced phase change materials, J. Heat
Transf. 134 (2012).
[43] L.-W. Fan, Z.-Q. Zhu, Y. Zeng, Q. Lu, Z.-T. Yu, Heat transfer during melting of
graphene-based composite phase change materials heated from below, Int. J. Heat
Mass Transf. 79 (2014) 94–104.
[44] L.-W. Fan, Z.-Q. Zhu, Y. Zeng, Q. Ding, M.-J. Liu, Unconstrained melting heat
transfer in a spherical container revisited in the presence of nano-enhanced phase
change materials (NePCM), Int. J. Heat Mass Transf. 95 (2016) 1057–1069.
[45] N. Hu, Z.-Q. Zhu, Z.-R. Li, J. Tu, L.-W. Fan, Close-contact melting heat transfer on a
heated horizontal plate: Revisited in the presence of nano-enhanced phase change
materials (NePCM), Int. J. Heat Mass Transf. 124 (2018) 794–799.
[46] N.S. Dhaidan, Nanostructures assisted melting of phase change materials in var-
ious cavities, Appl. Therm. Eng. 111 (2017) 193–212.
[47] Z. Ma, W. Lin, M.I. Sohel, Nano-enhanced phase change materials for improved
building performance, Renew. Sustain. Energy Rev. 58 (2016) 1256–1268.
[48] A. Kasaeian, L. bahrami, F. Pourfayaz, E. Khodabandeh, W.-M. Yan, Experimental
studies on the applications of PCMs and nano-PCMs in buildings: a critical review,
Energy Build., 154 (2017) 96-112.
[49] H.W. Chiam, W.H. Azmi, N.M. Adam, M.K.A.M. Ariffin, Numerical study of na-
nofluid heat transfer for different tube geometries – A comprehensive review on
performance, Int. Commun. Heat Mass Transfer 86 (2017) 60–70.
[50] A. Albojamal, K. Vafai, Analysis of single phase, discrete and mixture models, in
predicting nanofluid transport, Int. J. Heat Mass Transf. 114 (2017) 225–237.
[51] L. Godson, B. Raja, D. Mohan Lal, S. Wongwises, Enhancement of heat transfer
using nanofluids—an overview, Renew. Sustain. Energy Rev. 14 (2010) 629–641.
[52] M.S. Mojarrad, A. Keshavarz, A. Shokouhi, Nanofluids thermal behavior analysis
using a new dispersion model along with single-phase, Heat Mass Transf. 49
(2013) 1333–1343.
[53] S. Özerinç, A.G. Yazıcıoğlu, S. Kakaç, Numerical analysis of laminar forced con-
vection with temperature-dependent thermal conductivity of nanofluids and
thermal dispersion, Int. J. Therm. Sci. 62 (2012) 138–148.
[54] Y. Xuan, W. Roetzel, Conceptions for heat transfer correlation of nanofluids, Int. J.
Heat Mass Transf. 43 (2000) 3701–3707.
[55] S. Kumar, S.K. Prasad, J. Banerjee, Analysis of flow and thermal field in nanofluid
using a single phase thermal dispersion model, Appl. Math. Model. 34 (2010)
573–592.
[56] Y. Ding, D. Wen, Particle migration in a flow of nanoparticle suspensions, Powder
Technol. 149 (2005) 84–92.
[57] A. Behzadmehr, M. Saffar-Avval, N. Galanis, Prediction of turbulent forced con-
vection of a nanofluid in a tube with uniform heat flux using a two phase ap-
proach, Int. J. Heat Fluid Flow 28 (2007) 211–219.
[58] A. Malvandi, M.R. Safaei, M.H. Kaffash, D.D. Ganji, MHD mixed convection in a
vertical annulus filled with Al2O3–water nanofluid considering nanoparticle mi-
gration, J. Magn. Magn. Mater. 382 (2015) 296–306.
[59] S.M. Vanaki, P. Ganesan, H.A. Mohammed, Numerical study of convective heat
transfer of nanofluids: a review, Renew. Sustain. Energy Rev. 54 (2016)
1212–1239.
[60] G. Liang, I. Mudawar, Review of single-phase and two-phase nanofluid heat
transfer in macro-channels and micro-channels, Int. J. Heat Mass Transf. 136
(2019) 324–354.
[61] O. Mahian, L. Kolsi, M. Amani, P. Estellé, G. Ahmadi, C. Kleinstreuer,
J.S. Marshall, M. Siavashi, R.A. Taylor, H. Niazmand, S. Wongwises, T. Hayat,
A. Kolanjiyil, A. Kasaeian, I. Pop, Recent advances in modeling and simulation of
nanofluid flows-Part I: Fundamentals and theory, Phys. Rep. 790 (2019) 1–48.
[62] Fluent 19.0 User's Guide, in, 2019.
[63] N.S. Bondareva, B. Buonomo, O. Manca, M.A. Sheremet, Heat transfer perfor-
mance of the finned nano-enhanced phase change material system under the in-
clination influence, Int. J. Heat Mass Transf. 135 (2019) 1063–1072.
[64] M. Arıcı, E. Tutuncu, A. Campo, Numerical investigation of melting of paraffin
wax dispersed with CuO nanoparticles inside a square enclosure, Heat Transf. Res.
T. Xiong, et al.
49 (2018).
[65] Y. Khattari, T. El Rhafiki, N. Choab, T. Kousksou, M. Alaphilippe, Y. Zeraouli,
Apparent heat capacity method to investigate heat transfer in a composite phase
change material, J. Storage Mater. 28 (2020) 101239.
