Progress in Energy and Combustion Science 93 (2022) 101037

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

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

Micro/nano-encapsulated phase-change materials (ePCMs) for solar

photothermal absorption and storage: Fundamentals, recent advances, and
future directions
Samah A. Albdour a, Zoubida Haddad b, Omar Z. Sharaf a, Anas Alazzam a, c, Eiyad Abu-Nada a, *
a
Department of Mechanical Engineering, Khalifa University of Science and Technology, P.O. Box 127788, Abu Dhabi, UAE
b
Ecole Nationale Supérieur des Sciences de la Mer et de l’Aménagement du Littoral (ENSSMAL), Campus Universitaire de Dely Ibrahim Bois des Cars Dély, 16320
Ibrahim, Algeria
c
System on Chip Lab, Khalifa University, P.O. Box 127788, Abu Dhabi, UAE

A R T I C L E I N F O A B S T R A C T

Keywords: Building on their dual functionality for solar photothermal absorption and storage, slurries/dispersions of micro/
Phase change material nano-encapsulated phase-change materials (ePCMs) are capable of revolutionizing the solar-thermal industry.
Micro/nano encapsulation Yet, to facilitate their transition from the research and development stage into market adoption and penetration,
Solar thermal
there is a dire need for a methodical understanding of the design criteria, fabrication techniques, application
Thermal energy storage
Direct solar absorption
areas, and technical challenges of these novel solar concepts in light of state-of-the-art advances. This work
Encapsulated PCM slurry thoroughly addresses these needs with a focus on slurries/dispersions with solid-liquid PCM cores for latent heat
Optical properties storage and surface-engineered shells for solar radiation extinction. By dividing this study into four parts, we
Photothermal conversion start with an overview of the material types, desired attributes, and key challenges of PCMs; the different types of
Heat capacity PCM systems; and their potential applications in the solar energy industry. We then focus in the second part on
ePCMs in indirect (surface-based) and direct (volume-based) solar-absorption systems in terms of their functional
requirements, encapsulation methods, stability metrics and assessment, compositional and structural charac­
terization techniques, measurement of thermophysical properties, and key design parameters. The third part of
this work is dedicated to the theoretical foundation necessary to model and simulate solar ePCM systems,
including continuum, discrete, and multi-scale modeling approaches for flow and heat transfer in ePCM slurries/
dispersions; thermophysical property correlations; melting theory in PCM capsules; radiation transfer and optical
properties evaluation; and energy performance analysis. In the final part, recent breakthroughs in multi-
functional shell engineering, molten-salt encapsulation, multi-scale modeling, contrasting ePCMs and nano­
fluids, and ePCM-based optical filtration are highlighted. By striking a balance between fundamentals and ap­
plications, this work aims to serve as a comprehensive foundation for newcomers into this promising field of
research as well as an updated critique for experts looking to identify knowledge gaps, technical bottlenecks,
latest advances, and future directions.

materials, together with their low thermal conductivity.

The most promising way to solve the aforementioned issues is to
1 Introduction
encapsulate the PCM in a suitable shell material. This technique offers
the benefit of obtaining a larger surface area for better thermal prop­
The use of phase-change materials (PCMs) for thermal energy storage
erties of the PCM [2]. Capsules resulting from this technique are cate­
has been recognized as a viable method for balancing the in­
gorized primarily on three scales: macroscale (above 1 mm), microscale
compatibility of energy demand and supply. PCMs, in general, have a
(1 μm-1 mm), and nanoscale (less than 1 μm). The large size of macro­
high energy storage density, quasi-isothermal charging and discharging
capsules results in a temperature difference between the PCM core and
processes, and a high fusion enthalpy [1]. However, few pristine PCMs
boundary during the solidification process. The edge becomes solid,
have achieved commercial success due to leakage problems during the
whilst the center portion may remain liquid, obstructing effective heat
solid-liquid phase transition and incompatibility with surrounding

* Corresponding author.
E-mail address: eiyad.abunada@ku.ac.ae (E. Abu-Nada).

https://doi.org/10.1016/j.pecs.2022.101037
Received 17 January 2022; Received in revised form 16 August 2022; Accepted 20 August 2022
Available online 12 September 2022
0360-1285/© 2022 Elsevier Ltd. All rights reserved.
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Nomenclature MD Molecular dynamics

mf Mass fraction [-]
a Lattice constant MF Melamine formaldehyde
A Area [m2] ML Methyl laurate
AcCNF Acetylated cellulose nanofibrils MWCNT Multi-wall carbon nanotube
Bi Biot number [-] n Refractive index
cp Specific heat at constant pressure [J/kg•K] ṁ Mass flow rate [kg/s]
C Volumetric concentration M Mass [kg]
Cdr Drag coefficient [-] nA Mole number of reactant material
Clift Lift coefficient [-] npa Number of solid particles in a cell
Ctd Turbulent dispersion coefficient [-] N Number of capsules per unit volume
Cvm Virtual mass force coefficient [-] Nc Thermal conductivity number
CFD Computational fluid dynamics Nv Viscosity number
CNFs Carbon nanofibers NE-PCM Nano-enhanced phase-change material
CSP Concentrated solar power NIR Near infrared
CSS Conventional single-slope Nu Nusselt number [-]
CPV/T Concentrated photovoltaic/thermal system OA Oleic acid
DSC Differential scanning calorimetry P Pressure [Pa]
d Array spacing Po Electrical power output [W]
ds Shell thickness PCM Phase-change material
dpa Particle diameter [μm] PDA Polydopamine
→
D Electric field vector PETRA Pentaerythritol tetraacrylate
DASC Direct-absorption solar collector PEG Polyethylene glycol
DPD Dissipative particle dynamics PECA Poly(ethyl-2-cyanoacrylate)
DVB Divinylbenzene PMMA Polymethyl methacrylate
→ Pr Prandtl number [-]
E Electric field intensity
PS Polystyrene
ePCM Encapsulated phase-change material
PScEA Poly(styrene-co-ethylacrylate)
ETC Evacuated-tube collector
P(St-co-MAA) Poly(styrene-co-methacrylic-acid)
F Force [N]
→ PUF Poly(urea-formaldehyde)
F dr Drag force [N] PUR Polyurethane
→
F lift Lift force [N] PV Photovoltaic
→ →
F td Turbulent dispersion force [N] Q Local heat flux [W/m2]
→
F vm Virtual-mass force [N] Q Single microcapsule heat transfer [J]
FDM Finite difference method Qex,sc Scattering efficiency
FEM Finite element method Qex,a Absorption efficiency
FGM Phonon gas model Qex Extinction efficiency
Fo Fourier number [-] r Radial coordinate
FVM Finite volume method rGO Reduced graphene oxide
G Solar irradiance [W/m2] R Spherical core radius
GA Graphene aerogel R Gas constant [kJ/kmol•K]
GNP Graphite nanoplatelet RTE Radiative transfer equation
GO Graphene oxide ro Pipe radius [m]
Gr Grashof number [-] rpa Effective particle radius, [μm]
ħ Reduced Planck constant [1.054 × 10− 34J⋅s] Rcr Critical radius of solid nuclei, [μm]
h Convective heat transfer coefficient [W/m2⋅K] Ra Rayleigh number [-]
Hr Enthalpy of an endothermic reaction [J/mol] Re Real part of a complex number
Hs − l Latent heat of fusion [kJ/kg] Repa Reynolds number [-]
H Total enthalpy [kJ/kg] S Internal source [W/m3]
→ ̂s Unit vector
H Magnetic field vector
Sη Source function of radiation intensity
HTF Heat transfer fluid
Sr Scaling factor
IASC Indirect-absorption solar collector
SA Stearic acid
Iη Detected light intensities
SAH Solar air heater
Im Imaginary part of a complex number
SMA Styrene-maleic anhydride
J Heat flux vector
SS-PCM Shape-stabilized phase-change material
k Thermal conductivity [W/m•K]
SPH Smoothed particle hydrodynamics
Kn Knudsen number [-]
Ste Stefan number [-]
KB Boltzmann constant [1.38 × 10− 23 J/K]
SWH Solar water heater
ҡ Absorption index
SWPC Slurry without phase change
k Wave vector
t Time [s]
LBM Lattice Boltzmann method
T Temperature [K]
LPM Liters per minute
TA Styrene-maleic anhydride
MA Myristic acid
TES Thermal energy storage
MC Monte Carlo

2
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

TPE Two-phase Eulerian r Reaction

TSS Tubular solar still s Solid
u Velocity in axial direction [m/s] sh Shell
umax Maximum velocity in axial direction [m/s] sl Slurry
UF Urea formaldehyde td Turbulent dispersion force
UV Ultraviolet tot Total
vg Phonon velocity Tra Transverse
→v Pa Velocity of dispersed particle [m/s] vm Virtual mass force
vsound Longitudinal sound speed vib Vibration
V Volume [m3]
Greek symbols
̃
V Volume per mode of vibration
α Volume fraction
vTra Transverse speed of sound
γ Liquid fraction
vLon Longitudinal speed of sound
γo Surface free energy per unit area
w Shape factor of suspension particles
δ Infinitesimal change
x Pipeline location
ξ Bulk viscosity [ Pa•.s]
Y Transport coefficient of interest
η Wave number
Superscript ηPCM Encapsulation ratio
˙ Rate of change with respect to time ηth Thermal efficiency
ηelc Electrical efficiency
Subscripts ηtot Total efficiency
a Absorption λ Wavelength [m]
b Base liquid λb Phonon-boundary mean free path
char Charging process λd Phonon-defect mean free path
co Core λkn Molecular mean free path
conv Convection λph Phonon-phonon mean free path
cr Critical μ Shear viscosity [Pa•s]
in Internal μ0 Magnetic permeability
inl Inlet ση,a Absorption coefficient
dr Drag force ση,s Scattering coefficient
dis Discharging process ση,ex Extinction coefficient
e External τ Mean time between two phonon collisions
ex Extinction τrad Transmittance
eff Effective →τ Stress tensor
f Final τη Optical path length
j Summation index ρ Density [kg/m3]
i Initial ∅ Concentration
l Liquid ∅η Scattering phase angle
L Lift force χη Size parameter
Lon longitudinal Ω Solid angle
out Outlet ω Frequency
pa Particle ωη Single scattering albedo
m Melting point
mr Melting range

transfer [3]. Therefore, encapsulation at the macro scale is not as ad­
vantageous as the micro/nanoscale. Suspending micro/nano-ePCMs into
a carrier fluid to create a heat transfer fluid (HTF) is considered the
simplest and cheapest way to increase energy efficiency. This type of
HTF is referred to as a micro/nano-ePCM slurry/dispersion [4]. It is an
innovative flow state in which the slurry/dispersion acts as a heat carrier
while allowing the storage and release of large amounts of thermal en­
ergy with a minimum temperature rise [5].
The efficiency of solar photothermal systems can be enhanced by
using micro/nano-ePCM slurries/dispersions as working fluids. The
direct-absorption solar collector is one such example in which solar
radiation penetrates through the HTF to be directly absorbed by the
ePCM particles [6]. The efficiency here is directly correlated with the
optical properties of the photon-capturing shell material, i.e., its
extinction coefficient. In other applications, such as the optical filtration
of photovoltaic/thermal collectors [7], a micro/nano-ePCM slurry/dis­
persion has the potential to selectively absorb one or more bands of
sunlight while transmitting the remaining band(s) to the photovoltaic
receiver, avoiding the high temperature penalty on photovoltaic cells
[8].
Several authors have reviewed PCMs and micro/nano-ePCMs for
thermal energy storage and management systems, highlighting the as­
pects of core-shell material selection, preparation, characterization, and
heat transfer enhancement. Table 1 summarizes a number of selected
review studies on this topic. To the best of the authors’ knowledge, none
of the existing reviews considered the dual role of micro/nano-ePCMs
for photothermal absorption and storage. Therefore, this work pro­
vides a much-needed and critical review of the fundamentals and ap­
plications of ePCM slurries and dispersions as smart, multi-functional
fluids in next-generation solar photothermal conversion processes. By
surveying and comparing the most recent developments in the field,
technical bottlenecks and knowledge gaps are identified and future
research directions are recommended to facilitate the market uptake of
these novel solar concepts. By striking a balance between fundamentals
and applications, this work promotes the untapped potential of ePCM
slurries and dispersions while remaining suitable both as a compre­
hensive foundation to newcomers as well as an updated critique to
established experts.

3
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Table 1 2. An overview of phase-change materials (PCMs) and their role

A number of selected review articles on PCMs/ePCMs. in solar energy systems
Ref. Focus of study
2.1. Thermal energy storage technologies
[9] Provides a comprehensive overview of current advancements in latent heat
storage, thermal management, and TES applications. It covers PCM thermal
performance improvement techniques in depth. With the global focus on energy conservation and lowering green­
[10] Explores a list of shell materials with excellent thermal stability that could house gas emissions, renewable and sustainable energy has become a
provide a feasible solution for high-temperature TES. However, the thermal major scientific inquiry. Yet, intermittent availability and supply-
performance of shell and PCM combinations is not considered.
[11] Provides a summary of encapsulation strategies for inorganic PCMs and an
demand mismatch limit the potential of renewable energy sources and
examination of the effect of synthesis parameters on the thermophysical waste heat utilization. Thus, by combining thermal energy storage (TES)
properties of ePCM. systems with energy generation technologies, the use of energy gener­
[12] Discusses the development and characterization of eutectic organic PCMs and ated in times of high supply or low demand can be used in times of high
their utilization in form-stable systems.
demand or low supply [22]. Ultimately, TES systems should be able to
[13] Examines the performance of PCMs and ePCMs and their applications in
thermal management. In addition, it investigates the effect of various solar meet peak demand, non-peak demand, as well as daily and seasonal
collector and PCM settings on performance enhancement. needs, increasing the reliability and generation capacity of integrated
[14] Examines recent developments in the usage of PCMs in solar energy systems. energy systems [23].
[15] Investigates the performance and thermal management applications of PCMs The idea behind TES systems is to work reversibly while changing the
in solar thermal collectors and photovoltaic systems.
[16] Presents a complete assessment of recent developments and future
physical properties of a material, such as temperature or phase [24].
possibilities related to nano-enhanced PCMs in enhancing the performance of These reversible processes include cooling, heating, melting, solidifica­
PV/T systems. tion, vaporization, and condensation. The storage technologies are
[2] Investigates the effect of encapsulation parameters on the performance of TES classified as thermochemical, sensible, and latent, with each having
systems and the solidification and melting properties of ePCMs.
their own set of characteristics. The maturity and energy storage density
[17] Examines the various micro/nano-ePCM categories and their involvement in
solar thermal energy systems. This includes PCM thermal enhancement per unit volume of each technology are depicted in Fig. 1.
techniques, such as nanoparticles and skeletons. Thermochemical TES systems are based on reversible endothermic/
[4] Examines the flow and heat transfer characteristics of micro-encapsulated exothermic reactions between the heat source and the chemical re­
phase-change slurries, as well as the mechanisms and strategies for enhancing actants, with stored energy equal to the reaction enthalpy. As illustrated
heat transfer performance.
in Fig. 2(a), during the charging stage, heat is absorbed to dissociate the
[18] Provides a comprehensive analysis of PCMs and micro/nano-ePCMs and their
production techniques, considering both experimental and numerical original reactant into two or more products (an endothermic reaction).
investigations. The discharging stage involves the mixing of the products of the endo­
[19] Presents a thorough overview of the experimental, numerical, and theoretical thermic reaction at specific temperatures and pressures to reform the
studies of the heat transfer behavior and thermal conductivity augmentation
reactants and generate heat (exothermic reaction). The generated heat is
of PCMs loaded with nanoparticles in thermal energy systems.
[20] Covers a review of scientific literature as well as a compilation of technical converted into electricity or used in other thermally-powered applica­
and commercial information regarding PCM emulsions and micro-ePCM tions. Thermochemical TES systems outperform sensible and latent
slurries for usage as heat transfer fluids and thermal storage materials. storage in terms of energy density and volume requirements. They are;
[21] Focuses on the characterization of micro-ePCM slurries and their building however, toxic, produce corrosive products, and require extremely
applications, particularly the influence of physical stability and effect on heat
harsh reaction conditions [25]. The total amount of thermal energy
transfer performance.
stored or released in thermochemical TES is calculated using Eq. (1)
[25],
The workflow of the current review is organized into five major
Qthermochemical = nAΔHr , (1)
sections. In Section 2, we present an overview of the different types of
PCM systems, their desired characteristics, and key challenges, as well as
where nA is the mole number of the original reactant material and ΔHr is
their potential applications in the solar energy industry. In Section 3, an
the enthalpy of an endothermic reaction in J/mol.
elaborate description of ePCMs in indirect (surface-based) and direct
As shown in Fig. 2(b), the change in stored energy in sensible TES
(volume-based) solar-absorption systems is presented. This includes
systems is detected as a linear relationship with the change in temper­
PCM encapsulation methods, compositional and structural character­
ature. The phase of the used storage material does not change over the
ization techniques, stability requirements and stabilization strategies,
operating temperature range, but it undergoes volume change. Sensible
measurement of thermophysical properties, functional requirements for
TES materials are divided into two types based on their phase state: solid
the core and shell, and key design parameters. Then, Section 4 is dedi­
and liquid heat storage materials. Rocks, sand, and concrete are exam­
cated to the theoretical foundation necessary to model and simulate
ples of solid materials, whereas water, molten salt, and thermal oil are
solar ePCM systems, including continuum, discrete, and multi-scale
examples of liquid materials. Sensible TES systems are inexpensive (with
modeling approaches for flow and heat transfer in ePCM slurries/dis­
the exception of liquid metals) and widely used. Their thermal resilience
persions. This is in addition to presenting thermophysical property
and superior thermal conductivity make them popular for high-
correlations, theoretical background of thermal conductivity and spe­
cific heat capacity in PCMs, evaluation of radiation transfer and optical
properties, and energy performance analysis. In Section 5, recent ad­
vances in multi-functional shell engineering, implementing ePCMs and
nanofluids for direct-absorption solar collectors, ePCM-based optical
filtration, molten-salt encapsulation, and multi-scale modeling are
highlighted. Finally, in Section 6, conclusions and recommendations are
drawn as a roadmap for future research directions.

Fig. 1. Comparison between the main classes of thermal energy storage tech­
nologies (sensible, latent, and thermochemical) in terms of technical maturity
and volumetric energy storage density.