[66] S.N. Al-Saadi, Z. Zhai, Modeling phase change materials embedded in building
enclosure: a review, Renew. Sustain. Energy Rev. 21 (2013) 659–673.
[67] X. Jin, H. Hu, X. Shi, X. Zhou, X. Zhang, Comparison of two numerical heat
transfer models for phase change material board, Appl. Therm. Eng. 128 (2018)
1331–1339.
[68] Z. Andrássy, Z. Szánthó, Thermal behaviour of materials in interrupted phase
change, J. Therm. Anal. Calorim. 138 (2019) 3915–3924.
[69] Y. Zhang, K. Du, J.P. He, L. Yang, Y.J. Li, Impact Factors Analysis of the Enthalpy
Method and the Effective Heat Capacity Method on the Transient Nonlinear Heat
Transfer in Phase Change Materials (PCMs), Numer. Heat Transf., Part A: Appl. 65
(2014) 66–83.
[70] Y. Zhang, Modified computational methods using effective heat capacity model for
the thermal evaluation of PCM outfitted walls, Int. Commun. Heat Mass Transf.
108 (2019) 104278.
[71] E. Günther, S. Hiebler, H. Mehling, R. Redlich, Enthalpy of Phase Change Materials
as a Function of Temperature: Required Accuracy and Suitable Measurement
Methods, Int. J. Thermophys. 30 (2009) 1257–1269.
[72] M. Iten, S. Liu, A. Shukla, P.D. Silva, Investigating the impact of C p -T values
determined by DSC on the PCM-CFD model, Appl. Therm. Eng. 117 (2017) 65–75.
[73] M. Iten, S. Liu, A. Shukla, Experimental validation of an air-PCM storage unit
comparing the effective heat capacity and enthalpy methods through CFD simu-
lations, Energy 155 (2018) 495–503.
[74] H. Huang, Y. Xiao, J. Lin, T. Zhou, Y. Liu, Q. Zhao, Improvement of the efficiency
of solar thermal energy storage systems by cascading a PCM unit with a water
tank, J. Clean. Prod. 245 (2020) 118864.
[75] Z. Yinping, J. Yi, A simple method, the -history method, of determining the heat of
fusion, specific heat and thermal conductivity of phase-change materials, Meas.
Sci. Technol. 10 (1999) 201–205.
[76] Y. Qu, S. Wang, D. Zhou, Y. Tian, Experimental study on thermal conductivity of
paraffin-based shape-stabilized phase change material with hybrid carbon nano-
additives, Renew. Energy 146 (2020) 2637–2645.
[77] C. Yadav, R. Rekha Sahoo, Experimental analysis for optimum thermal perfor-
mance and thermophysical parameters of MWCNT based capric acid PCM by using
T-history method, Powder Technol. 364 (2020) 392–403.
[78] K.P. Venkitaraj, S. Suresh, Effects of Al2O3, CuO and TiO2 nanoparticles son
thermal, phase transition and crystallization properties of solid-solid phase change
material, Mech. Mater. 128 (2019) 64–88.
[79] Z. Ma, Y. Zhang, Solid velocity correction schemes for a temperature transforming
model for convection phase change, Int. J. Numer. Meth. Heat Fluid Flow 16
(2006) 204–225.
[80] B.L. Gowreesunker, S.A. Tassou, M. Kolokotroni, Improved simulation of phase
change processes in applications where conduction is the dominant heat transfer
mode, Energy Build. 47 (2012) 353–359.
[81] V.R. Voller, Implicit Finite—difference Solutions of the Enthalpy Formulation of
Stefan Problems, IMA J. Numer. Anal. 5 (1985) 201–214.
[82] J.C. Álvarez-Hostos, E.A. Gutierrez-Zambrano, J.C. Salazar-Bove, E.S. Puchi-
Cabrera, A.D. Bencomo, Solving heat conduction problems with phase-change
under the heat source term approach and the element-free Galerkin formulation,
Int. Commun. Heat Mass Transf. 108 (2019) 104321.
[83] V.R. Voller, C.R. Swaminathan, ERAL source-based method for solidification phase
change, Numer. Heat Transf., Part B: Fundam. 19 (1991) 175–189.
[84] J. Bony, S. Citherlet, Numerical model and experimental validation of heat storage
with phase change materials, Energy Build. 39 (2007) 1065–1072.
[85] (!!! INVALID CITATION !!! [72, 85]).
[86] X. Jin, H. Hu, X. Shi, X. Zhou, L. Yang, Y. Yin, X. Zhang, A new heat transfer model
of phase change material based on energy asymmetry, Appl. Energy 212 (2018)
1409–1416.
[87] G. Zhou, Y. Han, Numerical simulation on thermal characteristics of supercooled
salt hydrate PCM for energy storage: Multiphase model, Appl. Therm. Eng. 125
(2017) 145–152.
[88] S. Wu, D. Zhu, X. Li, H. Li, J. Lei, Thermal energy storage behavior of Al2O3–H2O
nanofluids, Thermochim. Acta 483 (2009) 73–77.
[89] Y. Liu, X. Li, P. Hu, G. Hu, Study on the supercooling degree and nucleation be-
havior of water-based graphene oxide nanofluids PCM, Int. J. Refrig. 50 (2015)
80–86.
[90] S. Kashani, A.A. Ranjbar, M. Abdollahzadeh, S. Sebti, Solidification of nano-en-
hanced phase change material (NEPCM) in a wavy cavity, Heat Mass Transf. 48
(2012) 1155–1166.
[91] S. Motahar, N. Nikkam, A.A. Alemrajabi, R. Khodabandeh, M.S. Toprak,
M. Muhammed, A novel phase change material containing mesoporous silica na-
noparticles for thermal storage: A study on thermal conductivity and viscosity, Int.
Commun. Heat Mass Transf. 56 (2014) 114–120.
[92] B. Águila V, D.A. Vasco, P. Galvez P, P.A. Zapata, Effect of temperature and CuO-
nanoparticle concentration on the thermal conductivity and viscosity of an organic
phase-change material, Int. J. Heat Mass Transf., 120 (2018) 1009-1019.
[93] Y. Dutil, D.R. Rousse, N.B. Salah, S. Lassue, L. Zalewski, A review on phase-change
materials: Mathematical modeling and simulations, Renew. Sustain. Energy Rev.
15 (2011) 112–130.
[94] M. Alomair, Y. Alomair, S. Tasnim, S. Mahmud, H. Abdullah, Analyses of Bio-
Based Nano-PCM filled concentric cylindrical energy storage system in vertical
orientation, J. Storage Mater. 20 (2018) 380–394.
[95] N.S. Dhaidan, J.M. Khodadadi, T.A. Al-Hattab, S.M. Al-Mashat, Experimental and
27
Applied Thermal Engineering 178 (2020) 115492
numerical study of constrained melting of n-octadecane with CuO nanoparticle
dispersions in a horizontal cylindrical capsule subjected to a constant heat flux,
Int. J. Heat Mass Transf. 67 (2013) 523–534.
[96] N.S. Dhaidan, J.M. Khodadadi, T.A. Al-Hattab, S.M. Al-Mashat, Experimental and
numerical investigation of melting of phase change material/nanoparticle sus-
pensions in a square container subjected to a constant heat flux, Int. J. Heat Mass
Transf. 66 (2013) 672–683.
[97] N.S. Dhaidan, J.M. Khodadadi, T.A. Al-Hattab, S.M. Al-Mashat, Experimental and
numerical investigation of melting of NePCM inside an annular container under a
constant heat flux including the effect of eccentricity, Int. J. Heat Mass Transf. 67
(2013) 455–468.
[98] J.H. Nazzi Ehms, R. De Césaro Oliveski, L.A. Oliveira Rocha, C. Biserni, M. Garai,
Fixed Grid Numerical Models for Solidification and Melting of Phase Change
Materials (PCMs), Appl. Sci. 9 (2019) 4334.
[99] A.D. Brent, V.R. Voller, K.J. Reid, Enthalpy-porosity technique for modeling
convection-diffusion phase change: application to the melting of a pure metal,
Numer. Heat Transf. 13 (1988) 297–318.
[100] M. Fadl, P.C. Eames, Numerical investigation of the influence of mushy zone
parameter Amush on heat transfer characteristics in vertically and horizontally
oriented thermal energy storage systems, Appl. Therm. Eng. 151 (2019) 90–99.
[101] M. Hameter, H. Walter, Influence of the Mushy Zone Constant on the Numerical
Simulation of the Melting and Solidification Process of Phase Change Materials, in:
Z. Kravanja, M. Bogataj (Eds.), Computer Aided Chemical Engineering, Vol. 38
Elsevier, 2016, pp. 439–444.
[102] O. Mahian, L. Kolsi, M. Amani, P. Estellé, G. Ahmadi, C. Kleinstreuer,
J.S. Marshall, R.A. Taylor, E. Abu-Nada, S. Rashidi, H. Niazmand, S. Wongwises,
T. Hayat, A. Kasaeian, I. Pop, Recent advances in modeling and simulation of
nanofluid flows—Part II: Applications, Phys. Rep. 791 (2019) 1–59.
[103] Y.-L. He, Q. Liu, Q. Li, W.-Q. Tao, Lattice Boltzmann methods for single-phase and
solid-liquid phase-change heat transfer in porous media: A review, Int. J. Heat
Mass Transf. 129 (2019) 160–197.
[104] I. Rasin, W. Miller, S. Succi, Phase-field lattice kinetic scheme for the numerical
simulation of dendritic growth, Phys. Rev. E, Stat., Nonlinear, Soft Matter Phys. 72
(2005) 066705.
[105] W.-S. Jiaung, J.-R. Ho, C.-P. Kuo, Lattice Boltzmann method for the heat con-
duction problem with phase change, Numer. Heat Transf., Part B: Fundam. 39
(2001) 167–187.
[106] R. Rojas, T. Takaki, M. Ohno, A phase-field-lattice Boltzmann method for mod-
eling motion and growth of a dendrite for binary alloy solidification in the pre-
sence of melt convection, J. Comput. Phys. 298 (2015) 29–40.
[107] Y. Feng, H. Li, L. Li, L. Bu, T. Wang, Numerical investigation on the melting of
nanoparticle-enhanced phase change materials (NEPCM) in a bottom-heated rec-
tangular cavity using lattice Boltzmann method, Int. J. Heat Mass Transf. 81
(2015) 415–425.
[108] Y. Huo, Z. Rao, Lattice Boltzmann investigation on phase change of nanoparticle-
enhanced phase change material in a cavity with separate plate, Energy Convers.
Manage. 154 (2017) 420–429.
[109] Q. Li, K.H. Luo, Q.J. Kang, Y.L. He, Q. Chen, Q. Liu, Lattice Boltzmann methods for
multiphase flow and phase-change heat transfer, Prog. Energy Combust. Sci. 52
(2016) 62–105.