4
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 2. The fundamental working mechanisms of a) thermochemical, b) sensible, and c) latent thermal energy storage technologies.

temperature applications [25]. The total quantity of thermal energy wax, have melting temperatures less than 100 ◦ C. Materials with melting
stored or released in a sensible TES system is calculated using Eq. (2) temperatures between 100 and 300 ◦ C are considered medium melting-
[25], point materials, such as fatty acids. Above 300 ◦ C, materials such as salt
hydrates and metal alloys are in the range of high melting temperatures.
∫Tf
The research and development of PCMs for thermal energy storage
Qsensible = M cp dT, (2)
began at the end of the twentieth century [29]. Following the energy
Ti
crisis of the 1970s, research on PCMs sparked interest in a variety of
promising applications, which can be generally classified into thermal
where M and cp represent the mass and specific heat at constant pressure
regulation and TES.
of the storage material, respectively. Tiand Tfare the initial and final
Thermal regulation applications aim to prevent temperature fluctu­
temperatures of the material, respectively.
ations in the absence of the needed energy input for a specific demand.
Latent heat storage (also called phase-change heat storage) makes
For instance, in terms of cooling and heating in buildings, PCMs with
use of phase-change materials that have the unique ability to store and
melting temperatures in the range of 17− 25 ◦ C can meet the conditions
release energy in response to changes in their temperature and/or
of human comfort and high-quality living standards by providing ther­
pressure while maintaining a nearly constant temperature throughout
mal barriers or insulation. PCMs can regulate the temperature of a
phase transitions. Therefore, latent TES incorporates sensible TES, as
building by modulating its optical properties such as transmission and
illustrated in Fig. 2(c). During the storage stage (charging), heat is
absorption, rather than by means of the absorbed/generated latent heat
accumulated at the molecular level inside the material, activating its
during phase transition [30]. Other applications for thermal regulation
massive storage ability and changing its states. However, during the
are electronics [31], photovoltaic systems [32], textiles [33], and
release stage (discharging), the opposite occurs. In addition to reducing
biomedical applications [34]. When it comes to heat storage, which is
heat losses due to operating at a nearly constant temperature, latent TES
currently the bottleneck in many energy sectors, PCMs can improve the
has a higher energy storage density than sensible TES, allowing the
efficiency of both concentrated and unconcentrated solar systems.
storage system to be smaller. However, it has the disadvantages of the
Furthermore, waste heat from industrial operations can be reused [35].
low thermal conductivity of the used PCM and the difficulty of designing
and selecting a heat transfer medium [25]. The following formula is used
to determine the total amount of thermal energy stored or released in 2.2. Classifications, properties, and challenges of PCMs
latent TES storage [25]:
⎛T ⎞ 2.2.1. Classification of PCMs according to phase transition
∫m ∫Tf
] Fig. 3 depicts the most common types of PCM transformations. Each
Qlatent = M ⎝ cp , s(T)dT + Hs − l + cp , l(T)dT ⎠, (3)
transformation is described briefly in the sections that follow.
Ti Tm

2.2.1.1. Liquid-gas transitions. The combination of TES with liquid-gas

where cp,sandcp,l are the material’s specific heat in solid and liquid states,
PCMs began in the 1970s. White et al. [36] investigated the use of a
respectively. The latent heat of fusion (J/kg) is denoted by Hs − l and the
transcritical CO2 heat pump to heat water to temperatures greater than
melting temperature is denoted byTm. It is worth mentioning that Eq. (3)
65 ◦ C while providing refrigeration at less than 2 ◦ C. The results showed
emphasizes the importance of selecting a material with an appropriate
mass, a high specific heat capacity, and a high heat of fusion to store
larger amounts of thermal energy.
Latent TES has attracted the attention of developers of storage sys­
tems due to its high energy storage per volume, which is approximately
5− 14 times that of sensible TES. To store the same amount of energy,
studies have shown that rocks (as a sensible TES material) require more
than seven, five, and eight times the storage volumes of paraffin wax
#116, medicinal liquid paraffin, and Na2SO4.10H2O (as latent TES
materials), respectively [26,27]. This is a result of the high heat capacity
of PCMs, which is reflected in their smaller storage volume requirements
[28].
PCMs can be organic, inorganic, or eutectic (details are presented in
Section 2.2.2). They are available in a variety of melting temperatures
and fusion enthalpies. PCMs can be classified according to their range of
melting temperatures. Low melting-point materials, such as paraffin
Fig. 3. Phase transformations in solid-liquid, liquid-gas, and solid-solid PCMs.

5
S.A. Albdour et al.
a linear increase in the heat transfer rate of the gas cooler and recu­
perator with increasing CO2 mass flowrate. Moreover, the heat capacity
was increased by 20% while using CO2 without lowering the coefficient
of performance. For application in solar-thermal systems, several types
of refrigerants such as HFC, CFC, and HCFC were adopted as HTFs [37,
38]. Solar-thermal collectors were more efficient than conventional
water-based collectors in the studies mentioned previously. While the
liquid-gas transformation has the highest latent heat of phase change, it
is difficult to use due to the presence of environmentally hazardous
substances. The enormous volume change during evaporation leads to
complexity of system design and installation, particularly regarding size
of the thermal storage containers and heat exchangers. This is in addi­
tion to the necessity of pressurized containers to store gas-phase species
[39]. Therefore, liquid− gas PCMs are considered impractical and not
commercially viable [40].
2.2.1.2. Solid-solid transitions. In solid− solid transformations (also
referred to as solid-state transformations), the material can retain its
solid bulk properties while changing from one crystalline or semi-
crystalline phase to another. As a result, it avoids the leakage problem
that is commonly observed in other types of PCM transformations. Solid-
solid PCMs also exhibit a small volume change during transition, which
increases their durability during thermal cycling. Because of these
properties, the materials can be used in practical applications and mixed
with other materials without needing to be encapsulated. Different
solid-solid PCMs exhibit a variety of phase transitions depending on
their chemistry and molecular structure, resulting in a wide range of
enthalpies, phase transition temperatures, and thermal conductivity
values. Based on their molecular structure, solid-solid PCMs are classi­
fied as polymeric, organic, organometallic, or inorganic [40].
Interestingly, when solid-solid PCMs undergo phase transitions, their
transparency changes. This interesting property may be exploited to
create a low-cost thermochromic system. For example, Guldentops and
van Dessel investigated the effect of using a thin layer of polymeric solid-
solid PCM in a solar-passive building enclosure [41]. The polymeric
material was used as a coating material on an exterior façade that is
highly reflective. At low outdoor temperatures during the winter, the
polymeric material was crystalline and opaque. Consequently, it
reduced the heating load by absorbing solar radiation at the outer sur­
face. On the other hand, the polymeric material became amorphous and
transparent during the summer season at high outdoor temperatures;
thus, it reduced the cooling load by allowing the reflective layer to
reflect solar radiation. It is worth mentioning that many solid-liquid
PCMs undergo transparency changes; however, leakage issues of the
liquid phase restrain their direct use in exposed-surface applications.
PCMs have a low thermal conductivity, which is one of their major
drawbacks. Solid-solid PCMs can overcome this shortcoming by
absorbing heat through radiation. Radiation penetrates the surface of
the material and gradually converts to heat as it penetrates deeper into
the material. Low thermal conductivity may be advantageous in this
case because it allows heat to be retained inside the material for a longer
period of time [40]. The quantity of heat emitted during the phase
change, on the other hand, is substantially lower than that generated
during other types of transformations [33].
2.2.1.3. Solid-liquid transitions. Solid− liquid PCMs have recently
sparked increased practical interest in latent TES systems due to their
high thermal storage capacity, relatively low volume change during
phase transition, and nearly constant phase-change temperature [42].
Fig. 4 presents the transformation concept of solid-liquid PCMs. The
course of the melting process begins as the temperature of the material
increases as it absorbs heat until the transition temperature is reached.
During this stage, the PCM behaves as a sensible TES material in the
solid phase. However, once the phase transition temperature is reached,
heat is exclusively used to change the phase of the material without
6
Progress in Energy and Combustion Science 93 (2022) 101037
Fig. 4. Schematic illustration of the working concept of solid-liquid PCMs.
While charging, the PCM stores energy as it transitions from solid to liquid,
whereas during discharging, the PCM releases energy as it transitions from
liquid to solid.
changing its temperature—an isothermal process. At this point, the
material changes its ordered crystalline structure to become a disor­
dered amorphous structure. Molecules then have enough energy to
break the supramolecular bonds while randomly moving around,
resulting in a randomly oriented liquid phase. Finally, the PCM returns
to its role as a sensible TES material, but this time in liquid form. The
entire process is referred to as charging, where the material stores
thermal energy.
In general, four hierarchically distinct regions occur during the
melting process of a PCM: (1) pure conduction, (2) mixed conduction
and natural convection, (3) dominant natural convection, and (4)
shrinking solid [43]. When the source of heat is removed, the material
gradually releases the stored latent and sensible heat via a process called
discharging. The temperature of melted PCM first drops to the freezing
point while remaining in liquid phase (sensible heat release) and then
starts to solidify (latent heat release), causing molecules to rearrange to
form a crystalline lattice. The type of molecule, rate of cooling, and
contaminants that act as nucleation agents all influence the shape and
number of crystals [40]. If further heat is released, the material tem­
perature further drops while remaining in solid phase (sensible heat
release).
The terms "charging" and "discharging" refer to the melting and so­
lidification processes of PCM, respectively. This is because heat is
effectively stored in and released from a PCM during melting and so­
lidification, respectively. Thus, in this scenario, the desired form of en­
ergy is heat. In some applications, however, such as air conditioning, the
desired form of energy is actually cold. Thus, during solidification, cold
energy is stored and released from the PCM during melting. In this
context, the terms "charging" and "discharging" refer to solidification
and melting, respectively. Thus, for the sake of clarity and generaliza­
tion, the term "charging" refers to melting, which is directly proportional
to the amount of heat gained or cold released by the PCM, and the term
"discharging" refers to solidification, which is directly proportional to
the amount of heat released or cold gained by the PCM.
2.2.2. Classification of PCMs according to material
A wide range of PCMs have been studied to develop efficient TES
solutions. PCMs are classified as organic, inorganic, or eutectic
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

according on their chemical composition [44], as shown in Fig. 5. Table 2

Table 2 displays the melting point and enthalpy of fusion of selected Thermal properties of selected PCMs.
PCMs from the previously mentioned categories. Category of PCM Molecular Melting Enthalpy Ref.
formula point of fusion
2.2.2.4. Organic PCMs. Organic PCMs are generally used in low- (◦ C) (kJ/kg)

temperature applications. In general, these materials have a high Organic Paraffin CH3 (CH2)10 CH3 − 10 216 [45]
latent heat of fusion, generate little vapor pressure during phase tran­ CH3 (CH2)11 CH3 − 5 160 [45]
CH3 (CH2)14 CH3 18-19 237 [45]
sitions, and self-nucleate with minimal supercooling. Furthermore, they
CH3 (CH2)16 CH3 28 242 [45]
survive repeated thermal cycling (cycles of charging and discharging) CH3 (CH2)18 CH3 36-37 247 [45]
without phase separation, i.e., the material melts and solidifies Non- CH₂O₂ 7.8 247 [45]
congruently. Organic PCMs have good compatibility with other mate­ Paraffin C8H16O2 16.3 149 [45]
rials, a suitable weight, no toxicity, and are environmentally safe. CH3(CH2)10COOH 49 178 [45]
CH3(CH2)13COOH 52.5 178 [45]
However, widespread use has been hampered by several shortcomings, CH3(CH2)16COOH 69.4 199 [45]
including significant volume change during the phase transition, low Inorganic Salts AlCl3 192 280 [28]
thermal conductivity (about 0.2 W/m•K) [44], and worst of all, the LiH 699 2678 [28]
leakage problem (more on this problem in Section 2.2.4). Organic PCMs LiF 849 1041 [46]
MgF2 1263 938 [46]
are further divided into two categories: paraffin and non-paraffin.
BaSO4 1680 175 [46]
Paraffin wax is regarded as a representative material of the paraffin Salt Na2P2O7⋅10H2O 70 184 [28]
group. It is a mixture of pure alkenes (CnH2n+2) and a synthetic chain hydrates Ba(OH)2⋅8H2O 78 266 [28]
consisting of n-alkanes (CH3-(CH2)-CH3). The amount of latent heat H12MgN2O12 89 140 [47]
released is determined by the crystallization of the CH3 chain. As the Mg(NO3)2⋅6H2O 89.3 150 [47]
MgCl2⋅6H2O 117 169 [47]
amount of carbon increases, the melting point of paraffin wax also in­ Metals Cu 1083 193.4 [28]
creases. Typically, paraffin wax has the same properties as pure alkanes. and alloys Al 660 397 [28]
However, the melting point is the average of all the melting points of Al− Cu 548 372 [28]
existing alkanes. Commercial paraffin wax has been shown to be ther­ (66.92:33.08 wt%)
Cu− Zn− P 720 368 [28]
mally stable after as many as 1500 thermal cycles [60]. Unlike paraffin
(69:17:14 wt%)
wax, non-paraffin PCMs have a broader range of properties. The most Al− Si (20:80 wt%) 585 460 [28]
recognizable PCMs in this category are fatty acids, which typically have Eutectic Organic- C12H24O2 / 18-24 140.8 [48]
an enthalpy of fusion comparable to that of paraffin wax. Fatty acids also organic C10H20O2 (35:65
exhibit reproducible melting and freezing behavior without super­ wt%)
C12H24O2 / 37.0 182.7 [49]
cooling [61].
C18H36O2
(75.5:24.5 wt%)
2.2.2.5. Inorganic PCMs. As illustrated in Table 2, inorganic PCMs have C12H24O2 / 21.3 151.5 [50]
a much higher enthalpy of fusion than organic ones. On the one hand, C14H30O (40:60 wt
%)
they have the advantages of high thermal conductivity, non-
C10H20O2 / 22.89 144.92 [51]
flammability, low cost, and most importantly, a high melting point. C16H34O (70:30 wt
On the other hand, they are subject to corrosiveness, phase segregation, %)
significant volume changes during phase transition, a high degree of C133H267N2O55P / 54 185 [52]
H(OCH2CH2)nOH
supercooling, and thermal and chemical stability issues. Salt hydrates
(20:80 wt%)
and metallic alloys are the two major categories of inorganic PCMs. Organic- Mn(NO3).6H2O 15-25 125.9 [53]
Salt hydrates have been extensively researched, and some are inorganic /MgCl2.6H2O
already commercially available [62]. They have the general formula CaCl2 / MgCl2 / 25 95 [54]
MxNy.nH2O, where MxNy is a metal carbonate, chloride, sulfate, phos­ 6H2O (50:50 wt%)
Ca(NO3)2⋅6H2O / 25 130 [54]
phate, or nitrite, and n is the number of water molecules [61]. For any
Zn(NO3)2 (45:55
salt hydrate, ion-dipole bonds or H-H bonds exist. The former consists of wt%)
an ion with a polar molecule. During phase transition, heat is absorbed LiNO3⋅3H2O / Zn 17.2 220 [55]
when the salt hydrate loses some or all of its water molecules (dehy­ (NO3)2.6H2O
(45− 52:48− 55 wt
dration), as shown in Eq. (4),
%)
Mx Ny ⋅nH2 O→Mx Ny ⋅mH2O + (n − m)H2 O. (4) C16H36BrN / 9 187 [56]
Na₂(B₄O₅(OH)₄)⋅
8H₂O (40:2 wt%)
Inorganic- LiOH / NaNO3 / 230 184 [57]
inorganic NaOH (6:67:27 wt
%)
LiNO3 / KNO3 133 150 [58]
(34:66 wt%)
KNO3 / KOH 214 83 [59]
(80:20 wt%)
LiCl / LiNO3 (9:91 244 342 [47]
wt%)
NaNO3 / NaOH 250 160 [59]
(86:14 wt%)

Similarly, heat is liberated when the salt hydrate gains water mole­
cules (hydration), as shown in Eq. (5),
Fig. 5. Classification of PCMs according to material into organic, inorganic, Mx Ny ⋅nH2 O→Mx Ny + nH2 O. (5)
and eutectic.

7
S.A. Albdour et al.
Another type of inorganic PCMs is metallic alloys. They have a high
latent heat of fusion per unit volume, better thermal conductivities than
most other PCMs, and a low vapor pressure during phase transition. Yet,
they saw little development as PCMs due to their high weight.
2.2.2.6. Eutectic PCMs. To attain a desired melting point, eutectic PCMs
are composed of two or more organic-organic, organic-inorganic, or
inorganic-inorganic PCM components. Eutectic PCMs consistently so­
lidify without segregation at temperatures typically lower than those of
their constituting components [44]. Unfortunately, they generally suffer
from foul odor, low thermal conductivity, high cost, and insufficient
available data on their thermophysical characteristics.
2.2.3. Desired properties and aspects in PCMs
Fig. 6 summarizes the desired physical, thermal, kinetic, economic,
safety, and technical characteristics to be considered when selecting a
PCM for TES. While some of these criteria are simple to manage, others
are regarded as serious defects, making most bulk pure PCM systems
unsuitable for direct use. As a result, while choosing a PCM for a certain
application, consideration should be given to both short- and long-term
behavior, as well as storage medium requirements.
2.2.4. Key challenges facing PCMs
This section presents a compilation of the most critical challenges
impeding PCM research and development efforts.
Poor thermal conductivity. The degree of success of latent heat storage
technology can be determined by the speed and quality of the charging
and discharging processes, which are correlated with the heat transfer
process from the surface to the innermost part of the PCM. Generally,
heat transfer can take place through conduction, convection, or radia­
tion. Thermal conduction has been confirmed as the primary mode of
heat transfer in a material (solid, liquid, or gas) without bulk motion.
The heat conduction process is a stochastic process through matter, and
this stochasticity produces a temperature gradient.
Fig. 6. Classification of the desired characteristics in PCMs into physical, thermal, kinetic, technical, economic, and safety properties and aspects.
8
Progress in Energy and Combustion Science 93 (2022) 101037
Conduction can be used to transfer heat during the early stages of
melting and solidification, while convection currents dominate in the
mushy zone. The poor thermal conductivity of a PCM decreases the rate
of heat storage and extraction during melting and solidification cycles,
and thus, the PCM’s overall power. Therefore, it is a critical factor to
consider while designing the latent heat storage system. The majority of
the data on PCM thermal conductivity that is available was obtained
experimentally. However, there is a lack of clarity in the theoretical
understanding of heat conduction through solid and liquid PCMs (details
are presented in Section 4.3).
Supercooling. Theoretically, the melting and freezing temperatures of a
PCM should be the same. However, most PCMs have solidification
temperatures lower than their melting temperatures. This is a phe­
nomenon known as "supercooling". When a PCM starts to solidify, it is
supposed to completely change its phase from liquid to solid by reducing
its temperature slightly below the solidification temperature (freezing
point), allowing the material to latently release thermal energy. Under
supercooling, the PCM can cool down to well below the solidification
temperature while still remaining in a liquid state (partial or no
freezing), as shown in Fig. 7. In other words, the PCM does not reach the
minimum temperature required for nucleation to start. Mathematically,
the degree of supercooling (also known as phase-change hysteresis) is
calculated by subtracting the freezing temperature from the melting
temperature [40]. It is also possible to express supercooling as follows
[63],
( )[ ]
4 Tm
Tsc = γo , (6)
3 (ρs Hs− l Rcr )
where γo is the surface free energy per unit area, Hs − lis enthalpy of
fusion, ρsis the solid density, and Rcr is the critical radius of solid nuclei.
Numerous variables can affect the supercooling of PCMs. The degree
of supercooling is definitely increased if the bulk volume is divided into
microscopic particles through encapsulation or an emulsion process,
S.A. Albdour et al.
Fig. 7. Schematic illustration of the phenomenon of supercooling (point 1
represents the start of the melting process, point 2 represents the completion of
the melting process and the initiation of the solidification process, and point 3
denotes the solidification process with supercooling effect).
because each capsule will have an insufficient number of impurities
[63]. Adachi et al. [64] reported that by decreasing the volume of
erythritol as a PCM from 16 to 0.025 cm3, a 60 ◦ C increase in the
supercooling degree took place.
The consequences of this process appear clearly in terms of the
thermal energy released during solidification that is converted to useful
energy. Generally, supercooling can cause two problems [65]. First,
there is a chance that the new freezing temperature will not be within
the temperature control range of the system. The system should function
within a specified temperature range for temperature control applica­
tions. If the risk of nucleation is 50% at 40◦ C but 90% at 25◦ C, the system
should be engineered to operate at a 15◦ C lower temperature, increasing
the system’s cost and inefficiency. Second, energy consumption will be
increased to reach the solidification temperature. Additionally, there is a
possibility that the PCM will not freeze fully, preventing stored heat
from being completely released. This is more common when the HTF
temperature is near the freezing point, as the random nature of super­
cooling complicates control of the latent TES system. Furthermore, if
nucleation and freezing do not occur during the next thermal cycle,
energy will be absorbed solely through sensible heating. Therefore,
temperatures can rise significantly above the allowable value. Thus, a
critical failure is expected for the whole system. It is worth mentioning
that several studies have shown that the solidification temperature is
affected by additives such as nucleation agents [61].
High volume change. According to the literature, most PCMs experience
a volume increase during phase transition, which cannot be neglected
and must be considered during the design of thermal storage containers
and heat exchangers. For instance, experiments have shown that three
distinct sets of transformations can be identified when paraffin wax is
heated, each with a different rate of volume change. As shown in Fig. 8,
in the first and third stages, the increase in temperature is accompanied
by an increase in sensible energy with relative volume changes of 2 and
3%, respectively. In the second stage, paraffin destroys its original
structure and changes from a compact structure to a less compact one
[66]. It expands by approximately 11% of its original volume within the
transition temperature range (50 − 70◦ C) [53], which is in good
agreement with other values found in the literature [67, 68]. Moreover,
many salts and salt composites (e.g., lithium fluoride) incur significant
volume changes that often exceed 10% and can reach up to 45% of their
9
Progress in Energy and Combustion Science 93 (2022) 101037
Fig. 8. Relative volume change of paraffin wax before (1st stage), during (2nd
stage), and after (3rd stage) phase transition as a function of temperature.
Within the transition temperature range (50− 70◦ C), the PCM expands by nearly
11% of its initial volume.
original volume [46].
Phase separation. Typically, the terms "phase separation" and "incon­
gruent phase melting" are used synonymously. Each time the PCM melts
incongruently, new solid and liquid phases with distinct compositions
precipitate from the original composition. As a result of the density
differential, some of the solid material settles to the bottom of the
container. The phase-transition process becomes irreversible as a result
of this process and further cycling diminishes the latent storage density.
The new compositions may, in extreme cases, have different melting and
solidification points than the original mixture. The material is unable to
participate in subsequent melting and solidification cycles when these
new compositions reach the charging and discharging temperatures, and
the latent TES drops to zero [69]. As a result, storage capacity declines
unless the temperature range is changed and the original composition is
restored.
PCM leakage. PCM leakage in liquid state is frequently encountered
during the solid-liquid phase transition. As a result, bulk PCM systems
are unreliable in actual applications. This problem limits the efficient
use of the latent heat of fusion for two reasons. First, when the leakage
occurs, it reduces the volume fraction of the participating PCM, which in
turn reduces the latent heat of fusion. Second, the leaking PCM can cause
contamination or damage to the surroundings. Leakage can be avoided
or decreased by encapsulating [70] or entrapping the PCM in porous
structures using a number of strategies [71]. Physical adsorption [72],
chemical bonding [73], or ionic cross-linking [74] between the PCM and
the supporting material are all examples of such strategies. However, it
is reported that during mechanical mixing of encapsulated PCMs with
concrete for building applications, PCMs can leak from the concrete as a
result of some of the PCM capsules breaking [75].
The moving-boundary problem. Predicting a PCM’s thermal behavior
during melting and solidification is deemed difficult due to the intrinsic
nonlinearity of the moving interface that separates the solid and liquid
phases during phase transition. As a result of this issue, predicting flow
and heat transfer parameters in a reliable manner is extremely difficult.
Thus, analytical solutions are only available for the 1D case with very
simplified boundary conditions. The rate at which the moving interface
displaces itself is determined by the amount of latent heat lost or
absorbed at the boundary. The Stephan condition describes this
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