[110] R. Huang, H. Wu, Phase interface effects in the total enthalpy-based lattice
Boltzmann model for solid–liquid phase change, J. Comput. Phys. 294 (2015)
346–362.
[111] R. Huang, H. Wu, A modified multiple-relaxation-time lattice Boltzmann model for
convection–diffusion equation, J. Comput. Phys. 274 (2014) 50–63.
[112] S.M. Rassoulinejad-Mousavi, Y. Zhang, Interatomic potentials transferability for
molecular simulations: a comparative study for platinum, gold and silver, Scient.
Rep. 8 (2018) 2424–12410.
[113] Y. Yu, Y. Tao, Y.-L. He, Molecular dynamics simulation of thermophysical prop-
erties of NaCl-SiO2 based molten salt composite phase change materials, Appl.
Therm. Eng. 166 (2020) 114628.
[114] M. Zhang, C. Wang, A. Luo, Z. Liu, X. Zhang, Molecular dynamics simulation on
thermophysics of paraffin/EVA/graphene nanocomposites as phase change ma-
terials, Appl. Therm. Eng. 166 (2020) 114639.
[115] H. Tafrishi, S. Sadeghzadeh, R. Ahmadi, F. Molaei, F. Yousefi, H. Hassanloo,
Investigation of tetracosane thermal transport in presence of graphene and carbon
nanotube fillers––A molecular dynamics study, J. Storage Mater. 29 (2020)
101321.
[116] H. Babaei, P. Keblinski, J.M. Khodadadi, Thermal conductivity enhancement of
paraffins by increasing the alignment of molecules through adding CNT/graphene,
Int. J. Heat Mass Transf. 58 (2013) 209–216.
[117] C.Y. Zhao, Y.B. Tao, Y.S. Yu, Molecular dynamics simulation of nanoparticle effect
on melting enthalpy of paraffin phase change material, Int. J. Heat Mass Transf.
150 (2020) 119382.
[118] F. Jabbari, A. Rajabpour, S. Saedodin, Thermal conductivity and viscosity of na-
nofluids: A review of recent molecular dynamics studies, Chem. Eng. Sci. 174
(2017) 67–81.
[119] J.M. Khodadadi, L. Fan, H. Babaei, Thermal conductivity enhancement of nanos-
tructure-based colloidal suspensions utilized as phase change materials for thermal
energy storage: A review, Renew. Sustain. Energy Rev. 24 (2013) 418–444.
[120] A. Einstein, Eine neue Bestimmung der Moleku¨ldimensionen, Ann. Phys. 19
(1906) 289–306.
[121] H.C. Brinkman, The Viscosity of Concentrated Suspensions and Solutions, J. Chem.
Phys., 20 (1952) 571-.
[122] M. Corcione, Empirical correlating equations for predicting the effective thermal
conductivity and dynamic viscosity of nanofluids, Energy Convers. Manage. 52
T. Xiong, et al.
(2011) 789–793.
[123] S.E.B. Maïga, S.J. Palm, C.T. Nguyen, G. Roy, N. Galanis, Heat transfer enhance-
ment by using nanofluids in forced convection flows, Int. J. Heat Fluid Flow 26
(2005) 530–546.
[124] C.T. Nguyen, F. Desgranges, G. Roy, N. Galanis, T. Maré, S. Boucher, H. Angue
Mintsa, Temperature and particle-size dependent viscosity data for water-based
nanofluids – Hysteresis phenomenon, Int. J. Heat Fluid Flow 28 (2007)
1492–1506.
[125] T.J.D.I.M. Krieger, A Mechanism for Non-Newtonian Flow in Suspensions of Rigid
Spheres, Trans. Soc. Rheol. 3 (1959) 137–152.
[126] I. Santamaria-Holek, C.I. Mendoza, The rheology of concentrated suspensions of
arbitrarily-shaped particles, J. Colloid Interface Sci. 346 (2010) 118–126.
[127] S.M.S. Murshed, K.C. Leong, C. Yang, Thermophysical and electrokinetic proper-
ties of nanofluids – A critical review, Appl. Therm. Eng. 28 (2008) 2109–2125.
[128] H. Chen, Y. Ding, C. Tan, Rheological behaviour of nanofluids, New J. Phys. 9
(2007) 367.
[129] R.S. Vajjha, Measurements of Thermophysical Properties of Nanofluids and
Computation of Heat Transfer Characteristics, in: Mechanical Engineering
Department, Vol. M.S., University of Alaska Fairbanks, Fairbanks, Alaska, 2009.
[130] B.C. Sahoo, R.S. Vajjha, R. Ganguli, G.A. Chukwu, D.K. Das, Det ermination of
Rheological Behavior of Aluminum Oxide Nanofluid and Development of New
Viscosity Correlations, Pet. Sci. Technol. 27 (2009) 1757–1770.
[131] P.K. Namburu, D.P. Kulkarni, D. Misra, D.K. Das, Viscosity of copper oxide na-
noparticles dispersed in ethylene glycol and water mixture, Exp. Therm Fluid Sci.
32 (2007) 397–402.
[132] R.S. Vajjha, D.K. Das, P.K. Namburu, Numerical study of fluid dynamic and heat
transfer performance of Al2O3 and CuO nanofluids in the flat tubes of a radiator,
Int. J. Heat Fluid Flow 31 (2010) 613–621.
[133] J. Zhou, M. Hu, D. Jing, The synergistic effect between surfactant and nanoparticle
on the viscosity of water-based fluids, Chem. Phys. Lett. 727 (2019) 1–5.
[134] U. Nithiyanantham, L. González-Fernández, Y. Grosu, A. Zaki, J.M. Igartua,
A. Faik, Shape effect of Al2O3 nanoparticles on the thermophysical properties and
viscosity of molten salt nanofluids for TES application at CSP plants, Appl. Therm.
Eng. 169 (2020) 114942.
[135] F. Wang, L. Han, Z. Zhang, X. Fang, J. Shi, W. Ma, Surfactant-free ionic liquid-
based nanofluids with remarkable thermal conductivity enhancement at very low
loading of graphene, Nanoscale Res. Lett. 7 (2012) 314.
[136] J. Liu, F. Wang, L. Zhang, X. Fang, Z. Zhang, Thermodynamic properties and
thermal stability of ionic liquid-based nanofluids containing graphene as advanced
heat transfer fluids for medium-to-high-temperature applications, Renew. Energy
63 (2014) 519–523.
[137] J.C. Maxwell, A treatise on electricity and magnetism, Clarendon press, Oxford,
1873.
[138] R.L. Hamilton, O.K. Crosser, Thermal Conductivity of Heterogeneous Two-
Component Systems, Ind. Eng. Chem. Fundam. 1 (1962) 187–191.
[139] J. Koo, C. Kleinstreuer, A new thermal conductivity model for nanofluids, J.
Nanopart. Res. 6 (2005) 577–588.
[140] S.K.N. Wakao, Heat and Mass Transfer in Packed Beds, Gordon and Breach Science
Publications, New York, 1982.
[141] R. Elbahjaoui, H. El Qarnia, Transient behavior analysis of the melting of nano-
particle-enhanced phase change material inside a rectangular latent heat storage
unit, Appl. Therm. Eng. 112 (2017) 720–738.
[142] Y.M.F. El Hasadi, J.M. Khodadadi, Numerical simulation of the effect of the size of
suspensions on the solidification process of nanoparticle-enhanced phase change
materials, J. Heat Transfer 135 (2013).
[143] K. Khanafer, K. Vafai, M. Lightstone, Buoyancy-driven heat transfer enhancement
in a two-dimensional enclosure utilizing nanofluids, Int. J. Heat Mass Transf. 46
(2003) 3639–3653.
[144] R.S. Vajjha, D.K. Das, Experimental determination of thermal conductivity of three
nanofluids and development of new correlations, Int. J. Heat Mass Transf. 52
(2009) 4675–4682.
[145] C.H. Chon, K.D. Kihm, S.P. Lee, S.U.S. Choi, Empirical correlation finding the role
of temperature and particle size for nanofluid (Al2O3) thermal conductivity en-
hancement, Appl. Phys. Lett. 87 (2005).
[146] C.-W. Nan, R. Birringer, D.R. Clarke, H. Gleiter, Effective thermal conductivity of
particulate composites with interfacial thermal resistance, J. Appl. Phys. 81 (1997)
6692–6699.
[147] S. Harish, D. Orejon, Y. Takata, M. Kohno, Thermal conductivity enhancement of
lauric acid phase change nanocomposite with graphene nanoplatelets, Appl.
Therm. Eng. 80 (2015) 205–211.
[148] Z. Xu, C. Kleinstreuer, Concentration photovoltaic–thermal energy co-generation
system using nanofluids for cooling and heating, Energy Convers. Manage. 87
(2014) 504–512.
[149] M. Bechiri, K. Mansouri, Analytical study of heat generation effects on melting and
solidification of nano-enhanced PCM inside a horizontal cylindrical enclosure,
Appl. Therm. Eng. 104 (2016) 779–790.
[150] S. Shaikh, K. Lafdi, K. Hallinan, Carbon nanoadditives to enhance latent energy
storage of phase change materials, J. Appl. Phys. 103 (2008) 94302.
[151] J.L. Zeng, Z. Cao, D.W. Yang, F. Xu, L.X. Sun, X.F. Zhang, L. Zhang, Effects of
MWNTs on phase change enthalpy and thermal conductivity of a solid-liquid or-
ganic PCM, J. Therm. Anal. Calorim. 95 (2009) 507–512.
[152] J. Wang, H. Xie, Z. Xin, Thermal properties of paraffin based composites con-
taining multi-walled carbon nanotubes, Thermochim Acta 488 (2009) 39–42.
[153] N.H. Mohamed, F.S. Soliman, H. El Maghraby, Y.M. Moustfa, Thermal con-
ductivity enhancement of treated petroleum waxes, as phase change material, by α
nano alumina: Energy storage, Renew. Sustain. Energy Rev. 70 (2017) 1052–1058.
28
Applied Thermal Engineering 178 (2020) 115492
[154] Z. Rao, S. Wang, F. Peng, Molecular dynamics simulations of nano-encapsulated
and nanoparticle-enhanced thermal energy storage phase change materials, Int. J.
Heat Mass Transf. 66 (2013) 575–584.
[155] N. Das, Y. Takata, M. Kohno, S. Harish, Melting of graphene based phase change
nanocomposites in vertical latent heat thermal energy storage unit, Appl. Therm.
Eng. 107 (2016) 101–113.
[156] N. Das, Y. Takata, M. Kohno, S. Harish, Effect of carbon nano inclusion di-
mensionality on the melting of phase change nanocomposites in vertical shell-tube
thermal energy storage unit, Int. J. Heat Mass Transf. 113 (2017) 423–431.