procedure, which is expressed as follows [57]:
( ) ( ) ( )
ds(t) δTs δTl
Hs− l ρ = ks − kl , (7)
dt δt δt
where Hs − lis the latent heat of fusion, ρ is density (without specifying
the phase), the surface position is denoted by s(t), T is temperature, t is
time, k is thermal conductivity, and the subscripts s and l refer to solid
and liquid phases, respectively.
The position and velocity of this boundary are unknown in advance.
Numerical simulation of the PCM during phase transition is often carried
out using computational packages (e.g., COMSOL Multiphysics, ANSYS-
FLUENT, Star-CCM+) within a specific temperature range. Making
appropriate assumptions is a typical strategy to simplify the moving-
boundary governing equations. Incompressible flow, constant density
or a linear density-temperature relationship using the Boussinesq
approximation, a negligible density difference between two phases,
and/or negligible internal thermal radiation are among the common
assumptions [76]. Because Josef Stefan was the first to report this
problem, it is often referred to as the "Stefan problem" [77].
Flammability. From surveying the literature, and despite the absence of
a proper fire assessment standard, PCM flammability was usually either
not specified or claimed to be zero or low [70]. To the best of the au­
thors’ knowledge, paraffin wax and fatty acid as organic PCMs are the
only investigated materials in building applications as a fire hazard [78].
Introducing flame retardant stabilizers such as silicon and magnesium
hydroxide is a suggested solution to overcome this problem [79].
2.3. An overview of PCM systems
2.3.1. Bulk PCM systems
PCM containers. In bulk PCM systems, the most important aspects to
consider after selecting a PCM are the size and geometry of the
container. The design of a PCM container has a great influence on the
level of heat exchange between the HTF and PCM, ultimately affecting
the melting/solidification rate and storage capacity in bulk PCM systems
[56]. As shown in Fig. 9, cylindrical, rectangular/square flat, and
spherical are the container configurations used in bulk PCM storage
systems [80]. The cylindrical geometry includes three key designs: pipe,
cylindrical, and shell-and-tube, as shown in Fig. 9. The pipe design is
distinguished by filling the shell with the PCM while the HTF flows
through a single-core pipe. In the cylindrical design, the PCM fills the
inner core pipe and the HTF flows through the outer shell. The
shell-and-tube model is divided into three classes based on the flow
orientation of the HTF: internal flow, parallel flow, and cross flow, as
illustrated in Fig. 9.
Several researchers [81] compared the pipe and cylindrical designs
based on the radius of the cylinder, inlet temperature, total volume of
PCM, and mass flow rate of the HTF. Results showed that the pipe model
had a shorter melting time, which was explained by the fact that the
thicker the mass of the PCM (in the radial direction), the longer the
required melting time. Moreover, since most of the heat provided by the
center in the pipe model is used to heat the surrounding PCM, this
container design has a lower rate of heat loss to the environment [80].
Agyenim et al. [82] compared a horizontal shell-and-tube heat
exchanger with four tubes to a pipe design. The used PCM had a melting
temperature of 117.7 ◦ C and belonged to the medium-temperature
range. Temperature gradients in the two systems’ axial, radial, and
angular directions were investigated and compared. Convection was
shown to be the dominant mode of heat transfer in the shell-and-tube
system, whereas conduction was found to be the dominant mode of
heat transfer in the pipe model. As a result, the authors recommended
using a shell-and-tube configuration for the charging process and
highlighted the need for future research into the shell-and-tube
approach because the solid-liquid interface was significantly altered
by forming multiple convective cells. Seddegh et al. [83] investigated
the optimal diameter ratio between the shell and tube by balancing the
amount of stored energy with the corresponding melting time. Their
findings revealed that the optimal ratio was around 5.4, which reduced
melting time by 68%.
Zhao et al. [84] used a digital camera to investigate the melting
process of n-octadecane within a rectangular container at seven tilt
angles (0, 15, 30, 45, 60, 75, and 90◦ ). The shortest melting time was
recorded at 60o, showing that free convection had a strong potential to

Fig. 9. Classification of the structure and design of commonly used PCM containers. This includes a) pipe, b) cylinder, c) shell-and-tube (subclassified based on the
flow direction of the HTF with respect to the PCM into internal, parallel, and cross flow designs), d) rectangular/slab, and e) spherical containers.

10
S.A. Albdour et al.
improve the heat transfer rate of the PCM. Other researchers [85]
numerically investigated the discharging process of erythritol in a
spherical container with 10, 20, 30, and 40 mm diameters with a solid
PCM content of 98.5%. The wall was heated to 10, 15, 20, 25, 30, and 40
K, all of which were lower than the phase-change temperature. The re­
sults revealed that the diameter of the container and the difference be­
tween wall temperature and phase-change temperature had a significant
effect on the liquid fraction and solidification time.
Melting behavior of PCMs inside containers. Before the PCM melting
process begins, the container is typically filled with a PCM with a
melting temperature of Tm and a portion of the volume is a gas void. At
an initial temperature of Ti < Tm, the PCM is assumed to be in the solid
phase. The initial location and volume of the gas void are determined
primarily by the gravitational field and the geometry of the container.
The container must then be heated to melt the PCM. This can be
accomplished via isothermal heating or by providing a constant heat-
flux. When heating is initiated, the solid phase melts adjacent to the
hot boundary, expanding the volume of the liquid region. When the PCM
reaches its melting point, an evolving solid-liquid interface forms and
the liquid-phase zone expands. Convection currents form within the
liquid phase, which are governed by the spatial extent of the liquid area
occupied, the temperature gradient within the liquid phase, and the
orientation of the gravitational field [86].
The melting process of PCMs inside a spherical, rectangular, or cy­
lindrical shell is classified into two categories: constrained and uncon­
strained melting. Constrained melting (also known as fixed or inward
melting) is unavoidable during experimental investigations due to the
positioning of thermocouples inside the container. The thermocouples
retain the solid phase, preventing it from sinking to the bottom or rising
to the top as a result of the density difference between the liquid and
solid phases. In effect, there is no direct contact of the solid PCM with the
wall of the container. However, in the absence of thermocouples and a
density difference between the liquid and solid phases, constrained
melting will continue to occur [86]. In contrast, unconstrained melting
(also known as unfixed or close-contact melting) occurs when there is no
anchor inside the container. As a result, the solid phase can move up and
down in response to the density difference, resulting in direct contact of
the solid PCM with the wall of the container [87].
Two heat transfer mechanisms, heat conduction and natural con­
vection, drive the melting process in the constrained model. First, heat
conduction between the heated container wall and the adjacent PCM is
associated with a high heat transfer rate and significant melting rate
during the early stage. Then, as time goes on, the area occupied by the
melted liquid increases. Thus, natural convection dominates, lowering
the heat transfer rate, decreasing the melting rate, and increasing the
charging time. The strength of the buoyancy-driven convection flow is
determined by the position of the heat source, the imposed boundary
conditions, and the thermophysical properties of the PCM. In contrast, in
the unconstrained model, the solid PCM continuously touches the
enclosure wall, resulting in increased heat transfer and melting rates.
Thus, for the same geometrical and operating conditions, unconstrained
melting demonstrates a faster melting rate than constrained melting
[86].
Tan [88] investigated constrained and unconstrained melting inside
a sphere at different initial wall temperatures and sub-cooling degrees.
Results showed that in unconstrained melting, heat conduction is
dominant at the beginning, then after the PCM begins to melt, it sinks to
the lower portion of the sphere. This movement creates pressure in the
liquid PCM. As a result, the warm liquid PCM between the solid PCM and
the inner walls is forced to rise and replace the cold liquid PCM. This
phenomenon boosts natural convection in the top half of the sphere
container. Melting continues to be faster in the bottom half than in the
top half due to the larger influence of heat conduction at the inner wall.
For constrained melting, heat conduction occurs only during the initial
11
Progress in Energy and Combustion Science 93 (2022) 101037
stages of melting, followed by natural convection. However, heat con­
duction is weaker relative to unconstrained melting. The difference
between the two modes of melting is illustrated in Fig. 10.
Sattari et al. [89] showed that, compared with the initial tempera­
ture of the PCM and size of the spherical container, the temperature of
the container wall was the factor controlling the heat transfer and
melting rates the most. Sparrow and Geiger [90] studied melting in a
horizontal tube and showed that the melting mass in the constrained
mode was lower than the unconstrained one. Additionally, they
demonstrated that unconstrained melting exhibits 2-D behavior,
whereas constrained melting exhibits 3-D behavior. Jianhua et al. [91]
examined the melting of n-octadecane in a rectangular chamber heated
from below by three separate heat sources. The temperature of the
surface was measured with thermocouples, and the mobility of the solid
and liquid phases was photographed. Constrained melting was observed
in the solid between the heaters, while unconstrained melting was
simultaneously observed above the heaters. Experimental findings
revealed that the larger the aspect ratio of the container, the more
rapidly melting proceeded and the more frequently unconstrained
melting occurred. Initial subcooling had an effect on the melting process
during the very early stages but vanished once the melting process
approached the unconstrained melting stage.
Thermal performance of bulk PCM systems. To effectively predict the
thermal performance of a PCM system, it is vital to have a thorough
understanding of the fundamental heat transfer processes. Numerous
correlations have been developed based on experimental and numerical
studies of the thermal characteristics of latent TES systems, including
liquid volume fraction, melting time, equivalent thermal conductivity,
temperature profile, and melting rate. Dimensionless numbers have
frequently been used in developed correlations to gain some universality
from the findings of each study and to extend these findings to subse­
quent studies [80]. Table 3 covers the most frequently used dimen­
sionless numbers in PCM research. Table 4 presents some of the reported
correlations for the melting and solidification processes of PCMs based
on these dimensionless numbers. It is worth mentioning that there is no
available study that correlates the available data since different authors
used different PCMs with different heat transfer features. Agyenim et al.
[80] used the same PCM, however, they implemented dimensionless
numbers within different ranges. Moreover, some researchers presented
their correlations without explicitly defining their adopted dimensional
numbers, making it impossible to further develop their research outputs.
Commercially available PCM suppliers. Table 5 presents a list of selected
commercial PCM manufacturers around the world.
2.3.2. PCM systems with extended surfaces
The incorporation of fins into PCM systems is an efficient method of
boosting the heat transfer area and rate. Owing to their ease of
manufacturing and low cost, many studies have been conducted on the
performance of fins in PCM systems [80]. The fin material is chosen
based on its thermal conductivity, density, cost, and corrosion resistance
[99]. High-conductivity materials are often used, including stainless
steel, carbon steel, graphite foil, aluminum, and copper, with thermal
conductivities of 20, 30, 150, 200, and 250 W/m•K, respectively [99].
A wide variety of fin structures are used in PCM-based heat ex­
changers, including longitudinal, radial/circular, and pin fins. The lon­
gitudinal and radial/circular configurations of fins are most commonly
used in high-temperature shell-and-tube devices [100]. Their configu­
rations are shown in Fig. 11. The main advantages of using annular fins
are their ease of design and manufacturing. However, several studies
have demonstrated that longitudinal fins outperform annular fins in
terms of performance because the former do not inhibit natural con­
vection during melting and thus aid in the solidification process. It is
critical to keep in mind that the use of fins should not obstruct or restrict
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 10. A schematic showing the heat transfer modes in a) unconstrained and b) constrained melting. In constrained melting, the solid part of the material does not
touch the container wall directly. In unconstrained melting, the solid part is in direct contact with the container wall.

duration of eight h. Relative to annular fins, results showed that longi­

Table 3
tudinal fins enhanced conduction and convection with a completed
Common dimensionless numbers used in the analysis of phase-change problems.
melting process. Moreover, the amount of charged energy was found to
Dimensionless Equation Definition Ref. be lower with annular fins.
number
Other authors employed numerical simulations (based on the
Stefan number Ste = Ratio of sensible heat to latent heat.
[2] method of finite volume) to understand the effects of the number of fins,
Cp(Tf − Ti)
fin height, and fin thickness on a vertically-finned PCM tube [102].
ΔH
Nusselt number hl Ratio of convective to conductive [92] Results showed that inserting annular fins into the PCM could reduce the
Nu =
k heat transfer across a boundary. It total melting time by 65%. To maximize thermal performance, the op­
determines the actual heat transfer timum fin parameters were as follows: the number of fins was 31, the
rate.
ratio of fin thickness to tube length was 0.0248, and the ratio of fin pitch
Biot number hl Ratio of convective to conductive [93]
Bi =
k heat transfer inside the body. It to tube length was 0.0313.
determines uniformity of
temperature in solid media. 2.3.3. Cascade PCM systems
Rayleigh number gβΔTl3 Determines the regime of natural [92]
Ra = The primary disadvantage of employing a single bulk PCM in a TES
αv convection. Below a critical value,
heat transfer is mainly by
system is the length of time required for charging and discharging. To
conduction. overcome this issue, one approach is to use latent heat storage in
Grashof number
Gr =
gβΔTl3 Approximate ratio of buoyancy [94] conjunction with various PCMs with varying melting temperatures. To
v3 forces to viscous forces. understand the motivation behind this method, let us consider the shell-
Prandtl number v Ratio of momentum diffusivity to [92]
Pr = and-tube model discussed in Section 2.3.1.1. The temperature differ­
α thermal diffusivity.
Reynolds DV Ratio of the inertial forces to viscous [94] ential between the HTF and the phase-change temperature of the PCM
Re =
number μ forces. affects the charging and discharging processes. During the charging
Fourier number Fo =
α A measure of heat conducted [95] process, the HTF enters the tube at a temperature significantly above the
(l2/t) through a body relative to heat melting temperature of the PCM, causing the PCM to rapidly melt. The
stored within it.
temperature differential between the PCM and HTF, on the other hand,
decreases along the axial flow direction.
natural convection during the melting process [100]. Despite this, The temperature difference is largest near the entry section and
employing fins in a shell-and-tube device will always influence the total lowest near the exit section. As a result, the amount of melted PCM near
amount of PCM that can be placed in the annular space, reducing the the entry section would be greater than in the exit area, resulting in a
total storage capacity. Thus, as a compromise, the number of fins and spatially non-uniform melting process throughout the tube. During the
their dimensions should be carefully considered so as to balance the discharging process, the HTF enters at a temperature lower than the
enhancement in heat transfer with the amount of stored energy. freezing point of the PCM, gaining heat from the PCM. The temperature
A comparison has been made to compare the effects of longitudinal of the HTF rises as it flows along the axial direction; therefore, the
and radial/circular fins when implemented in a horizontal shell-and- temperature difference between the HTF and PCM falls. Similar to the
tube PCM heat exchanger [101]. In the comparison, eight copper fins charging process, this results in non-uniform solidification. This het­
were used with a thickness of 0.001 m for each type. The length of the erogeneity during the charging and discharging processes frequently
longitudinal fins was 0.95 m and the diameter of the circular fins was results in a delay in the overall melting and solidification times [102].
0.134 m. An amount of 20.2 kg of erythritol PCM was used irrespective According to studies, replacing a single bulk PCM with multiple
of fin geometry. The comparison was held in terms of the melting time PCMs arranged in decreasing or increasing order (based on the type of
and charged energy under the same operation conditions for a fixed storage, hot or cold) in terms of their phase-change temperature and

12
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Table 4
A selected number of derived correlations for melting and solidification pro­
cesses using dimensionless numbers.
PCM Derived correlation Explanation of Ref.
geometry the correlation