[157] N. Das, M. Kohno, Y. Takata, D.V. Patil, S. Harish, Enhanced melting behavior of
carbon based phase change nanocomposites in horizontally oriented latent heat
thermal energy storage system, Appl. Therm. Eng. 125 (2017) 880–890.
[158] K. Kant, A. Shukla, A. Sharma, P. Henry Biwole, Heat transfer study of phase
change materials with graphene nano particle for thermal energy storage, Sol.
Energy 146 (2017) 453–463.
[159] F. Iachachene, Z. Haddad, H.F. Oztop, E. Abu-Nada, Melting of phase change
materials in a trapezoidal cavity: Orientation and nanoparticles effects, J. Mol. Liq.
292 (2019) 110592.
[160] R.P. Singh, S.C. Kaushik, D. Rakshit, Melting phenomenon in a finned thermal
storage system with graphene nano-plates for medium temperature applications,
Energy Convers. Manage. 163 (2018) 86–99.
[161] K. Chu, C.-C. Jia, W.-S. Li, Effective thermal conductivity of graphene-based
composites, Appl. Phys. Lett. 101 (2012).
[162] R.P. Singh, H. Xu, S.C. Kaushik, D. Rakshit, A. Romagnoli, Charging performance
evaluation of finned conical thermal storage system encapsulated with nano-en-
hanced phase change material, Appl. Therm. Eng. 151 (2019) 176–190.
[163] R.P. Singh, H. Xu, S.C. Kaushik, D. Rakshit, A. Romagnoli, Effective utilization of
natural convection via novel fin design & influence of enhanced viscosity due to
carbon nano-particles in a solar cooling thermal storage system, Sol. Energy 183
(2019) 105–119.
[164] K.W. Shah, Y. Lu, Morphology, large scale synthesis and building applications of
copper nanomaterials, Constr. Build. Mater. 180 (2018) 544–578.
[165] A.A. Rabienataj Darzi, M. Jourabian, M. Farhadi, Melting and solidification of
PCM enhanced by radial conductive fins and nanoparticles in cylindrical annulus,
Energy Convers. Manage. 118 (2016) 253–263.
[166] S. Liu, Y. Li, Y. Zhang, Mathematical solutions and numerical models employed for
the investigations of PCMs‫ ׳‬phase transformations, Renew. Sustain. Energy Rev. 33
(2014) 659–674.
[167] M. Jourabian, M. Farhadi, A.A. Rabienataj Darzi, Outward melting of ice enhanced
by Cu nanoparticles inside cylindrical horizontal annulus: Lattice Boltzmann ap-
proach, Appl. Math. Model., 37 (2013) 8813-8825.
[168] H.E. Patel, T. Sundararajan, T. Pradeep, A. Dasgupta, N. Dasgupta, S.K. Das, A
micro-convection model for thermal conductivity of nanofluids, Pramana 65
(2005) 863–869.
[169] M. Jourabian, M. Farhadi, K. Sedighi, On the expedited melting of phase change
material (PCM) through dispersion of nanoparticles in the thermal storage unit,
Comput. Math. Appl. 67 (2014) 1358–1372.
[170] M. Jourabian, M. Farhadi, A. Rabienataj Darzi, Constrained ice melting around
one cylinder in horizontal cavity accelerated using three heat transfer enhance-
ment techniques, Int. J. Therm. Sci. 125 (2018) 231–247.
[171] S.F. Hosseinizadeh, A.A.R. Darzi, F.L. Tan, Numerical investigations of un-
constrained melting of nano-enhanced phase change material (NEPCM) inside a
spherical container, Int. J. Therm. Sci. 51 (2012) 77–83.
[172] N. Hajighafoori Boukani, A. Dadvand, A.J. Chamkha, Melting of a Nano-enhanced
Phase Change Material (NePCM) in partially-filled horizontal elliptical capsules
with different aspect ratios, Int. J. Mech. Sci. 149 (2018) 164–177.
[173] M.T. Kohyani, B. Ghasemi, A. Raisi, S.M. Aminossadati, Melting of
cyclohexane–Cu nano-phase change material (nano-PCM) in porous medium
under magnetic field, J. Taiwan Inst. Chem. Eng. 77 (2017) 142–151.
[174] Z. Li, A. Shahsavar, A.A.A.A. Al-Rashed, P. Talebizadehsardari, Effect of porous
medium and nanoparticles presences in a counter-current triple-tube composite
porous/nano-PCM system, Appl. Therm. Eng. 167 (2020) 114777.
[175] M. Parsazadeh, X. Duan, Numerical study on the effects of fins and nanoparticles
in a shell and tube phase change thermal energy storage unit, Appl. Energy 216
(2018) 142–156.
[176] M. Ghalambaz, A. Doostani, A.J. Chamkha, M.A. Ismael, Melting of nanoparticles-
enhanced phase-change materials in an enclosure: Effect of hybrid nanoparticles,
Int. J. Mech. Sci. 134 (2017) 85–97.
[177] A.J. Chamkha, A. Doostanidezfuli, E. Izadpanahi, M. Ghalambaz, Phase-change
heat transfer of single/hybrid nanoparticles-enhanced phase-change materials
over a heated horizontal cylinder confined in a square cavity, Adv. Powder
Technol. 28 (2017) 385–397.
[178] M. Esapour, A. Hamzehnezhad, A.A. Rabienataj Darzi, M. Jourabian, Melting and
solidification of PCM embedded in porous metal foam in horizontal multi-tube
heat storage system, Energy Convers. Manage. 171 (2018) 398–410.
[179] R. Hossain, S. Mahmud, A. Dutta, I. Pop, Energy storage system based on nano-
particle-enhanced phase change material inside porous medium, Int. J. Therm. Sci.
91 (2015) 49–58.
[180] J.M. Mahdi, E.C. Nsofor, Melting enhancement in triplex-tube latent heat energy
storage system using nanoparticles-metal foam combination, Appl. Energy 191
(2017) 22–34.
[181] Y. Pahamli, M.J. Hosseini, A.A. Ranjbar, R. Bahrampoury, Effect of nanoparticle
dispersion and inclination angle on melting of PCM in a shell and tube heat ex-
changer, J. Taiwan Inst. Chem. Eng. 81 (2017) 316–334.
[182] S. Ebadi, S. Humaira Tasnim, A. Abbas Aliabadi, S. Mahmud, Geometry and na-
noparticle loading effects on the bio-based nano-PCM filled cylindrical thermal
T. Xiong, et al.
energy storage system, Appl. Therm. Eng. 141 (2018) 724–740.
[183] S. Ebadi, S.H. Tasnim, A.A. Aliabadi, S. Mahmud, Melting of nano-PCM inside a
cylindrical thermal energy storage system: Numerical study with experimental
verification, Energy Convers. Manage. 166 (2018) 241–259.
[184] M. Parsazadeh, X. Duan, Numerical and statistical study on melting of nano-
particle enhanced phase change material in a shell-and-tube thermal energy sto-
rage system, Appl. Therm. Eng. 111 (2017) 950–960.
[185] A.V. Arasu, A.S. Mujumdar, Numerical study on melting of paraffin wax with
Al2O3 in a square enclosure, Int. Commun. Heat Mass Transfer 39 (2012) 8–16.
[186] M. Arıcı, E. Tütüncü, M. Kan, H. Karabay, Melting of nanoparticle-enhanced
paraffin wax in a rectangular enclosure with partially active walls, Int. J. Heat
Mass Transf. 104 (2017) 7–17.
[187] Z.-J. Zheng, Y. Xu, M.-J. Li, Eccentricity optimization of a horizontal shell-and-
tube latent-heat thermal energy storage unit based on melting and melting-soli-
difying performance, Appl. Energy 220 (2018) 447–454.
[188] A. Pizzolato, A. Sharma, K. Maute, A. Sciacovelli, V. Verda, Design of effective fins
for fast PCM melting and solidification in shell-and-tube latent heat thermal en-
ergy storage through topology optimization, Appl. Energy 208 (2017) 210–227.
[189] S. Riahi, W.Y. Saman, F. Bruno, M. Belusko, N.H.S. Tay, Impact of periodic flow
reversal of heat transfer fluid on the melting and solidification processes in a latent
heat shell and tube storage system, Appl. Energy 191 (2017) 276–286.
[190] A. Sathishkumar, V. Kumaresan, R. Velraj, Solidification characteristics of water
based graphene nanofluid PCM in a spherical capsule for cool thermal energy
storage applications, Int. J. Refrig 66 (2016) 73–83.
[191] L.-W. Fan, Z.-Q. Zhu, M.-J. Liu, A similarity solution to unidirectional solidifica-
tion of nano-enhanced phase change materials (NePCM) considering the mushy
region effect, Int. J. Heat Mass Transf. 86 (2015) 478–481.
[192] R.P. Singh, S.C. Kaushik, D. Rakshit, Solidification behavior of binary eutectic
phase change material in a vertical finned thermal storage system dispersed with
graphene nano-plates, Energy Convers. Manage. 171 (2018) 825–838.
[193] M. Alizadeh, K. Hosseinzadeh, M.H. Shahavi, D.D. Ganji, Solidification accelera-
tion in a triplex-tube latent heat thermal energy storage system using V-shaped fin
and nano-enhanced phase change material, Appl. Therm. Eng. 163 (2019) 114436.
[194] J.M. Khodadadi, S.F. Hosseinizadeh, Nanoparticle-enhanced phase change mate-
rials (NEPCM) with great potential for improved thermal energy storage, Int.
Commun. Heat Mass Transfer 34 (2007) 534–543.
[195] M. Abdollahzadeh, M. Esmaeilpour, Enhancement of phase change material (PCM)
based latent heat storage system with nano fluid and wavy surface, Int. J. Heat
Mass Transf. 80 (2015) 376–385.
[196] R. Elbahjaoui, H. El Qarnia, Thermal analysis of nanoparticle-enhanced phase
change material solidification in a rectangular latent heat storage unit including
natural convection, Energy Build. 153 (2017) 1–17.
[197] S. Tiari, S. Qiu, M. Mahdavi, Discharging process of a finned heat pipe–assisted
thermal energy storage system with high temperature phase change material,
Energy Convers. Manage. 118 (2016) 426–437.
[198] S. Lohrasbi, S.Z. Miry, M. Gorji-Bandpy, D.D. Ganji, Performance enhancement of
finned heat pipe assisted latent heat thermal energy storage system in the presence
of nano-enhanced H2O as phase change material, Int. J. Hydrogen Energy 42
(2017) 6526–6546.
[199] S. Lohrasbi, M. Sheikholeslami, D.D. Ganji, Discharging process expedition of
NEPCM in fin-assisted Latent Heat Thermal Energy Storage System, J. Mol. Liq.