Rectangle V/Vi = 4.73Fi0.906Ste1.538Ra0.002 Melting volume [92]

fraction
Time-averaged
Nu =
Nusselt number
( )
H for the entire
0.0219Ra0.387Pr0.0191 0.0621
δ melting process
Where,
8.56 × 106 ≤ Ra ≤ 4.78 × 107
804 ≤ Pr ≤ 1055
δistheaverageinterfacelocation
Horizontal [ d(τ)]1/4 Equivalent [96]
keq (τ) = 0.22∅Ra(τ)1/4 1 −
cylinder D thermal
conductivity
∫τ Dimensionless
A(τ)[1 − ln(A(τ))] = 1 − 4 keq(τ)dτ melting rate (1-A
0 (τ))
Fig. 11. a) Longitudinal and b) radial/circular fins employed in shell-and-tube
Where,
9.62 × 106 ≤ Ra ≤ 7.97 × 107 PCM-based heat exchangers.
d(τ) is equivalent diameter of the unmelted solid
∅ = 1 represents concentric cylinders and ∅ < 1 for the the PCM initiates and terminates its phase change simultaneously, the
melting process inside a cylinder
phase change rate is identical and constant throughout the phase-change
Concentric t* = 0.853 − 3.73 × 10− 5Ra − Melting time [97]
cylinders 0.04778(Ste/Tcon) process. For this reason, it is difficult to find a single bulk PCM that
Where, produces a parabolic or even linear temperature distribution profile.
3500 ≤ Re ≤ 8500 Fortunately, cascaded PCMs can approximate a parabolic temperature
0.3 ≤ Ste ≤ 0.65 profile. Moreover, compared with a single PCM, the melting time could
0.3 ≤ Tcon ≤ 0.4
Insulated − 2kΔT Average heat flux [98]
be decreased by 60, 50, and 33% for spherical, cylindrical, and flat-plate
q = [1 + (0.1210 + PCMs, respectively. Li et al. [104] investigated three cascaded PCMs for
slab, l
cylinder, 0.0424ω)St0.764] a shell-and-tube heat storage unit in a high-temperature solar-thermal
or sphere l2 Duration of the
tf = [1 + (0.25 + application. The chosen materials were K2CO3(51%)− Na2Co3(49%),
2α(1 + w)St melting process
0.17ω0.7)St] Li2CO3(20%)− K2CO3(20%)− Na2CO3(60%), and Li2CO3(32%)−
Q = qtf Total heat input Na2CO3(33%)− K2CO3(35%) for PCM1, PCM2, and PCM3 along the flow
per unit surface direction of the HTF with melting temperatures of 983, 823, and 670 K,
area respectively. Results revealed that the inlet temperature of the HTF (air)
Where,
and the length/amount of loaded PCM had a significant impact on the
0 < St ≤ 4
⎧
⎨ 0, for insulated PCM slab reduction of melting time for each PCM.
ω = 1, for PCM cylinder Li et al. [105] mathematically investigated the overall exergy effi­
⎩
2, for PCM sphere ciency of two cascaded PCMs for concentrated solar power (CSP) plants
based on finite-time thermodynamics. The effects of melting tempera­
tures and the number of heat transfer units for each PCM were investi­
gated. Exergy efficiency improved by 19.0-53.8% when two cascaded
Table 5 PCMs were used instead of a single bulk PCM. The authors recom­
Commercial PCM manufacturers around the world.
mended the PCM melting temperatures for application in CSP plants to
Trademark name/ PCM Website address(Accessed be 1000-1150 K for the first PCM and 750-900 K for the second one.
Manufacturer temperaturerange (◦ C) on Jun 20th, 2021) Michels and Pitz-Paal [106] investigated a cascaded TES system both
RUBITHERM − 3 to 100 www.rubitherm.eu experimentally and numerically for parabolic-trough CSP plants with
Mitsubishi Chemical 9.5 to 118 www.mfc.co.jp five alkali nitrate salt PCMs; namely, MgCl2/KCl/NaCl, KOH, KNO3,
TEAP − 50 to 78 www.teappcm.com
KNO3/KCl, and NaNO3 with melting temperatures of 380, 360, 335,
Doerken − 22 to 28 www.doerken.de
EPS Ltd − 114 to 164 www.epsltd.co.uk 320, and 306 K, respectively. Their investigation showed that the
Cristopia − 33 to 27 www.cristopia.com cascaded PCMs were more complex in a high-temperature range (more
Climator − 18 to 70 www.climator.com than 100 ◦ C). The authors also emphasized the importance of over­
SAVENRG − -20 to 100 www.rgees.com/products. coming the problem of low thermal conductivity in PCMs to fully utilize
php
this promising technology in CSP plants.

HTF flow direction enhances PCM melting near the inlet or exit
compared with a single PCM. Fig. 12 displays a typical cascaded PCM
TES system for cold and hot storage applications. During charging of the
hot storage system, PCMs are placed in descending order of melting
temperature along the flow direction of the HTF. The order is reversed in
the case of cold heat storage. However, it should be noted that replacing
a single PCM that has a high latent heat of fusion with a number of PCMs
with different properties can decrease the overall latent heat of fusion.
According to some studies [103], the phase-change process with a
parabolic temperature distribution profile is more homogeneous. Since
2.3.4. Emulsified PCM systems
Generally, an emulsion is a mixture in which insoluble substances are
dispersed in a continuous liquid phase with the help of surfactants. An
emulsion in which a PCM is dispersed in a continuous phase to form
droplets is known as an emulsified PCM system. Because of their higher
heat capacity than single-phase liquids and superior fluidity compared
to bulk PCMs, emulsified PCMs exhibit dual functionality; namely, en­
ergy storage and heat transfer [20].
Based on the dispersed phase and carrier liquid, emulsified PCMs are
classified into direct emulsion oil-in-water, inverse emulsion water-in-
oil, oil-in-oil, and multiple emulsions (W/O/W, O/W/O, W/O/O)

13
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 12. A typical cascaded latent TES system for hot and cold storage. In hot storage, during the charging process, PCMs are placed in descending order of melting
temperature along the flow direction of the HTF. For cold storage, the order is reversed. The desired form of energy output in hot storage is heat, whereas it is “cold”
in cold storage.

[107], as shown in Fig. 13. The last two types are the most complex in
terms of preparation. Oil-in-water emulsions have lower densities and
higher conductivities than water-in-oil ones, making them favorable for
reducing pumping power. Another classification is based on droplet size
[108], which can be controlled by the preparation method. According to
this classification, emulsified PCM systems can be grouped into macro­
emulsions with droplet diameters of over 1 μm, miniemulsions with
diameters in the range of 100 − 1000 nm, and microemulsions with di­
ameters of between 10 and 100 nm. The key to the thermodynamic
stability of an emulsion is maintaining very low interfacial tension at the
oil-water interface. Microemulsion droplets that spontaneously form
with the help of surfactants and mild agitation (the energy input is
negligible) are the only type that is classified as thermodynamically
stable [108]. This fact is explained by the main role of the surfactant/­
cosurfactant in lowering the energy required to increase the surface
area, i.e., low interfacial tension at the oil-water interface. After the
optimal amount of surfactant/cosurfactant is added, Gibbs free energy
becomes negative, which is below the free energy of the separate phases
(oil and water) [108].
Emulsion components. Typically, an emulsified PCM system consists of
paraffin oil-in-water and a surfactant [107]. The heat capacity of the
emulsion is increased by increasing the concentration of paraffin oil.
However, this does not have any impact on emulsion diameter [109]. A
surfactant is used to kinetically stabilize water and paraffin oil in the
emulsion as they are naturally unstable due to their immiscibility. Sur­
factants are structured to have two portions: a hydrophilic part that is
water attracting and a hydrophobic part that is water resisting. When a
surfactant is applied to a paraffin oil/water emulsion, it accumulates at
the paraffin oil/water interface, with the hydrophilic group facing water
and the hydrophobic group facing paraffin oil. Thus, surfactants act as a
protective layer between the droplet and the surrounding continuous
phase, preventing the droplet from breaking and reducing the interfacial
tension between oil and water. A low interfacial tension results in less
energy being required to create an emulsion [110].
Emulsion stability. Droplet size, dispersion, supercooling, and phase
separation are the leading indicators of the degree of stability in an
emulsified PCM system. In general, for emulsions, two types of stability
should be considered: kinetic stability and mechanical-thermal load

Fig. 13. Classification of emulsions into oil-in-water (O/W) direct emulsions, water-in-oil (W/O) inverse emulsions, oil-in-oil (O/O) emulsions, and multiple
emulsions (W/O/W, O/W/O, W/O/O).

14
S.A. Albdour et al.
stability. The former is related to the ability of the emulsion to be stored
for a long period of time. It is intrinsically linked to the chemical com­
pounds employed to create the emulsion, more precisely the paraffin
and surfactant types. Six types of instabilities appear under the category
of kinetic stability; namely, creaming, sedimentation, flocculation,
phase inversion, coalescence, and Ostwald ripening, as shown in Fig. 14
[111].
The emulsion may become unstable through creaming or sedimen­
tation if the dispersed and continuous phases have a density difference
and are stored for a long time without a suitable stabilization procedure.
If the density of the dispersed phase is lower than that of the continuous
phase, droplets travel upward and split from the continuous phase,
establishing a distinct layer on top of the continuous phase. Creaming is
the term for this phenomenon. Sedimentation, on the other hand, occurs
when the density of the dispersed phase is higher than that of the
continuous phase, pushing droplets to travel downward to create a
stationary layer at the bottom of the continuous phase [112]. Floccu­
lation is the process of connecting droplets without rupturing the sur­
factant’s stable, protective barrier to generate huge clumps or flocs that
rise or settle faster in the emulsion than individual droplets [113].
Phase inversion takes place when the original continuous phase in­
verts to become the dispersed phase, while the dispersed phase becomes
the continuous phase [109]. Phase inversion can be induced by changing
the affinity of the emulsifier from one phase to the other, a process
known as transitional phase inversion. It can also be triggered by a
change in the emulsion’s water-to-oil ratio, which results in a phe­
nomenon called catastrophic phase inversion [114]. Coalescence is
when two or more droplets completely merge together to form a single
droplet. Emulsion coalescence is triggered by the thinning and disrup­
tion of the liquid film between the droplets. This can occur when
emulsion droplets form a cream layer, a floc, or during Brownian
diffusion [115]. Ostwald ripening is caused by changes in solubility
between oil droplets of various sizes. Smaller droplets have a higher
solubility than bigger ones, and when molecules diffuse from small to
large droplets over time, the size distribution shifts to larger values.
Ostwald ripening and coalescence result in an increase in overall droplet
size, a decrease in interfacial area, and an increase in droplet dispersion.
An emulsion is deemed to have mechanical-thermal load stability
when it is stable under repeated cycles of melting and solidification and
during circulation. It is strongly affected by the surfactant type and
concentration and emulsion viscosity [111].
Fig. 14. Schematic representation of a stable emulsion and the different forms of emulsion instabilities, including creaming, sedimentation, flocculation, phase
inversion, coalescence, and Ostwald ripening.
15
Progress in Energy and Combustion Science 93 (2022) 101037
2.3.5. Nano-enhanced PCM (NE-PCM) systems
A key disadvantage of bulk PCM systems is their low thermal con­
ductivity, with values reported to vary between 0.2 and 0.7 W/m•K
[116]. Low thermal conductivity mainly affects the charging and dis­
charging speeds. As a general rule, the faster the charging and dis­
charging processes, the more effective the PCM is in storing and
releasing thermal energy. To address this issue, focus is drawn to
forming a thermally conductive network inside the PCM. Due to their
high thermal conductivity, nanoparticles were proposed to be dispersed
in PCMs [117]. In this approach, the nanoparticles (ranging in size from
1 to 100 nm) are directly impregnated at the optimum weight percent
and surfactant amount to ensure homogeneous distribution within the
PCM, often by employing some mechanical techniques.
Nano-additives could be metallic (e.g., Cu, Au, Ag, and Al), metal
oxides (e.g., CuO, Al2O3, and TiO2), or carbon-based (e.g., single- or
multi-wall carbon nanotube (SWCNTs/MWCNTs), graphene, and
graphite) [118, 119]. The advantage of having a large ratio of surface
area to volume in nanoparticles provides new paths for conduction heat
transfer [119]. Since surface atoms in a material dominate its in­
teractions with the surroundings, the large area-to-volume ratio in
nanoparticles allows them to exhibit unexpected optical, physical, and
chemical properties [120]. Additionally, due to their small size, nano­
particles have less momentum, resulting in fewer erosion issues.
At room temperature, the thermal conductivity of some nano­
particles, such as MWCNTs, can exceed 3000 W/m•K, and for single-
layer graphene, it can range between 4840 and 5300 W/m•K [121].
However, and as illustrated in Fig. 15, several factors must be considered
to achieve high thermal conductivity in a nano-enhanced PCM
(NE-PCM) system. Overall, increasing the concentration of nanoparticles
increases thermal conductivity [117]. However, there is an optimum
concentration for effective heat transfer inside the PCM [122]. When
particle concentrations are high (above the optimum), the slip velocity
between nanoparticles and fluid may not be zero. However, the migra­
tion of nanoparticles results in non-uniform concentrations and thermal
property distributions throughout the flow region, which is an unfa­
vorable situation [120]. As previously stated, the outstanding charac­
teristics of nanoparticles are derived from their high area-to-volume
ratio. The enhancement in the thermal conductivity of a fluid when
doped with nanoparticles has been explained by Brownian motion,
defined as the chaotic movement of particles due to random collisions
with liquid molecules [113]. A higher surface area increases the surface
energy of nanoparticles. Thus, their Brownian motion is accelerated,
inducing nanoscale convection [120].
S.A. Albdour et al.
Fig. 15. The main factors affecting the thermal conductivity of nano-enhanced
PCM systems.
Nanoparticles can be produced as spheres, cubes, or cylinders. A
spatially homogeneous distribution of nanoparticles is an essential
aspect that is expected to affect the thermophysical properties of a NE-
PCM system [123]. Due to their high surface activity, nanoparticle
clustering can take place as a result of the strong van der Waals forces
that attract nanoparticles to each other [124]. The diameter of a cluster
of nanoparticles is larger than the diameter of primary particles. This
may lead to sedimentation and phase separation if clusters reach the
microscale [124]. To resolve this issue, surfactants are often used to
prevent nanoparticle clustering by creating a molecular barrier against
interparticle collisions and changing the surface activity [125]. How­
ever, there is an optimum value for the surfactant-to-nanoparticles
loading ratio [125]. Polyvinyl pyrrolidone (PVP) [125] and sodium
dodecylbenzene sulfonate (SDBS) [117] are examples of surfactants
used to prepare NE-PCMs.
Along with the use of surfactants, some techniques can be used to
reduce clustering, including ultrasonication [126], high-pressure shear
homogenization [127], ball milling [128], mechanical mixing (by stir­
ring or shaking) [129], or magnetic stirring [130]. Ultrasonication is
most widely used in the nanofluid community [131]. Ultrasonic devices
generate ultrasonic waves, which cause cavitation and agitation of the
fluid. Ultrasonication processes vary according to the device type,
power, and sonication time.
Kumar et al. [118] highlight that the thermal properties of NE-PCMs
depend on the weight concentration of nanoparticles and the primary
melting behavior of the PCM. In an experimental campaign [132], the
effect of three types of individual nanoparticles (TiO2, CuO, and GO) on
the performance of a solar still was studied. Each nanoparticle was
impregnated at 0.3 wt% in paraffin with the same
surfactant-to-nanoparticles ratio of 1:1. Results showed an increase in
thermal conductivity by 25.0, 28.8, and 101% and a reduction in
melting temperature by 7.87, 7.08, and 9.44% for TiO2, CuO, and GO,
respectively. Furthermore, a reduction in the solidification temperature
by 6.77, 6.77, and 5.08% was achieved after adding TiO2, CuO, and GO
nanoparticles compared with pristine paraffin. In addition, water pro­
ductivity increased by 23.0, 39.3, 43.2, and 18.0% using paraffin, TiO2,
CuO, and GO, respectively, compared with the productivity of a con­
ventional still. In another study, the effect of adding spongy graphene on
the thermal performance of docosane was investigated [133]. Both
16
Progress in Energy and Combustion Science 93 (2022) 101037
thermal conductivity and latent heat increased after adding the spongy
graphene. Thermal conductivity rose from 0.26 to 0.59 W/m•K while
latent heat rose from 256.1 to 262.2 J/g. These findings indicate that the
molecular structure of docosane remained unchanged in the docosa­
ne/graphene composite. The thermophysical properties and thermal
performance of a selected number of NE-PCMs reported in the literature
are summarized in Table 6.
2.3.6. Shape-stabilized (porous matrix-supported) PCM systems
Impregnating a PCM into a porous medium is considered a promising
solution to resolve both the low thermal conductivity and leakage
problems in pristine PCMs. This process results in what is known as
shape-stabilized PCM (SS-PCM) [142], also known in some literature as
form-stable or porous matrix-supported PCM. According to this tech­
nique, the PCM in the liquid phase is impregnated and retained by
another material with a porous structure via the capillarity effect [11].
Based on the pore size, porous supports are characterized as macro­
porous (pore size > 50 nm), mesoporous (pore size is 2-50 nm),
microporous (pore size < 2 nm), and hierarchically porous (pore size
varies from macro to micro) [143]. In comparison, when moving from a
large pore size to a smaller one, the porosity increases and its structure
changes from a disordered pore arrangement to an ordered one [143].
Macroporous materials have received little attention because of their
less reliable immobilization of PCMs, which is attributed to their weak
capillary force. In contrast, the smaller pores and greater surface area of
materials at the meso and micro scales enable more intense interactions
between the PCM (guest) and support structure (host), thereby pre­
venting leakage [144]. Hierarchically porous materials with pore sizes
ranging from macro to micro present a uniquely interesting case as the
macropores serve as a cavity to retain the PCM, mesopores act as a
transport network, and micropores induce capillary forces to immobilize
the PCM, leading to extremely high energy storage capacities. Unfor­
tunately, relevant reports on this type of SS-PCM systems are still few
[143].
Porous materials for SS-PCMs
Metal foam-based SS-PCMs. Metal foam is an example of a typical
macroporous material (0.1− 5 mm) with high open porosity (85− 98%)
and specific strength [145]. The high thermal conductivity of metal
foams is their most intrinsic property, which is why many researchers
have adopted them as a means to improve the PCM charging and dis­
charging processes. Various types of metal foams have been used with
PCMs, including stainless steel foam (16.3 W/m•K) [146], nickel foam
(91.4 W/m•K) [147], aluminum foam (237.0 W/m•K) [148,149], and
copper foam (398 W/m•K) [147,150].
Overall, the higher the porosity of a metal foam, the higher the
effective thermal conductivity of the SS-PCM [151]. In general, the
thermal conductivity of a continuous skeleton structure with inter­
connected pores is greater than that of closed pores. For the same
porosity, a larger pore size means fewer and more interconnected pores.
Despite the advantages of high thermal conductivity, leakage occurs due
to the large size of metal foam pores compared to the size of the
phase-change cores (which is usually in nanoscale), especially if the
PCM loading is extensive [145]. Furthermore, it was found that the
latent heat of metal foam-based SS-PCMs was reduced due to the lack of
PCM inside porous media [151]. In general, metal foams with high
thermal conductivity, appropriate pore size, and high porosity may
improve the thermal performance of the PCM.
Porous carbon-based SS-PCMs. Porous carbon exhibits strong guest-
host interactions, such as van der Waals force, hydrogen bond, capil­
lary force, and/or surface tension, due to its high surface area and
possibility of surface modifications [145]. Porous carbon SS-PCMs
include expanded graphite, carbon nanotubes, graphene, and carbon
aerogels, with a summary of their properties shown in Fig. 16.
Porous oxide-based SS-PCMs. Numerous types of porous oxides are
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Table 6
Thermophysical properties and thermal performance and stability of selected NE-PCMs.
NE-PCM type NE-PCM thermal properties Heat transfer behavior Thermal stability Ref.
Thermal conductivity Latent heat

Tetradecanol (TD) enhanced
with (0.662-58.9 wt%) of
Cu nanowires
Methyl ester enhanced with
(0.05-0.5 wt%) of Cu- TiO2
hybrid nanocomposite
Paraffin enhanced with CuO
(0.1-5 wt%)
Paraffin enhanced with (0.1-
5 wt%) of PANI
Paraffin wax enhanced with
(10 and 20.0 wt%) of
Fe3O4 nanoparticles
Water enhanced with (0.1 wt
%) of CuO nanoparticles
Pentaerythritol enhanced
with (0.1, 0.5, and 1%) of
Al2O3 nanoparticles
Organic ester enhanced with
(0.1, 0.5, 1.0, 2.0, and 5.0
wt%) of Ag nanoparticles
Paraffin wax enhanced with
(1, 2, 3, and 4 wt%) of
CNFs
- Thermal conductivity was 9 times Dropped linearly with the Melting speed was accelerated. The weight loss [134]
higher than pristine TD. increase of Cu concentration. speed was slower
- 13.4 wt% of Cu was a turning point than pristine TD.
in thermal conductivity
enhancement.
- When the load exceeded 13.4 wt%,
thermal conductivity increased
significantly.
Enhanced from 0.228 to 0.347 W/ Dropped by 7.5% during Melting and solidification times Stable over 1000 [135]
m•K in solid PCM phase and from freezing and 7.3% during dropped by 70.9 and 77.9%, thermal cycles and
0.212 to 0.323 W/m•K in liquid PCM melting. respectively. up to 216◦ C.
phase.
Enhanced by 63.5%. Enhanced by 7.81%. Not reported. Stable after 200 [136]
thermal cycles.
Enhanced by 46.7%. Enhanced by 8.2%. Not reported. Stable after 200 [136]
thermal cycles.
Enhanced by 48 and 67% for 10 and Enhanced by 3.3 and 8.8% for Melting temperature was unchanged. Stable after 500 [137]
20 wt% of Fe₃O₄, respectively. 10 and 20 wt% of Fe₃O₄, thermal cycles.
respectively.
Not reported. Insignificantly changed. - Solidification time dropped by 35%. Not reported. [138]
- Accelerated charging was recorded
during the first 25% of solidification
time, in which 50% of the total mass
solidified.
Increased with the increase of Al2O3 Dropped with the increase the - Time for energy storage/release Stable up to 100 [139]
concentration as follows: 0.1282, concentration of Al2O3 by an dropped by 17.2, 20.5, and 23% for thermal cycles.
0.1412, and 0.1609 W/m-K for 0.1, average of 5% of the original Al2O3 concentrations of 0.1, 0.5, and
0.5, and 1%, respectively. value. 1 wt%, respectively.
- Transition temperature was
unchanged after adding 0.1% of
Al2O3.
Enhanced by 10 and 67% for 0.1 and 5 At 5 wt% of Ag, latent heat Solidification and melting times FTIR results [140]
wt% of Ag, respectively. dropped by 7.88 and 8.91% dropped by 30.8 and 11.3%, confirmed thermal
during freezing and melting, respectively. and chemical
respectively. stability.
Enhanced with the increase of carbon Dropped with the increase of - Solidification time dropped with the Not reported. [141]
concentration. carbon concentration. increase of carbon concentration.
- Heat dissipation was higher than
pure paraffin wax.
- Output power increased with the
increase of carbon concentration.

suitable for use as supports in SS-PCMs due to their superior thermal
stability, chemical compatibility, high surface area, and even better
thermal conductivity than porous carbon. Porous clay mineral-based SS-
PCMs are a common and well-known family of SS-PCMs, including
expanded perlite, fly ash, diatomite, sepiolite, attapulgite, and vermic­
ulite. Clay mineral-based SS-PCMs offer the advantages of thermal sta­
bility and reliability, high chemical compatibility, and a wide variety of
interactions with PCMs [145]. Due to their tunable pore size and high
surface area, mesoporous silica-based SS-PCMs are another promising
type of porous oxide supports. The pore size is smaller than clay min­
erals, porous carbon, and metal foams. Interestingly, the confinement of
PCMs with nano-porous silica showed that material properties no longer
determine the melting point, which can be changed based on the hier­
archical pore structure [145]. Epoxy resin, polystyrene-graft-poly
(ethylene glycol) copolymers (PS-g-PEG), and poly(styr­
ene–butadienestyrene) are examples of porous polymers used in
SS-PCMs [145].
chosen based on the material of the core and the encapsulation method
used [152]. Compatibility between the core and shell materials is an
important requirement for the successful encapsulation of PCMs. Pre­
treatment of the core material is used in some cases to improve
compatibility [153].
Benefits of encapsulation. The importance of encapsulation can be sum­
marized as follows [2, 153]:
• Containing the PCM and isolating it from the surroundings.
• Controlling the amount of PCM that participates in thermal cycles.
• Increasing the rate of heat transfer.
• Enhancing structural and mechanical stability.
• Improving compatibility with the surrounding materials.
• Enhancing processability (dispersibility and flowability).
• Reducing the foul odor of some PCMs.
• Safely handling toxic PCMs.

2.3.7. Encapsulated PCM (ePCM) systems
Encapsulation is a widely used technique for improving the handling
of PCMs, particularly those undergoing solid-liquid transitions. It is
generally defined as the process of enclosing the PCM with an inert
coating or shell material. As a result, the two main components are the
core and shell. The core is the intrinsic component that contains the
active PCM. The extrinsic part is the shell, which can be made of organic
polymers, metal oxide, hydroxide, or silica. The material of the shell is
Classification and morphology of encapsulated PCMs. The resultant
products of the PCM encapsulation process can be classified into three
groups based on the core size to be coated: macro-encapsulated PCMs
(above 1 mm), micro-encapsulated PCMs (from 1 to 1000 μm), and
nano-encapsulated PCMs (from 1 to 1000 nm) [154]. Because of the
critical difference in the size of encapsulated PCMs, different encapsu­
lation techniques have been used, which have a significant impact on the
shell shape and selected PCM.

17
S.A. Albdour et al.
Fig. 16. Key characteristics of the main types of porous carbon-based shape-stabilized PCMs. This includes expanded graphite, CNTs, graphene, and carbon aerogel.
The encapsulation process at the macro-scale can be carried out by
filling a pre-prepared shell with PCM in the liquid phase. However,
encapsulation at the micro- and nano-scales is more complicated.
Nonetheless, the micro/nano-encapsulation of PCMs is known to more
effectively improve the rate of heat transfer relative to macro-
encapsulation. To draw general observations regarding ePCMs,
Figs. 17 and 18 show the latent heats of melting and solidification of a
variety of ePCMs in relation to their melting and solidification temper­
atures. It is noticeable that the melting and solidification temperatures
and latent heats for the same ePCM are not identical, and there is no
definite relationship or pattern that dictates which is higher. The ma­
jority of the ePCMs have melting temperatures lower than 100◦ C. A
small number of studies has been dedicated to medium (100-300◦ C) and
high (above 300◦ C) melting-temperature ePCMs. The reason behind this
is that using conventional techniques of encapsulation is not suitable for
such temperature ranges. For instance, since molten salts dissolve easily
in water, traditional encapsulation methods like the sol-gel method are
ineffective [155]. For micro/nano-encapsulated PCM techniques, they
are divided into three broad groups: physical, chemical, and
physical-chemical (more details are provided in Section 3). In the
physical techniques, the shell is mechanically applied around the micro
core [156]. This has the advantage of having a negligible negative
impact on the environment. However, physical techniques are limited to
producing particles smaller than 100 μm, making them suitable for
micro-encapsulated PCMs. In contrast, chemical techniques can produce
encapsulated PCM particles that are significantly smaller, making them
ideal for nano-encapsulated PCMs [157]. It is reported that physical
techniques result in a rougher surface and a significant drop in latent
heat of fusion compared to chemical ones [2, 158]. A stable particle can
be produced by a physicochemical technique that includes ionic gela­
tion, coacervation, and sol-gel [156].
Organic PCMs can be encapsulated using a variety of techniques
[152], while approaches for encapsulating inorganic PCM are confined
18
Progress in Energy and Combustion Science 93 (2022) 101037
to solvent extraction and evaporation. In this method, a large amount of
non-volatile organic solvents (e.g., toluene, chloroform, carbon tetra­
chloride, and acetone) is employed. This means that micro-encapsulated
inorganic PCMs are more expensive than organic ones [159]. Among the
chemical approaches investigated, in-situ polymerization was deter­
mined to be the preferred way for encapsulating organic PCM due to its
superior shell structure and reduced capsule size [160] (more details are
provided in Section 3).
Different types of particles can be created depending on the physi­
cochemical parameters of the core-shell and the encapsulation process
utilized, as demonstrated in Fig. 19. Many factors affect the size distri­
bution of PCM capsules [157], which can be summarized as follows:
• The mixing rotational speed during the emulsifying stage (smaller
sizes are obtained at higher mixing speeds).
• The amount of surfactant (smaller sizes are obtained for higher
surfactant amounts).
• The ratio of core material to nucleating agent.
• The shell material.
Nomenclature of ePCMs. While dealing with ePCMs, it is important to
keep in mind that not all ePCMs can achieve the original role of efficient
latent heat storage. Because of shell existence, molecular motion is
confined and the phase change may not completely occur [161]. In this
regard, the concept of encapsulation ratio, ηPCM, is introduced to
quantify the adequate performance of PCM inside a shell based on the
enthalpy of fusion, as follows [162],
(ΔHs − l)ePCM
ηPCM = . (8)
(ΔHs − l)PCM
Theoretically, the melting and freezing points of a PCM are the same.
However, in reality, they are not. Therefore, the encapsulation
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 17. Latent heat of melting and melting temperature of various types of ePCMs.

efficiency, E, as a more comprehensive concept, is introduced and given 2.4. Applications of PCMs in thermal management systems
by the following equation [163],
Electronic products such as integrated-circuit boards, batteries, re­
(ΔHs − l)ePCM + (ΔHl − s)ePCM
E= , (9) sistors, transistors, and microprocessors have become an intrinsic part in
(ΔHs − l)PCM + (ΔHl − s)PCM
human lives. This significant increase in consumer electronics means
that their effective thermal management is pivotal to maintain perfor­
where (ΔHs − l)ePCM and (ΔHs − l)PCM are the enthalpies of melting with
mance consistency and product lifetime. Thereby, researchers are
and without encapsulation, respectively. (ΔHl − s)ePCM and (ΔHl − s)PCM
continuously attempting to make cooling systems more effective and
are the enthalpies of solidification with and without encapsulation,
compact. At present, the thermal management of electronic devices is
respectively. A higher encapsulation efficiency is an indication of higher
one of the most important aspects in their development and design.
mechanical stability and leak-proof strength.
According to previous research studies, overheating is one of the leading
The core-to-shell mass ratio is another important parameter deter­
reasons for electronic equipment failure. Therefore, it is necessary to
mining the functional, structural, and mechanical stability of ePCMs. A
regulate the operating temperature of electronic components to guar­
lower core-to-shell ratio means the shell is thick, reducing the amount of
antee their efficiency and reliability [164].
contained PCM. Meanwhile, a higher core-to-shell ratio increases the
For the thermal management of many electronic devices, passive
chance of leakage to the surroundings and deteriorates the strength of
cooling is a more practical choice compared to active cooling, although
PCM. It is reported that the optimum core-to-shell ratio to balance these
it suffers from a lower heat dissipation rate. Integrating heat sinks with
effects is 3:1 [2]. Ghosh [153] established a formula for calculating the
PCM technology has received great attention to circumvent such trade-
shell thickness based on the core-to-shell ratio, assuming that the density
offs when using passive cooling systems. PCMs often suffer from poor
of the core and shell materials is identical, as follows:
[( ] thermal conductivity, which reduces the efficiency and performance of
)1/3
ws heat sinks. Therefore, fins are generally added to PCM heat sinks to boost
ds = (r − rc ) = +1 − 1 rc , (10) their thermal conductivity and enhance heat transfer. Various fin con­
wc
figurations have been developed for PCM heat sinks that operate under
where ds is shell thickness, rc and r are the core and whole capsule radii, constant and variable thermal loads [165]. It was revealed that the
respectively, and ws/wc is the ratio of shell weight to core weight. thermal performance of PCM heat sinks depends on the substrate and fin
thickness, volume fraction of PCM, PCM type, fin height, number of fins,
and fin shape. However, there is an optimal number of fins beyond

19
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 18. Latent heat of solidification and solidification temperature of various types of ePCMs

Fig. 19. Morphology of common a) macro-encapsulated (spherical, tubular, cylindrical, and rectangular) and b) micro/nano-encapsulated (mononuclear, poly­
nuclear, matrix, and multi-shell) PCMs

which the base temperature declines, and this number is dependent on PCM completely melts over a short period of time [167]. The
the amount of PCM and heat sink size [166]. The melting onset was enthalpy-porosity approach was found to be the better model to simulate
shown to be delayed by increasing the number of fins. However, the phase-change processes. Moreover, metallic PCMs have shown higher

20
S.A. Albdour et al.
performance than non-metallic ones [165].
Although the combination of heat sink, fins, and PCM enhances the
thermal performance of the cooling system, it increases its weight. In
addition, the insertion of fins reduces the PCM volume; hence, a lower
amount of energy can be stored. To bypass these drawbacks, an alter­
native method was proposed to improve the thermal conductivity of
PCMs. It was found that the addition of highly conductive nanoparticles
to the PCM makes the heat sink a more suitable choice for electronics
cooling [168]. Convection currents are inhibited with the addition of
nanoparticles due to the increase in viscosity which affects the thermal
performance of the heat sink [169]. However, by carefully choosing the
concentration and type of nanoparticles, the increase in thermal con­
ductivity may outweigh the increase in viscosity [170]. In fact, the
addition of nanoparticles can enhance the thermal performance of PCM
heat sinks through reducing the heating time by almost 22% [171].
Furthermore, it was shown that at low power loads, the addition of
nanoparticles has a positive impact at regulating the base temperature,
but at higher power loads, the addition of nanoparticles has a negative
impact [172]. The nanoparticle type may also have a significant impact
on the cooling system. Alumina nanofluids with a volume fraction of
0.5% resulted in a 6% increase in the convection heat transfer coeffi­
cient, while CNT nanofluids with a volume fraction of 0.25% at a flow
velocity of 21 mL/s produced the greatest heat transfer boost (about
13%) [173].
Using nanoparticles can improve the thermal properties of PCMs,
and hence can be used for different cooling systems. However, the
optimal cooling technique not only offers a higher heat transfer rate, but
should also provide superior heat absorption capacity at a desired
temperature range. Micro/nano-ePCM slurries and dispersions, which
are produced by dispersing micro/nano-ePCMs into a pure fluid, possess
larger heat capacities when the ePCMs experience a phase change and
are favorable if the cooling system parameters are adequately tailored to
utilize their latent heat of fusion. Therefore, micro/nano-ePCMs seem to
provide a viable avenue for meeting these cooling requirements. Using
nano-ePCMs to cool lithium-ion batteries showed that increasing the
volume fraction of the ePCM up to 3% increased the heat transfer rate of
lithium-ion batteries by 8.2− 13.6% [174]. Choi et al. [175] adopted a
micro-ePCM slurry for the cooling of telecommunication equipment
with high power and heat densities. According to their findings, when
the mass flow rate increased, the heat transfer rate of the unit cooled
with a micro-ePCM slurry rose. Moreover, the cooling performance of
the slurry-cooled unit was superior to that of the water-cooled one.
Using a micro-ePCM slurry, Sharma et al. [176] investigated
hotspot-targeted integrated liquid cooling of multicore microprocessors
to optimize energy efficiency and decrease chip temperature. Using a
micro-ePCM slurry, they were able to control the surface temperature of
the equipment chip as required. Experimental data of LED thermal
management systems reveal that an increase in micro-ePCM concen­
tration does not necessarily result in an enhancement in cooling per­
formance, while phase transition and thermophysical properties of the
micro-ePCM play an important role [177].
As another efficient and promising approach for improving the
thermal performance of cooling systems, the use of metal foams (such as
graphite, carbon, copper, and aluminum) has attracted a great deal of
interest and has been evaluated in a wide range of applications [178].
PCM-based metal foam cooling systems demonstrated superior perfor­
mance over pure PCM and nanoparticle-PCM systems with a significant
decrease in melting time. It was observed that metal foam composites
exhibit a thermal conductivity improvement of up to 218 times [179]. A
comparison among finned surfaces, nanoparticles, and metal foams has
revealed that the combination of metal foam and nanoparticles offers
the best heat transfer performance, where the metal foam is the primary
source of enhanced heat transfer [180]. Since the metal foam is
described by its pore density, pore size, and porosity, it is crucial to
assess the impact of these factors in a PCM-based thermal management
system. The literature has demonstrated that lower porosities lead to a
21
Progress in Energy and Combustion Science 93 (2022) 101037
higher heat transfer [181], while a higher porosity indicates less mass
and volume and hence lower heat storage capacity [182]. Concerning
pore density, investigations have shown minimal [183], small [184], or
considerable [185] impacts on the heat transfer rate. However, it is
almost agreed upon that porosity is more important than pore density in
terms of the heat transfer performance of PCM-based metal foam com­
posites [182]. The use of micro-ePCM-saturated metal foams for passive
thermal management has shown that micro-ePCMs were not appropriate
for thermal management. However, integrating micro-ePCMs with
metal foams at high pore densities provides better thermal control
[186].
2.5. Applications of PCMs in solar energy systems
2.5.1. An overview of solar thermal energy
The World Energy Council stated that the total energy produced by
the sun every day is 3.8×1023 MW, with only 1.08×1014 KW of that
reaching the surface of earth. Despite its relatively small magnitude, it
has been reported that if only 0.1% of the solar energy intercepted by the
earth could be converted to electricity with a 10% efficiency, it would
supply approximately 3000 GW, or four times the world’s total energy
demand [187]. Fig. 20 shows the types of solar-thermal collectors and
their classification into non-concentrating and concentrating collectors.
Generally, a solar photothermal collector is a specialized device in
which incident solar irradiation is absorbed and converted to thermal
energy carried by a HTF. This heat can subsequently be extracted and
utilized to heat buildings, heat domestic water, or generate electricity
via power cycles [188,189].
Fig. 21 displays the energy flow through a conventional solar-
thermal collector, consisting of a glass cover, absorber plate, HTF, and
insulated housing. When sunlight strikes the glass surface, it is trans­
mitted and absorbed by the absorber plate, which has a selective
absorber coating that maximizes absorption in the solar spectrum and
minimizes emission in the thermal spectrum. The function of the
absorber plate in this case is to convert solar energy into thermal energy,
which is then transferred to the HTF. This is dominantly realized
through forced convection between the HTF and the inner surface of the
absorber plate. The surface temperature of the absorber plate will
unavoidably increase over time, posing several problems:
• Heat loss into the surroundings due to thermal radiation emission
and natural air convection. Both are closely related to surface tem­
perature; therefore, thermal efficiency drastically drops with an in­
crease in absorber temperature [191].
• Oxidation and peeling of the coated layer deteriorates the optical
properties of the absorber plate (stability issue) [6].
To maximize the useful energy extracted by the HTF as it passes
through the collector, two aspects should be considered; namely,
maximizing solar radiation absorption and reducing heat loss to the
surroundings. Accordingly, the thermal efficiency of any solar-thermal
collector is defined as the ratio of useful thermal energy gained by the
HTF to the total solar radiation input, as follows [192]:
ṁcp (Tout − Tinl )
ηth = , (11)
GA
where ṁ represents mass flow rate, cp is specific heat of the working
fluid, Tout and Tinl are outlet and inlet temperatures of the HTF,
respectively, G is solar irradiance, and A is the aperture area.
Non-concentrating collectors and concentrating collectors are the
main two main categories of solar-thermal collectors, depending on
their design and the temperature at which they operate. In non-
concentrating collectors, the aperture and receiver areas are equal.
These collectors utilize both the beam and diffuse components of solar
radiation, and thus, do not require a tracking system. They operate at
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 20. Types of solar-thermal collectors and their classification into non-concentrating and concentrating collectors (CR is solar concentration ratio) [190]. (Reused
with permission from Elsevier).