221 (2016) 833–841.
[200] S. Lohrasbi, M. Sheikholeslami, D.D. Ganji, Multi-objective RSM optimization of
fin assisted latent heat thermal energy storage system based on solidification
process of phase change Material in presence of copper nanoparticles, Appl.
Therm. Eng. 118 (2017) 430–447.
[201] M. Sheikholeslami, S. Lohrasbi, D.D. Ganji, Response surface method optimization
of innovative fin structure for expediting discharging process in latent heat
thermal energy storage system containing nano-enhanced phase change material,
29
Applied Thermal Engineering 178 (2020) 115492
J. Taiwan Inst. Chem. Eng. 67 (2016) 115–125.
[202] M. Sheikholeslami, O. Mahian, Enhancement of PCM solidification using inorganic
nanoparticles and an external magnetic field with application in energy storage
systems, J. Cleaner Prod. 215 (2019) 963–977.
[203] M. Sheikholeslami Kandelousi, KKL correlation for simulation of nanofluid flow
and heat transfer in a permeable channel, Phys. Lett. A 378 (2014) 3331–3339.
[204] J.M. Mahdi, E.C. Nsofor, Solidification of a PCM with nanoparticles in triplex-tube
thermal energy storage system, Appl. Therm. Eng. 108 (2016) 596–604.
[205] J.M. Mahdi, E.C. Nsofor, Solidification enhancement in a triplex-tube latent heat
energy storage system using nanoparticles-metal foam combination, Energy 126
(2017) 501–512.
[206] J.M. Mahdi, E.C. Nsofor, Solidification enhancement of PCM in a triplex-tube
thermal energy storage system with nanoparticles and fins, Appl. Energy 211
(2018) 975–986.
[207] H. Vatanparast, F. Shahabi, A. Bahramian, A. Javadi, R. Miller, The Role of
Electrostatic Repulsion on Increasing Surface Activity of Anionic Surfactants in the
Presence of Hydrophilic Silica Nanoparticles, Sci. Rep. 8 (2018) 7251.
[208] S. Sen, V. Govindarajan, C.J. Pelliccione, J. Wang, D.J. Miller, E.V. Timofeeva,
Surface Modification Approach to TiO2 Nanofluids with High Particle
Concentration, Low Viscosity, and Electrochemical Activity, ACS Appl. Mater.
Interfaces 7 (2015) 20538–20547.
[209] H.W. Xian, N.A.C. Sidik, R. Saidur, Impact of different surfactants and ultra-
sonication time on the stability and thermophysical properties of hybrid nano-
fluids, Int. Commun. Heat Mass Transfer 110 (2020) 104389.
[210] B. Munkhbayar, M. Bat-Erdene, B. Ochirkhuyag, D. Sarangerel, B. Battsengel,
H. Chung, H. Jeong, An experimental study of the planetary ball milling effect on
dispersibility and thermal conductivity of MWCNTs-based aqueous nanofluids,
Mater. Res. Bull. 47 (2012) 4187–4196.
[211] J. Wensel, B. Wright, D. Thomas, W. Douglas, B. Mannhalter, W. Cross, H. Hong, J.
Kellar, P. Smith, W. Roy, Enhanced thermal conductivity by aggregation in heat
transfer nanofluids containing metal oxide nanoparticles and carbon nanotubes,
Appl. Phys. Lett., 92 (2008) 023110-023110-023113.
[212] Y. Hwang, J.K. Lee, C.H. Lee, Y.M. Jung, S.I. Cheong, C.G. Lee, B.C. Ku, S.P. Jang,
Stability and thermal conductivity characteristics of nanofluids, Thermochim Acta
455 (2007) 70–74.
[213] X.-J. Wang, X. Li, S. Yang, Influence of pH and SDBS on the Stability and Thermal
Conductivity of Nanofluids, Energy Fuels 23 (2009) 2684–2689.
[214] X. Li, D. Zhu, X. Wang, Evaluation on dispersion behavior of the aqueous copper
nano-suspensions, J. Colloid Interface Sci. 310 (2007) 456–463.
[215] S. Salyan, S. Suresh, Study of thermo-physical properties and cycling stability of d-
Mannitol-copper oxide nanocomposites as phase change materials, J. Storage
Mater. 15 (2018) 245–255.
[216] S. Madruga, G.S. Mischlich, Melting dynamics of a phase change material (PCM)
with dispersed metallic nanoparticles using transport coefficients from empirical
and mean field models, Appl. Therm. Eng. 124 (2017) 1123–1133.
[217] N. Sezer, M.A. Atieh, M. Koç, A comprehensive review on synthesis, stability,
thermophysical properties, and characterization of nanofluids, Powder Technol.
344 (2019) 404–431.
[218] Y.M.F. El Hasadi, Numerical simulation of the melting process of nanostructured
based colloidal suspensions phase change materials including the effect of the
transport of the particles, J. Mol. Liq. 287 (2019) 110886.
[219] J. Lv, C. Hu, M. Bai, L. Li, L. Shi, D. Gao, Visualization of SiO2-water nanofluid
flow characteristics in backward-facing step using PIV, Exp. Therm Fluid Sci. 101
(2019) 151–159.
[220] S. Motahar, N. Nikkam, A.A. Alemrajabi, R. Khodabandeh, M.S. Toprak,
M. Muhammed, Experimental investigation on thermal and rheological properties
of n-octadecane with dispersed TiO2 nanoparticles, Int. Commun. Heat Mass
Transf. 59 (2014) 68–74.