low-to-medium temperatures (around 60-100◦ C) and are consequently

Fig. 21. Energy flow in a conventional solar-thermal collector where heat is the
desired output from the photothermal conversion process.
commonly utilized for space heating and residential hot water supply
[193]. The flat-plate collector (FPC) is the centerpiece of any solar en­
ergy collection system intended for operation at low or moderate tem­
peratures. A FPC absorbs solar energy, converts it into heat, and
transfers that heat to a flow of liquids or gases. At temperatures above
80◦ C, an evacuated-tube collector (ETC) allows for the extraction of
more heat than a FPC since it combines the effects of a highly-selective
surface coating with vacuum insulation of the absorber element [194].
Several improvement techniques, including turbulators and ferrofluids,
have been employed in non-concentrating collectors to enhance their
performance. Turbulators, which are composed of wire coils and twisted
tape, have been utilized to enhance the heat transfer rate by turning
laminar flow into turbulent flow. Due to the reduced flow area, the flow
velocity increases with a slight increase in pressure drop [195]. Ferro­
fluids are composed of magnetic nanoparticles (e.g., Fe, Fe3O4, etc.) and
base liquids. This combination offers both fluidity and magnetism.
Scholars are interested in ferrofluids due to the fact that, by modifying
the direction and intensity of the magnetic field, these fluids can exhibit
a variety of unique features. Ferrofluids can be manipulated by an
external magnetic field, leading to better mixing within the fluid layers
and improved thermal efficiency [196].
For concentrating collectors, the interceptor has a greater surface
area than the absorber. They are typically used in high-temperature
solar power plants (above 350◦ C) [193]. Concentrating collectors are
of two general types: line-focused and point-focused. In line-focused
collectors, the incident radiation is focused to a linear receiver (e.g.
parabolic trough and linear Fresnel reflector), whereas in point-focused
collectors, the incident radiation is focused on a point (e.g., parabolic
dish and central receiver) [197]. Among them, parabolic trough

22
S.A. Albdour et al.
collectors are most widely used, accounting for more than 95% of global
concentrated solar collector installations [198].
As shown in Fig. 22, CSP plants are made up of three major com­
ponents; the solar field, TES system, and power block. In the solar field,
solar radiation is concentrated to heat thermal oil to high temperatures
while remaining in the liquid phase [199]. The hot oil is then utilized in
oil/water heat exchangers to generate steam, which is used to drive a
turbo-generator in the power block for electricity production. The hot oil
is also used to supply heat to the TES system during the charging stage.
TES systems in CSP plants are divided into two types: direct and indirect
storage. In the direct approach, the working fluid serves as both a HTF in
the solar field and a storage medium in the TES system, whereas in the
indirect approach, the HTF is different than the storage medium, as
shown in Fig. 23. Molten salt is most commonly used in commercial CSP
plants as a sensible and latent high-density storage medium that can
maintain high cycle efficiency [200]. One of the main difficulties facing
CSP plants is the need for cost-effective and reliable energy storage
media and HTFs for operation over prolonged periods of time at high
temperatures [201].
A promising development in the field of CSP is direct steam gener­
ation (DSG) technology, in which steam is produced directly within the
absorber tubes of the solar field by boiling and superheating water,
resulting in a two-phase flow. The primary benefit of this technique is
that the same fluid is used in both the solar field and the power cycle,
thereby eliminating the expenses and dangers associated with employ­
ing thermal oils that degrade in the solar field. Additionally, the
complexity, cost, and thermal losses caused by the massive heat ex­
changers between the solar field and the power block are eliminated,
and much higher process temperatures may be achieved, hence,
enhancing the heat-to-power conversion efficiency in the power block
[203]. However, the most significant disadvantage of DSG is the need for
expensive absorber tubes and interconnections as well as sophisticated
control systems to safely manage the high temperatures and pressures
that occur inside the two-phase water flow in the solar field [204].
Even if the conversion efficiency of the aforementioned collectors
has generally increased over time, it must still be further improved to
maximize solar-to-thermal performance. For that purpose, numerous
coolants have been designed for a variety of operating temperatures.
Typically, pure liquid coolants have insufficient heat transfer perfor­
mance to absorb considerable amounts of heat. Nanofluids, which are
homogeneous mixtures of a liquid and nanoparticles, present a
tremendous possibility to boost the thermal efficiency of solar collectors
[205]. Nanofluids can offer improved thermophysical properties, such
as thermal conductivity [206,207,208]. For example, Vijayakumaar
et al. [209] conducted studies to examine the effect of CNT/water
nanofluid on flat-plate solar collectors. Using a nanofluid containing
0.5% CNTs increased the efficiency by 39% compared to water. Anin
Vince and Natarajan [210] experimentally evaluated the performance of
Fig. 22. The major components in a CSP-TES power plant. This includes the
solar field, TES system, and power block [202]. (Reused with permission
from Elsevier).
23
Progress in Energy and Combustion Science 93 (2022) 101037
a FPC employing GO nanofluids with forced circulation using a pump.
To make the nanofluids, graphene was suspended in deionized water at
the different mass concentrations of 0.005, 0.01, and 0.02. Compared to
a collector employing water, the collector employing a nanofluid with a
GO loading of 0.02 at a mass flow rate of 0.0167 kg/s exhibited a
maximum thermal efficiency improvement of 7.3%. Also, the overall
heat transfer coefficient went up by 8.03, 10.93, and 11.5% for nano­
fluids with 0.005, 0.01, and 0.02% GO, respectively.
Iranmanesh et al. [211] conducted an experiment to assess the in­
fluence of a graphene nanoplatelets/water nanofluid on the heat transfer
performance of an evacuated-tube solar water heater. At the varied flow
rates of 0.5, 0.1, and 1.5 L/min, the thermal efficiency of the collector
was measured. The collector efficiency reached a maximum of 90.7%
when the greatest graphene nanoplatelet concentration of 0.1% and the
highest flow rate of 1.5 L/min were utilized. Compared to distilled
water, this indicated a thermal efficiency boost of 35.8%. Fayaz et al.
[212] analyzed the influence of flow rate on the performance of a PV/T
system employing a MWCNT nanofluid. The concentration of MWCNTs
ranged from 0 to 1 wt%. Preliminary numerical results revealed that the
thermal efficiency of the PV/T system increased with increasing nano­
fluid concentration up to 0.75 wt%, after which it began to deteriorate.
Recent experiments; however, show that adding solid nanoparticles
like copper and alumina to pure fluids does not result in significant in­
creases in thermal conductivity [213, 214]. It has also been found that
the efficiency of the conventional solar collector drops at higher nano­
particle concentrations. This is because viscous forces increase, which
decreases the heat transfer rate and increases the pumping power [215].
This is in addition to abrasion and sedimentation issues [216].
The mismatch of energy demand and solar energy supply in terms of
time and place is the greatest disadvantage for both photothermal and
photovoltaic solar conversion processes [217]. This is compounded by
operational transients in CSP plants during warm-up, cool-down, and
cloud-disturbance periods [218]. Several advancements in the use of
PCMs to mitigate these energy mismatch and prolonged transient issues
have been made over the years, propelling solar energy to the forefront
of the energy sector [171]. This is achieved by keeping the HTF or PV
cell temperature approximately constant during phase transition, which
helps in avoiding problems associated with excessive temperatures [61].
2.5.2. PCMs in solar stills
Since conventional water desalination and purification technologies
consume a lot of fossil fuels or electricity, a solar still is an alternative,
sustainable technology capable of extracting freshwater from salty water
using solar radiation in an environmentally friendly manner. Moreover,
ultraviolet radiation adds a unique feature to solar stills by killing vi­
ruses, bacteria, and parasites. Therefore, this method is appealing for
rural and remote regions where clean drinking water is scarce. A solar
still offers fresh water at a low cost and uses simple designs. Neverthe­
less, the low water productivity and system efficiency are its main
disadvantages.
Manoj Kumar et al. [219] undertook an experimental campaign to
study the effects of integrating a conventional single-slope (CSS) solar
still with paraffin PCM doped with SiO2 nanoparticles. Their research
was conducted in three parts: without PCM, with pure PCM, and with
PCM enhanced with SiO2 nanoparticles (NE-PCM). Results showed that
water productivity for the NE-PCM case was the highest, followed by the
one with PCM only. Daily freshwater production was measured at 4100,
6200, and 6850 ml for the cases without PCM, with pure PCM, and with
NE-PCM, respectively. The daily yield improvement was estimated at
51.2 and 67.1%, respectively, when using PCM and NE-PCM compared
with the CSS solar still. Kabeel et al. [220] investigated the possibility of
improving potable water production in a tubular solar still (TSS) by
using a PCM doped with GO nanoparticles. Their investigation covered
TSS, TSS with PCM, and TSS with NE-PCM. Their results revealed that
the total cumulative freshwater yields in the TSS, TSS using PCM, and
TSS using NE-PCM were 2.59, 3.35, and 5.62 kg, respectively. Results
S.A. Albdour et al.
Fig. 23. Concentrated solar power plants with a) direct and b) indirect thermal energy storage.
also showed that the daily efficiency of TSS using NE-PCM was improved
by up to 116.5% with reference to the other cases.
2.5.3. PCMs in photovoltaic (PV) and PV/thermal (PV/T) collectors
The photoelectric solar collector is the most efficient technique for
directly turning solar energy into electricity. Solar cells are energy
conversion devices that convert sunlight into electricity via the photo­
electric effect. Solar cells and other auxiliary components make up a
photovoltaic system. However, photovoltaic cells face a substantial
challenge in that their electrical production is highly reliant on cell
temperature. For instance, increasing the temperature of crystalline
silicon cells by 1 ◦ C reduces the solar-to-electrical conversion efficiency
by 0.5% [221]. The temperature of photovoltaic cells can be regulated
by removing accumulated heat.
On the other hand, a new technology has evolved that combines both
solar-thermal collectors and photovoltaic collectors into one, known as a
hybrid photovoltaic/thermal collector. In these hybrid collectors, a
portion of solar radiation is converted to electricity by photovoltaic
cells, while another portion is converted to heat carried by a HTF [222].
The overall efficiency of a photovoltaic/thermal collector is calculated
as the sum of its thermal and electrical efficiencies, as follows:
ηtot = ηth + ηelc , (12)
Po
ηelc = , (13)
GA
where Po is the electrical power output.
PCMs can be utilized to regulate the temperature of PV cells and store
thermal energy for solar heating systems. Ho et al. [223] numerically
investigated a PV/T system based on PCMs in which a water-saturated
micro-ePCM layer was attached on the backside of the PV panel
floating over water. For a PCM container thickness of 5 cm and a melting
point of 30 ◦ C, the PV cell temperature decreased by 1.8 ◦ C while
electrical efficiency increased by 2.1%. Maatallah et al. [224]
24
Progress in Energy and Combustion Science 93 (2022) 101037
experimentally studied the performance of a water-based PV/T collector
using paraffin wax RT-30 under the weather conditions of Kottayam,
India. Results revealed that the thermal, electrical, and total efficiencies
increased by 26.9, 17.3, and 40.6%, respectively, compared with a
conventional PV panel.
Qiu et al. [225] carried out experimental work to study a PV/T
collector employing a micro-ePCM slurry as the working fluid. They
evaluated the performance of the PV/T collector under various param­
eters, including solar radiation intensity, slurry Reynolds number, and
ePCM concentration. Due to the fact that the temperature of the PV/T
collector was a direct factor affecting its performance, they revealed that
it could be decreased by lowering the solar intensity and increasing the
slurry concentration and Reynolds number. To achieve total efficiencies
of 80.8-83.9%, the recommended optimum values for each parameter
were as follows: solar intensity of 500− 700 W/m2, slurry concentration
of 10%, and Reynolds number of 3000. Hossain et al. [226] designed and
developed a PCM-based PV/T system to assess energy, exergy, and
economic performance under typical Malaysian weather conditions.
They used lauric acid in aluminum foil packets to avoid leakage and
placed them around the two sides of a serpentine flow channel. Their
results were compared to those of a reference photovoltaic module
operating at volumetric flow rates of 0.5 to 4 liters per minute (LPM). At
4 LPM, the highest electrical power output and maximum electrical ef­
ficiency were 160.29 W and 14.42%, respectively, which were 14 and
4.72% greater than the reference photovoltaic panel. The authors
highlighted that in the proposed PCM-based PV/T system, for every 100
W/m2 increase in solar intensity, the power output increased by 13.12
W, whereas the electrical efficiency dropped by 0.55%. The maximum
exergy output was recorded at 134.10 W for 0.5 LPM.
2.5.4. PCMs in concentrated solar power (CSP)
Several researchers have been investigating the use of PCMs as
thermal storage media to improve the dispatchability and marketability
of CSP plants [227]. Three designs are commonly reported in the
S.A. Albdour et al.
literature [228]; namely, a packed-bed storage tank filled with ePCMs, a
shell-and-tube heat exchanger in which the PCM is placed on the shell
side, and a cascaded PCM storage system. Laing et al. [229] studied a
prototype storage tank with different PCMs as follows: NaNO3,
KNO3− NaNO2− NaNO3, and KNO3− NaNO3, with melting temperatures
of 306, 222, and 142 ◦ C, respectively. Steam was used as the HTF. In the
tank, seven steel tubes with graphite or aluminum fins were impreg­
nated, depending on the melting temperature of the used PCM. Graphite
fins were used for temperatures up to 250◦ C, while aluminum fins were
used for temperatures above 250◦ C. After up to 172 thermal cycles, the
prototype demonstrated excellent thermal stability with no degradation
in the graphite/aluminum-finned tubes.
Galione et al. [230] proposed filling a storage tank with solid ma­
terials (quartzite rocks and sand) and ePCMs, with molten salt acting as a
working fluid to form a multilayer packed bed. The proposed design
included PCM packed bed layers at both ends of the storage tank. The
authors developed a numerical model and validated it against experi­
mental data. Simulations were then carried out for different configura­
tions, namely, solid material only, single PCM, multilayered solid-PCM,
and cascaded PCM filler materials. Results revealed that the proposed
multilayered solid-PCM design had a much higher efficiency compared
with the conventional TES system. Moreover, compared to the cascaded
PCM design, the new multilayered approach had the merit of using less
ePCMs for almost the same amount of stored energy.
Prieto and Cabeza [231] investigated a cascaded PCM TES system for
a parabolic-through CSP plant. The cascaded PCM configuration
included four buckets. In each bucket, PCMs were arranged based on
their melting temperatures and latent heats of fusion as follows: NaNO3
in the first bucket, a mixture of LiCl− 43%/KCl− 24%/NaCl− 33% in the
second bucket, NaOH− 80%/NaCl− 20% in the third one, and a combi­
nation of MgCl2− 60%/KCl− 20.4%/NaCl− 19.6% in the fourth one. The
main drawback was that the cascaded PCM and commercial indirect
two-tank molten salt designs showed similar results in terms of cumu­
lative annual power generation. However, the authors emphasized the
importance of performing a levelized cost analysis to validate the use of
PCMs for TES in solar power plants.
Similarly, Michels and Pitz Paal [106] conducted experimental and
numerical studies on cascaded latent heat storage for parabolic-trough
power plants. Their findings revealed that the cascaded TES system
provided a uniform outlet temperature and made better use of the
possible phase change over time. Additionally, it was found that NaNO3
was the most suitable PCM in terms of its heat of fusion and corrosion
resistance.
2.5.5. PCMs in building-integrated passive heating and cooling systems
Globally, the building sector consumes a significant amount of en­
ergy for heating and cooling applications, accounting for roughly 40% of
total energy consumption [232]. According to the International Energy
Agency, if no energy efficiency improvements are made in the building
sector, energy consumption could increase by 50% by 2050 [233]. As a
result, the concept of smart energy systems emerged to take advantage
of the synergy between reducing energy consumption in buildings and
increasing the efficiency of district heating and cooling networks.
A PCM is a common strategy to improve cooling and heating systems.
It has been shown to significantly reduce energy consumption in the
building industry, reduce energy costs by 10-20%, reduce harmful
emissions by 50%, and provide operational flexibility [234]. PCMs can
be incorporated into a variety of building materials in a variety of ways,
such as direct incorporation, immersion, encapsulation, and SS-PCMs
[235]. The most straightforward and economic method is to directly
impregnate PCMs into gypsum, concrete, mortars, or cement paste to
form a mixed-type PCM in the building wall (direct incorporation). The
immersion method includes submerging construction elements (e.g.,
concrete and brick blocks) in liquid PCM and allowing the PCM to be
absorbed through capillary force. In the case of direct incorporation and
immersion, leakage might occur. Alternatively, the PCM can be encased
25
Progress in Energy and Combustion Science 93 (2022) 101037
prior to being integrated into structural elements.
As previously discussed, PCM encapsulation can be at the macro or
micro scales, where the PCM is encapsulated before incorporation with
construction elements. The SS-PCM process involves melting the PCM at
a high temperature, blending it with the supporting material, and then
cooling it to below the transition temperature till the PCM fully solid­
ifies. Support materials for shape stabilization, including high-density
polyethylene, butadiene, diatomite, expanded perlite, and styrene,
have been widely employed in building-integrated passive heating and
cooling systems [235].
Wang et al. [236] performed a parametric study using PCMs in
concrete walls provided with a single glass window under Shanghai’s
summer conditions to reduce the solar energy gain. They investigated
the variation of heating load reduction with different PCM melting
temperatures, thicknesses, locations, and window dimensions. The re­
sults indicated that by incorporating PCMs into walls, the heat transfer
rate and average inner surface temperature were significantly reduced
during working hours. Additionally, liquid fraction analysis was used to
determine the effective fraction of total PCM that should be used to
optimize the PCM layer design. RT42 with a 20-mm-thick layer resulted
in nearly a 34.9% net reduction of heat flux. Similarly, Zhang et al. [237]
conducted an experimental study at Xinjiang University from 2011 to
2014 on a radiant floor heating system based on solar PCMs. The pro­
posed system could keep room temperatures up to 5-7 degrees Celsius
higher.
Barzin et al. [238] performed a series of experiments on the use of a
PCM underfloor heating system with PCM wallboard in two identical
test huts at the Tamaki campus, University of Auckland. Total energy
and electricity cost savings over five days amounted to 18.8 and 28.7%,
respectively. The biggest energy savings obtained over this period were
35%, equating to a 44.4% cost savings. Griffiths and Eames [239]
investigated a chilled ceiling system with an aqueous suspension of
micro-ePCMs (with a transition temperature of 18 ◦ C) over a period of
four months. The micro-ePCM was easily pumped through the cooling
and heating circuits using commercially available pumps with reduced
flow rates, thus reducing noise from the system. Results revealed that a
suspension with a concentration of 40% ePCMs was good enough to be
used as the HTF in the chilled ceiling system.
Liu et al. [240] studied the optical and thermal performances of a
PCM-based glazing system under the effects of solar irradiance, PCM
melting temperature, and PCM layer thickness in terms of transmittance,
temperature difference between the upper and bottom glazing surfaces,
and indoor temperature. They used a commercial solar simulator with a
solar intensity level that varied from 200 to 1200 W/m2. Results showed
that increasing the thickness of the PCM layer in the glazing system
decreased heat losses. The optimum PCM thickness for the best optical
performance (transmittance) was found to be 16 mm. The effect of
increasing melting temperature on thermal and optical performance was
deemed negligible. Moreover, when the PCM was in liquid phase, the
thermal performance and transmittance of the glazing system filled with
PCM were 50% higher than those supplied with air. PCMs are not only
used to heat liquids and rooms. They can also be used to cool buildings.
For instance, PCMs can be used as a cold storage medium in the heating,
ventilation, and air conditioning (HVAC) system of a building. Air
conditioning systems, free cooling systems, absorption cooling systems,
and heat exchangers are all examples of cooling applications that can use
PCMs [234].
De Falco et al. [241] investigated an air conditioning system based
on PCM. The cold TES system tank was integrated into a conventional
chiller fan system, consisting of RT5HC PCM and distilled water. The
co-axial heat exchanger was immersed in the PCM volume. Such a
configuration allowed heat exchange through direct contact between
the PCM and chilled water (cold charging) and was warmed by the user
during cold TES system discharging. This configuration was validated by
a 5-KWh prototype tested in a real environment. Results showed that the
5-kWh storage tank could be ultimately charged in 54 min if the
S.A. Albdour et al.
maximum cooling power of the chiller was 5.7 kW. Additionally, by
reducing the amount of water in the system and increasing the amount
of PCM, stored energy was increased. If the PCM volume was 75% rather
than 60%, the stored energy would have climbed to 6.2 KWh instead of 5
KWh. It is worth mentioning that the 75% PCM volume fraction was
given considering the minimum amount of water head needed to
maintain PCM suction in the exchange circuit.
When the temperature of the outside air at nighttime is lower than
the room temperature, the cooled air can flow through the PCM storage
unit to absorb heat from the liquid PCM. Therefore, at a specific tem­
perature, the PCM begins to solidify. This process comes to an end when
the ambient temperature approaches that of the solid PCM. Later on, the
solid PCM starts to melt after absorbing heat from the hot indoor air.
Cold stored in the PCM is released and circulated when the room tem­
perature increases beyond comfortable levels. This whole process is
known as "free cooling" [242].
Because there is a slight temperature difference between the cold
source and the human comfort temperature level, using a PCM as the
storage medium is recommended to allow for high energy density during
phase change. However, the major obstacle to this technology is the
difficulty of ensuring complete solidification of the PCM if the temper­
ature does not sufficiently drop below the phase-transition temperature.
This problem can be overcome by improving the thermal conductivity of
the PCM [243]. De Gracia et al. [244] experimentally investigated the
ventilated façades of two identical houses under summer conditions,
where one of them was integrated with macro-ePCMs in its air cavity.
Experimental results showed that free cooling during nighttime was
likely to effectively reduce the cooling load of the building. In addition,
thermal resistance of the outer layer of the façade had to be increased;
otherwise, the cold storage system could not be efficiently used.
With varying cold and hot seasons, using a single PCM is not the ideal
strategy to allow for the maximum storage capacity in very extreme
climatic conditions. As a result, combining two or more PCM types with
different properties to form a system capable of operating over a more
comprehensive temperature range is an interesting hybrid solution.
Kheradmand et al. [245] investigated such a solution by using three
different PCMs to prepare plastering mortars for façade walls. The three
PCMs were placed inside the mortar in equal masses. As a binder,
Portland cement was used. Additionally, industrial sand was utilized as
an inert filler. Then, the mortar was mixed. Thermal performance was
analyzed based on realistic daily temperature profiles. The proposed
prototype showed that when compared to conventional mortars (i.e.,
without PCM) or even mortars composed entirely of a single type of
PCM, incorporating multiple PCMs into plastering mortars had the po­
tential to significantly reduce the heating/cooling loads required to
maintain a comfortable interior temperature.
2.6. Conclusions and future research directions
In comparison to liquid-gas and solid-solid PCMs, solid-liquid PCMs
are most frequently used in latent TES applications (e.g., energy storage
in CSP plants, cooling of electronics, and thermal comfort in buildings)
due to their high thermal storage capacity and low volume change
during phase transition. Solid-liquid PCMs particularly offer a great
untapped potential in solar-thermal applications by virtue of their
ability to store heat during exposure to solar radiation and liberate it to
be used during hours of little or no irradiance while maintaining an
almost constant temperature throughout the phase-change transition.
Yet, the most critical challenges hindering the commercial uptake of
solid-liquid PCMs are their poor thermal conductivity (which de­
termines the rate and quality of the charging and discharging processes)
and leakage problems during phase transition. A number of strategies
aimed at mitigating these issues have been developed over the years,
each with their own set of advantages and challenges.
Using fins as extended surfaces to enhance the heat transfer area was
one of the first approaches used to enhance the thermal conductivity of
26
Progress in Energy and Combustion Science 93 (2022) 101037
PCMs. This approach is advantageous due to the low cost and ease of
manufacture of fins, as well as the flexibility of selecting materials with
excellent thermal conductivity. However, their potential is limited by
weight, corrosion, and leakage issues. Cascaded PCM systems are
another approach to accelerate the charging and discharging processes
by replacing a single PCM with multiple PCMs with varying melting
temperatures. Selecting PCMs with proper melting temperatures in a
cascade system is the key to overcoming heterogeneity during the
charging and discharging processes and, therefore, the overall delay in
melting and solidification processes. However, replacing a single PCM
that has a high latent heat of fusion with a number of PCMs with
different properties almost always decreases the overall storage
capacity.
Emulsified PCM systems exhibit dual functionality because of their
higher heat capacity than single-phase liquids and superior fluidity
compared to bulk PCMs. However, microemulsion droplets that spon­
taneously form with the help of surfactants and mild agitation are the
only type that is classified as thermodynamically stable. Moreover, long-
term stability under cyclic loading is poorly investigated. Relative to all
alternatives, the nano-enhanced PCM technique is considered the most
investigated strategy to enhance the poor thermal conductivity of PCMs.
This technique has shown some improvements in thermal conductivity;
however, issues pertaining to leakage and stability remain largely un­
resolved. Most recently, both shape-stabilized and encapsulated PCM
systems were found to effectively boost heat conductivity through
increasing exposed surface area. These two strategies are the most
promising with further investigations necessary to resolve mechanical
stability, leakage, and supercooling issues.
In addition to these mitigation strategies for the low-thermal-
conductivity and leakage issues, it is recommended for future research
in PCMs to be directed towards investigating PCM flammability (espe­
cially for building-integrated applications), understanding the moving
boundary interface mechanism, and optimizing and testing the hierar­
chically porous configuration of shape-stabilized PCM systems (which
has been shown to offer extremely high energy storage capacities).
3. An introduction to micro/nano-ePCMs for solar photothermal
conversion
3.1. Encapsulation methods of PCMs
Encapsulation is a widely employed technique in different industries,
such as pharmaceuticals, agriculture, cosmetics, food, and fragrances
[246,247]. This technique has recently been used for PCMs to enhance
their thermal and physical characteristics. Nano- or micro-PCMs are
coated with a thin shell to protect and isolate the PCM from the envi­
ronment and prevent leakage during the melting process. They can be
fabricated using a variety of methods, depending on the characteristics
of the PCM to be encapsulated and the type of shell. These methods are
categorized as physical, chemical, and physical-chemical methods,
which will be discussed in the following sections. Fig. 24 shows a
detailed classification of various PCM encapsulation methods. Further­
more, the advantages and disadvantages of different encapsulation
methods are summarized in Table 7.
3.1.1. Physical methods
Using physical methods, the fabrication of PCM capsules includes
only physical procedures, namely dehydration, drying, and adhesion.
ePCMs are made using a variety of physical methods, such as spray-
drying, solvent evaporation, air suspension coating, pan coating,
vibrational nozzle, and centrifugal extraction. A number of important
observations regarding the suitability of these methods for encapsu­
lating PCMs are as follows:
S.A. Albdour et al.
Fig. 24. The main physical, chemical, and physical-chemical methods for the encapsulation of PCMs.
• In the pan coating technique, the melting temperature of the PCM
must be greater than the melting temperature of the shell. Therefore,
this technique cannot be employed for PCM encapsulation [156].
• The air suspension coating method was developed for the food and
pharmaceutical industries, as well as cosmetic products, but was
found to be unsuitable for encapsulating PCMs [248,249].
• The encapsulation of PCMs using centrifugal extraction and vibra­
tional nozzle techniques has not been reported in the literature.
• Spray-drying and solvent extraction/evaporation techniques are the
most prevalent physical methods for encapsulating PCMs.
Spray drying method. The spray-drying technique involves an emulsion
where the PCM (the core material) is dispersed in a concentrated liquid
to form the shell, until the desired capsule size is achieved. The droplets
or particles obtained by pulverized emulsion are dried upon contact with
a hot medium where fast evaporation of the water or solvent occurs
instantly, thus allowing the PCM to be trapped within an encapsulating
material. This method is reported to be appropriate for encapsulating
materials with heat sensitivity. Therefore, it is commonly employed in
the pharmaceutical and food industries [250]. As shown in Fig. 25, this
technique consists of 1) spraying the emulsion in small particles or
droplets using an atomizer, 2) placing the mixture in contact with the
heated gas at a desired temperature for solvent evaporation, and 3)
using cyclones and/or filters to separate the solid particles transported
by the gas stream [157,251].
The spray drying method was only used for organic micro-ePCMs,
resulting in microcapsules with a size range of 0.5− 1000 µm, an
encapsulation efficiency of 71− 87%, and a core content of 29− 80%
[225–227].
Solvent extraction/evaporation method. PCMs can be encapsulated using
a solvent extraction evaporation method (also known as a phase-
separation method) via the following steps: 1) preparation of a poly­
mer solution via shell dissolution in a volatile solvent, 2) addition of
27
Progress in Energy and Combustion Science 93 (2022) 101037
PCMs to the solution to produce an O/W emulsion, 3) formation of shells
on droplets via solvent evaporation, and 4) capsule formation via drying
and filtration. A schematic overview and detailed description of the
process of encapsulating PCMs using this method are reported in [252].
Several researchers used the solvent evaporation method to micro­
encapsulate organic [253] and inorganic [212] PCMs. This method leads
to capsules with a size range of 0.5− 10 µm, encapsulation efficiency of
56− 64%, and a core content of 43− 53%. In contrast, studies on the
fabrication of nano-ePCMs using this method have not been reported in
the literature.
3.1.2. Chemical methods
In general, chemical methods are based on condensation or poly­
merization processes of oligomers, prepolymers, and monomers as raw
substances to produce shells at the O/W interface. The most common
chemical methods for PCM encapsulation are emulsion polymerization,
suspension polymerization, interfacial polymerization, and in-situ
polymerization. An overview of these polymerization methods is more
thoroughly described below.
Interfacial polymerization. In the interfacial polymerization (or poly­
condensation) method, as illustrated in Fig. 26, lipophilic and hydro­
philic monomers (A and B) are dissolved in a mixture of two immiscible
phases (aqueous solution and oil), and then polymerization takes place
at the oil-water interface. The following are the general steps in inter­
facial polymerization: 1) preparing an oil-in-water emulsion that con­
tains hydrophobic monomer and core material, 2) polymerization
occurs by adding a hydrophilic monomer under suitable conditions, and
3) micro- or nano-capsules are filtered, washed, and dried [254].
Several studies have been carried out to fabricate micro-ePCMs using
the interfacial polymerization method [159,163,255–261,247,249–251,
253,254]. It is revealed that this method is used for both organic and
inorganic PCMs and results in microcapsules with a size range of 2-30
µm, encapsulation efficiency of 82-90.7%, and a core content of
46-74%. On the other hand, limited studies have reported the
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Table 7
Advantages and disadvantages of different encapsulation methods.
Method Advantages Disadvantage(s)

Physical Spray drying • Versatile. • High temperature

methods • Large-scale range.
production. • Low encapsulation
• Easily controlled efficiency.
and scaled-up. • Presence of
• Low cost. uncoated particles.
• Agglomeration of
particles.
• Limitation in
achieving a very
small particle size.
Solvent • Low-cost process. • Lab-scale
evaporation • Easy to scale-up. production.
Chemical Interfacial • Versatile. • High wall
methods polymerization • Controllable to permeability.
produce • Difficulty in
homogeneous control.
morphology. Fig. 25. A schematic illustration of the spray drying method (physical method)
• Degradability. for encapsulating PCMs.
• Mechanical
resistance.
substance, and a monomer or polymer is added to form the shell.
• Protective
atmosphere is not
Polymerization occurs via three possible ways after the system has been
required. emulsified [247]: 1) propagation of monomers by adding a free radical
• Low cost. into the emulsifier micelle, 2) as the chain length of the free radical
Emulsion • Uniform coating. • Uniform size in exceeds the solubility limit of the medium, it precipitates and forms a
polymerization Low cost. only oiled systems.
particle nucleus, or 3) propagation can ensue after adding monomer
•
• Fast production. • Limited for liquid
PCMs. droplets containing the PCM, which is produced by proliferation of free
• Multiphases of radicals in the medium. The method of miniemulsion polymerization is
solution. similar to that of emulsion polymerization, with the exception that
In-situ • Nano/micro-scale • High cost and skill.
smaller droplets can be produced due to the effect of high shear forces.
polymerization production.
• Uniform
The emulsion polymerization technique is widely employed for
morphology and producing PCM microcapsules [159, 243–251,264,265]. The published
coating. data indicated that this method is used for both organic and inorganic
• Good chemical PCMs and results in microcapsules with a size range of 0.14-2 µm,
and thermal
encapsulation efficiency of 83%, and a core content of 28-81%. The
stability.
Suspension • Controllable. • High-cost fabrication of nano-ePCMs is also possible mostly via the mini-emulsion
polymerization • Low cost. equipment. polymerization method. For example, Baek et al. [266] fabricated
• Heat can be • Not all monomers nano-ePCMs with octadecane as the PCM and PS as the shell. Fang et al.
controlled during are water soluble.
[267] prepared nano-ePCMs for a cold TES system using PS as the shell
reaction.
Physical- Coacervation • Uniform • Agglomeration of
and n-tetradecane as the core material. Their results indicated that all
Chemical method morphology. particles. the nano-ePCMs were coated and had a spherical morphology with a
methods • Low temperature • Difficulty in mean diameter of 132 nm. In another study [268], the PCM was replaced
range. control. by n-octadecane instead of n-tetradecane. The nano-ePCMs showed a
• Efficient control of • Limited to scale up.
spherical shape with mean diameter ranging from 100 to 123 nm.
particle size.
Sol-gel method • Shell with high • Used only for Fuensanta et al. [269] produced nano-ePCMs by using paraffin as the
thermal inorganic shell. core and styrene butyl acrylate copolymer as the shell. The capsules
conductivity. showed a spherical shape with an encapsulation efficiency of 80 wt%
and a particle size range of 52− 112 nm. Wang et al. [270] successfully
nano-encapsulated EASA with PMMA. The morphology characteristics
nanoencapsulation of PCMs using this method. Shi et al. [262] produced
indicated that the size of the nano-ePCMs was 46 nm while the encap­
nano-ePCMs with PMMA as a shell and paraffin as a PCM. The obtained
sulation ratio was 68.8%. Graham et al. [271] synthesized nano-ePCMs
ePCMs were spherical with a mean diameter of 200− 400 nm and a core
with poly(ethyl-2-cyanoacrylate) (PECA) as the shell and Mg
content of 52.95%. Nikpourian et al. [263] prepared nano-ePCMs with
(NO3)2⋅6H2O as the PCM. The nano-ePCMs possessed a spherical shape
paraffin wax as the PCM and polyurethane (PUR) as the shell. The
with a mean diameter of 100-200 nm.
produced nano-ePCMs had a spherical shape with a mean diameter of
25− 185 nm and a core content of almost 80%.
In-situ polymerization. In this method, the ePCMs are formed in the same
way as in the direct emulsion technique, where the formation of capsules
Emulsion/ Mini-emulsion polymerization. The method of emulsion poly­
is generated in micelles formed in a system of two immiscible sub­
merization, as shown in Fig. 27, includes the formation of droplets or
stances. The fundamental difference is that the shell is formed with the
particles through the emulsion of a lipophilic substance in another hy­
addition of a pre-polymer, where the polymerization occurs only in the
drophilic substance, which is known as direct emulsion. On the other
continuous phase. To accomplish this, no reactants are used in the core
hand, the formation of an emulsion of a hydrophilic substance in a
substance. The following steps outline the process: 1) a PCM emulsion is
lipophilic substance is called an indirect or inverse emulsion. In both
formed in water, 2) PCMs are encapsulated by adding pre-polymers to
direct and indirect emulsions, the addition of a surfactant or an emul­
the agitated emulsion, and 3) the PCM capsules are washed and dried.
sifier which modifies the interfacial activity is required to make the
One of the limitations associated with this process for inorganic PCMs is
system stable [11]. The encapsulated PCM is dissolved in another

28
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 26. A schematic illustration of the interfacial polymerization method (chemical method) for encapsulating PCMs.

Fig. 27. A schematic illustration of the emulsion/miniemuslion polymerization method (chemical method) for encapsulating PCMs.

that other reactive components and monomers must be water-soluble,
particularly for salt-based PCMs [272]. Fig. 28 depicts the in-situ poly­
merization technique used for PCM encapsulation.
The in-situ polymerization method has attracted the interest of many
researchers [249,164]. The produced capsules had a size of 0.1− 0.5 µm,
encapsulation efficiency of 80− 82.2%, and a core content of 8− 60%.
Similarly, several studies have been performed on the fabrication of
nano-ePCMs using this method. For example, Hu et al. [273,274] syn­
thesized nano-ePCMs by using carboxymethyl cellulose-melamine
formaldehyde as a shell and paraffin as the core. The obtained cap­
sules were spherical with a 50-nm mean diameter. Fang et al. [268]
produced nano-ePCMs using n-tetradecane as the PCM and
urea-formaldehyde (UF) as the shell. They observed that the
nano-ePCMs had a diameter of 100 nm with a mass content of 60%. Niu
et al. [275] micro/nano-encapsulated n-octadecane with
melamine-formaldehyde (MF). Karthikeyan et al. [276] prepared
nano-ePCMs using UF as a shell and PEG as a PCM. The obtained
nano-ePCMs showed a spherical morphology with a 141-nm mean
diameter.
Suspension polymerization. The fabrication of ePCMs using the suspen­
sion polymerization method usually follows two main steps. The first is
the preparation of a suspension containing monomers, PCMs, and ini­
tiators as droplets in an aqueous continuous liquid phase using
mechanical stirring and surfactants. The second step involves initiation
of polymerization at the desired thermal condition until completion
[277]. The size of the obtained capsules is affected by the concentration
of surfactants and the monomer phase, stirring rate, and viscosity of the
droplets and suspension medium [278,279]. The suspension polymeri­
zation method is illustrated in Fig. 29.
Various researchers have prepared micro-ePCMs using the suspen­
sion polymerization method [280,271]. The reported data revealed that
this method is only used for organic PCMs and leads to microcapsules
with a size range of 0.72− 237 µm, an encapsulation efficiency of
78− 100%, and a core content of 20− 75.3%. In contrast, no research
studies have been reported on the preparation of nano-ePCMs using the
suspension polymerization method.
3.1.3. Physical-Chemical methods
The physical-chemical technique is a mixture of the chemical and
physical methods that have been described earlier. The most widely
utilized and representative physical-chemical methods for microencap­
sulation are the coacervation (or phase separation) and sol-gel methods,
as described below.
Coacervation method. The coacervation process can be divided into two
variants—complex and simple coacervation. The microcapsule produc­
tion technique is the same in both cases [281], with the difference lying

Fig. 28. A schematic illustration of the in-situ polymerization method (chemical method) for encapsulating PCMs.

29
S.A. Albdour et al.
Fig. 29. A schematic illustration of the suspension polymerization method (chemical method) for encapsulating PCMs.
in the way the phase separation is accomplished. Complex coacervation
takes place through the interaction of two polymers that are oppositely
charged [282], while in simple coacervation, a coacervating (or des­
olvating) agent is introduced for phase separation. The interaction be­
tween a low molecular material and a dissolved polymer results in a
simple coacervation process. Complex coacervation produces micro­
capsules with higher stability and more homogeneous morphologies and
sizes. In this method [283], there are three different steps: 1) the
emulsion is prepared through the addition of PCM to an aqueous poly­
mer solution, 2) the shell material is then deposited onto the PCM by
introducing another aqueous polymer solution, followed by the addition
of salt, modifying the temperature, adjusting the pH, or diluting the
medium, and 3) the microcapsules are then stabilized using desolvation,
crosslinking, or thermal treatment. An overview of the coacervation
method is illustrated in Fig. 30.
A number of studies have been performed on the microencapsulation
of PCMs using the coacervation method [284,158]. This method is used
only for inorganic PCMs and results in a capsules size of 2− 1200 µm, an
encapsulation efficiency of 80− 95%, and a core content of 26− 67%. In
contrast, no studies have been performed on the nano-encapsulation of
PCMs based on this method.
Sol-gel method. The term “sol-gel” corresponds to the abbreviation "so­
lution-gel". The "sol" is a colloidal suspension of oligomers with a
diameter of only a few nanometers. Subsequently, this "sol" can be
evolved, through chemical reactions, into a network with infinite vis­
cosity, called a “gel”. This network is linked by covalent and hydrogen
bonds and van der Waals forces [285]. The sol-gel method is an
economical technique for synthesizing PCM capsules. The following are
the main steps in the preparation of ePCMs using this method: 1) the
reactive substances (including precursor, solvent, PCMs, and emulsifier)
are suspended in a continuous solution to obtain a colloidal suspensions
via a hydrolysis mechanism, 2) a three-dimensional oxide network (gel)
is formed via condensation polymerization, and 3) sintering, curing, and
drying processes are used to create the ePCMs [285]. The sol-gel process
is depicted in Fig. 31.
Many studies have been reported on the micro-encapsulation of
PCMS using this method [161,286–290,306–310]. The reported data
has shown that this method is used for both organic and inorganic PCMs
and led to capsule sizes of 2− 30 µm, an encapsulation efficiency of
82− 90.7%, and a core content of 46− 74%. However, very few studies
have been conducted at the nanoscale. Latibari et al. [291] prepared
Fig. 30. A schematic illustration of the coacervation method (physical-chemical method) for encapsulating PCMs.
30
Progress in Energy and Combustion Science 93 (2022) 101037
nano-ePCMs containing silica as a shell and PA as a PCM. The obtained
capsules were spherical with sizes of 722.5, 466.4, and 183.7 nm at the
pH values of 12, 11.5, and 11, respectively. The encapsulation ratio and
efficiency at a pH of 11 were 83.25% and 82.53%, respectively. In
another study, Latibari et al. [292] synthesized nano-ePCMs with titania
as a shell material and SA as the PCM. Their results revealed that the
nano-capsules had spherical profiles with mean diameters in the range
of 317.6 to 946.4 nm and an encapsulation ratio in the range of 30.36 to
64.76%. Yuan et al. [293] prepared nano-ePCMs with silica as a shell
and SA as the PCM. The nano-ePCMs were found to be well dispersed
and spherical, with a mean diameter of approximately 350 nm.
Recently, Lee and Jo [294] nano-encapsulated a PCM mixture of 40 wt%
KNO3 and 60 wt% NaNO3 by silica shells. It was found that the
nano-ePCM diameter was almost 420 nm.
3.2. Compositional, morphological, and structural characterization
techniques of ePCMs
Various techniques have been used to identify the morphology, size,
core@shell structure, stability, and thermophysical properties of ePCMs.
The most widely used characterization techniques can be classified into:
1) microscopy techniques (SEM, TEM, and AFM), 2) X-ray techniques
(XRD, EDX, XPS, SAXS, and WAXS, 3) non-X-ray spectroscopic tech­
niques (FTIR, Raman spectroscopy, and UV-Vis-NIR), and 4) thermal
techniques (DSC and TGA). In the following sections, a detailed
description of each characterization technique is provided. Moreover,
some of the results obtained by using these techniques are presented.
Fig. 32 shows a detailed classification of various ePCM characterization
techniques.
3.2.1. Electron microscopy techniques
Scanning electron microscopy (SEM). Scanning electron microscopy
(SEM) is based on the scanning of a high-energy electron beam (e.g., 20
keV) over the surface of the material. Three signals are produced when
the electron beam is focused on the surface of the sample; namely,
backscattered electrons (electrons that are reflected by the sample),
secondary electrons (electrons that are emitted from the sample), and X-
rays. Details on the morphology and elemental composition of the
sample are revealed from these signals [295]. The produced image has a
resolution of almost 5 nm and a high magnification of 100,000. SEM is
used to visualize and characterize particle size distribution, surface
S.A. Albdour et al.
Fig. 31. A schematic illustration of the sol-gel method (physical-chemical method) for encapsulating PCMs.
Fig. 32. Compositional, morphological, and structural characterization tech­
niques for encapsulated PCMs.
morphology, agglomeration of particles, particle shape, single-particle
analysis, and surface functionalization. The main drawback of SEM is
that the process takes place under a high vacuum. Consequently, wet
samples cannot be analyzed or characterized via SEM. Several studies
have been reported on the morphology, crystallography, and chemical
composition of different types of ePCMs using the SEM technique. For
example, recently, Zhu et al. [296] presented SEM images of SnBi58/­
TiO2 micro-ePCMs, where it was shown that the capsules had a spherical
shape with a size of 30 ± 15 μm without surface defects.
Transmission electron microscopy (TEM). Transmission electron micro­
scopy (TEM) is the most widely used technique for characterization of
ePCMs. TEM uses a beam of electrons (100− 1000 keV), which is
described by the wave-particle duality concept. A TEM device consists of
an electromagnetic lens, an electron emission source, and an electron
detector. The electron beam is produced, accelerated, and then focused
by the lenses on the sample. The beam alters and imprints the image of
the sample as it travels through it. The image is then magnified by lenses
and detected [295]. TEM allows magnification and chemical identifi­
cation of very thin samples down to atomic dimensions. The limitations
of the TEM technique are that it is very time-consuming, expensive, and
requires a high level of skill. Various research studies have been con­
ducted on analyzing the microstructure of ePCMs using TEM. Lan et al.
[297] showed the TEM results of nano-ePCMs containing n-octadecane
31
Progress in Energy and Combustion Science 93 (2022) 101037
as PCM and SiO2/BN as a shell. It was observed that all nano-ePCMs
possessed a core@shell structure, indicating that the PCM was well
encapsulated by the shell. The shell thickness, diameter, and
core-to-shell ratio of nano-ePCMs were also measured using TEM.
Atomic force microscopy (AFM). Atomic force microscopy (AFM) is a
surface analysis technique employed for analyzing nanomaterials. AFM
measures various forces (including magnetic forces), adhesion strength,
and mechanical properties. It provides information on the physical
properties of the sample, including morphology, size, surface roughness,
and texture. Statistical information, including area, particle distribution,
and size, can also be determined. A wide variety of particle sizes can be
characterized (1 nm-8 µm) using AFM. Different surface measurements
are provided with 3D topography so that it is possible to measure the
nano/microparticle height. Furthermore, AFM is simple to operate and
very cost-effective. However, there are some limitations, such as sample
breakage during detection and limited magnification [298]. For
example, Huang et al. [299] measured the roughness of ePCMs made of
MF as the shell and n-octadecane as the core using AFM. The measured
root-mean-square roughness and the average roughness were 21.09 and
17.12 nm, respectively.
3.2.2. X-ray techniques
X-ray diffraction (XRD). X-ray diffraction (XRD) is used to measure the
average spacing between layers or rows of atoms, find the crystalline
structure, measure the size, determine the orientation of a single crystal,
and evaluate whether the material is crystalline or amorphous [300].
XRD is similar to the diffraction of neutrons or electrons. However, the
only difference is in the mechanism of scattering. In addition to some
size limitations (measuring small crystalline structures is inaccurate), a
disadvantage of this technique is that the sample must be homogeneous,
single-phased, and very small. Lin et al. [301] reported the XRD analysis
of micro-ePCMs with MA as the PCM and ethyl cellulose as the shell. It
was demonstrated that the shell possessed a good crystalline structure
and that the PCM maintained a complete and stable crystal state. Wang
et al. [302] analyzed the structure of nano-encapsulated palmic acid
with silica using XRD analysis. The XRD patterns of silica powder indi­
cated that the silica was amorphous, while the XRD patterns of the
nano-ePCMs revealed the coexistence of amorphous silica and crystal­
lized PCM in the nano-capsules.
Energy-dispersive X-ray spectroscopy (EDX). Energy dispersive X-ray
spectroscopy (EDX, EDS, EDXS or XEDS), also known as energy-
dispersive X-ray microanalysis (EDXMA) or energy-dispersive X-ray
analysis (EDXA), is an analytical technique which uses X-rays generated
by the solid sample during electron beam bombardment to quantify and
identify the chemical composition of the sample at the micro or
S.A. Albdour et al.
nanoscale [303]. EDX systems are usually used in conjunction with an
electron microscope, such as an SEM or TEM. The main disadvantages of
this method are: 1) it can be destructive in many cases, 2) peaks are
obtained with poor energy resolution, 3) surface senility, and 4) quan­
titative examination of heterogeneous materials often yields inaccurate
results. Chai et al. [290] used an EDX spectrometer coupled with SEM to
determine the chemical composition of micro-ePCMs containing
n-eicosane as the core and titania as the shell. The EDX pattern revealed
the existence of two peaks corresponding to O and Ti elements, which
indicates the formation of a titania shell. Moreover, the calculated mole
ratio of O/Ti indicated an O2− TiO2 shell with a higher number of hy­
droxyl groups. Karthikeyan et al. [276] performed an elemental analysis
of nano-ePCMs made of PEG as the PCM and urea UF as the shell. EDX
results demonstrated that the PCM consisted of C and O atoms. The
encapsulation of the PCM with UF was confirmed by the presence of N
atoms. The chemical composition of the PCM was 55 wt% C, 38 wt% O,
and 55 wt% C, while that of the nano-ePCM was 27 wt% O, 38 wt% C,
and 35 wt% N.
X-ray photoelectron spectroscopy (XPS). X-ray photoelectron spectros­
copy (XPS), also known as electron spectroscopy for chemical analysis
(ESCA), is a technique for determining the elemental composition of
mesoporous samples based on the electronic state of the elements pre­
sent in a powder sample. During the measurement, high-energy X-rays
impinge on the sample, causing the generation of photoelectrons via the
ejection of core electrons from the sample. Then, the kinetic energy of
the photoelectrons is collected and measured by the spectrometer so that
the binding energy can be calculated. From the binding energy, we can
evaluate the oxidation state of elements and which element the electron
came from [304]. The main drawbacks of this method are the size
limitation and the high vacuum environment. XPS spectra of n-eicosa­
ne@TiO2 micro-ePCMs were presented by Chai et al. [290]. They
observed two signals corresponding to Ti2p3/2 and Ti2p1/2 at 458.7 and
464.5 eV, respectively, indicating the presence of Ti in a trivalent state.
Moreover, the absorption characteristics revealed the presence of the
shell in the micro-ePCM. The obtained results of the XPS analysis
showed that the core-shell structure was successfully produced.
Small-angle X-ray scattering (SAXS). Small angle X-ray scattering (SAXS)
is an analytical technique for measuring the scattered X-ray intensities
Fig. 33. Schematic illustration of WAXS and SAXS techniques. Both techniques can be performed simultaneously or interchangeably by adjusting the sample-to-
detector distance.
32
Progress in Energy and Combustion Science 93 (2022) 101037
with respect to the incident beam direction. Measurements are per­
formed at very small angles between 0.1 and 5 degrees. SAXS is a pri­
mary structural characterization technique of nanocomposites and
nanomaterials. The sample can be solid, powder, gel, or liquid, and it
can be amorphous, crystalline, or semi-crystalline. From evaluation of
the measured diffusion profiles, information about the structure and
properties of the material can be obtained, such as the particle shape,
size, and distribution, aggregation behavior, and liquid crystal phases.
One of the main limitations of this method is the high cost and
complexity of instrumentation [305]. It should be noted that very few
studies have examined ePCMs using SAXS. In one such study, Li et al.
[306] used SAXS measurements to confirm the absence of leakage
during heating/cooling cycles.
Wide-angle X-ray scattering (WAX). Wide-angle X-ray scattering (WAXS)
and SAXS are complementary techniques. WAXS has an atomic resolu­
tion of 1-0.1 nm, while SAXS has a nanoscale resolution of 1-100 nm. As
a result, SAXS is often employed to investigate the larger scale bulk
microstructure inside a sample, whereas WAXS is more akin to XRD and
can observe atomic features [305]. SAXS and WAXS can be done
concurrently and easily interchanged. This simply involves moving the
sample and detector farther apart or closer to each other, as illustrated in
Fig. 33. It should be mentioned that studies on the characterization of
ePCMs using this technique are rarely reported. For example, He et al.
[307] confirmed the crystallinity of micro-ePCMs containing n-octade­
cane as core and silica as shell. They indicated that the silica wall was
amorphous using a WAXS analysis.
3.2.3. Non-X-ray spectroscopic techniques
Fourier-transformed infrared spectroscopy (FTIR). Fourier-transformed
infrared spectroscopy (FTIR) is used to identify inorganic or organic
samples. It measures the IR absorption of the sample as a function of
wavelength. The absorption bands in the IR spectra describe the mo­
lecular structures and components of the sample. When IR radiation is
absorbed by the sample, molecules are excited into a higher vibrational
state. The energy difference between the excited and at-rest vibrational
states is a function of the wavelength of the absorbed IR. The absorbed
wavelengths are characteristic of the molecular structure [308]. FTIR
spectra are generally presented as plots of the percentage of light
S.A. Albdour et al.
absorbance or transmittance at each wavenumber. One of the main
limitations of this method is that it can only be used for samples that
completely absorb IR. Zhang et al. [309] investigated the chemical
stability and composition of nano-ePCMs using FTIR, where the core and
shell were respectively confirmed to be composed of n-octadecane and
pentafluorostyrene.
3.2.3.44. Raman spectroscopy. Similar to FTIR, Raman spectroscopy is a
molecular spectroscopy technique that relies on the interaction of light
with matter to determine the composition and characteristics of the
sample under study. While IR spectroscopy is based on the absorption of
light, the information obtained by Raman spectroscopy results from the
process of light scattering. Raman spectroscopy provides information on
intramolecular and intermolecular vibrations. FTIR and Raman spec­
troscopies define the characteristic spectrum of the vibrations of a
molecule (chemical fingerprint) to identify a substance. However,
Raman spectroscopy provides additional information on lower fre­
quency modes and on the vibration characteristics of crystal lattices and
molecular structures. The main drawbacks of this method are: 1) it
cannot be employed for alloys or metals and 2) the material can be
destroyed if it is heated by intense laser radiation [310]. It should be
emphasized that studies on the characterization of ePCMs using this
technique are rarely reported. Yuan et al. [311] employed Raman
spectroscopy to identify the grapheme oxide (GO) on the silica shell of
micro-ePCMs containing paraffin as PCM and silica/GO as the shell. The
Raman spectrum of paraffin@silica/GO micro-ePCMs showed two peaks
of graphene, while no peaks were observed for paraffin@silica, indi­
cating that the grapheme was successfully impregnated in the silica
shell.
Ultra-violet-visible- near infrared spectroscopy (UV− Vis− NIR). Ultra-vio­
let–visible–near infrared (UV–Vis–NIR) spectroscopy examines a wide
range of wavelengths. The wavelengths measured in the UV–Vis region
range from around 200 to 800 nm. When a molecule absorbs visible or
UV radiation, it causes transitions between its electronic energy levels.
This technique is suitable for determining the electrical and optical
properties of a wide range of materials, including powders, films, liq­
uids, and solids. Wavelengths of 800-2500 nm are used in the NIR region
of the spectrum. The measured transitions in this region are related to
electronic transitions as well as vibrational motions. This technique can
only be used for samples of high absorbance. Huang et al. [312] used
UV–Vis–NIR spectroscopy to determine the optical properties of
micro-ePCMs, fabricated with n-eicosane as a core and two different
shells (PMMA and PMMA/BPs). It was shown that micro-ePCMs with
and without modified BPs exhibited high and low light absorption ca­
pacities, respectively.
3.2.4. Thermal techniques
Differential scanning calorimeter (DSC). DSC is a thermo-analytical
technique that measures the heat flow to or from a material as a func­
tion of time while the material is subjected to controlled temperature. It
is a very effective method to examine such material properties such as
melting, glass transition temperature, specific heat capacity, purity,
thermal stability, variations in material oxidation, crystallinity, and
composition. DSC analysis is used to evaluate a variety of materials,
including organic materials, polymers, composites, plastics, metals, and
coatings. The main limitations of this technique are as follows: 1)
quantitative analysis of individual processes is impossible, 2) result
interpretation is frequently difficult, 3) it is sensitive to any sample
changes, and 4) optimizing both resolution and sensitivity during
measurement is not possible [313]. Methaapanon et al. [314] used DSC
analysis to study the latent heat of fusion, crystallization, and melting
point of microencapsulated methyl palmitate and n-octadecane with a
silica shell. They found that the melting temperature of the micro-ePCMs
33
Progress in Energy and Combustion Science 93 (2022) 101037
was slightly higher than that of the PCM.
Thermogravimetric analysis (TGA). Thermogravimetric analysis (TGA),
or simply thermogravimetry, is another type of thermal analysis
commonly employed to evaluate change in the chemical and physical
properties of ePCMs. TGA measurements are conducted as a function of
time by considering both temperature and mass loss constant, or as a
function of temperature at a fixed heating rate. Through TGA analysis,
chemical (such as dehydration or decomposition) and physical (such as
vaporization, phase transition, or desorption) phenomena can be
examined. Moreover, the thermal stability of PCMs can be measured.
The limitations of this method are that 1) it is only relevant to solid
particles and 2) temperature measurements are not very accurate. Ma
et al. [315] used TGA to show that micro-encapsulated paraffin and
butyl stearate with PUR/PU degraded in three different steps at a rela­
tively low temperatures, indicating that these micro-ePCMs possessed
high thermal stability.
3.3. Stability of ePCM slurries/dispersions
Slurries and dispersions of ePCMs, also called latent functionally
thermal fluids (LFTFs), are generally prepared by suspending ePCM
particles of different sizes, shapes, and core@shell types in a carrier
fluid. It is important to note that the terms "dispersion" and "slurry" both
refer to the two-phase solid-liquid system formed by suspending solid
particles in the carrying fluid. However, in the case of a dispersion, the
particles are so small that they do not settle in the absence of flow, which
is attributed to their Brownian motion (e.g., many nano-ePCMs). On the
other hand, in a slurry, the particle size is typically larger, such that
particles will sediment and settle in the absence of flow (e.g., most
micro-ePCMs). Suspension is a more general term that can incorporate
both nano- and micro-ePCMs.
Slurries and dispersions offer the following benefits: 1) storing and
releasing large amounts of thermal energy with minimal temperature
changes, 2) having a large heat capacity during the phase-change pro­
cess, 3) having higher heat transfer rates at constant temperatures, and
4) having good stability under higher shear forces and during heating/
cooling cycles. In the following, we will present the most important
requirements for ePCMs to reach the state of thermal, chemical, and
physical stability. Also, the adopted stabilization strategies and stability
evaluation techniques related to ePCM slurries/dispersions are reported.
3.3.1. Stability requirements for an ePCM
The main challenge of ePCMs is their stability while being used in
their intended application. Therefore, enhancing the stability of ePCMs
and understanding their physical, chemical, and thermal behavior is
highly desired before commercialization and long-term use. The most
common techniques for measuring the stability of ePCMs are AFM, TGA,
DSC, SEM, and FTIR. This section therefore reviews the research studies
devoted to the stability of ePCMs.
Physical stability. The physical (or mechanical) stability of ePCMs is an
important factor that determines their failure or success in practical
deployments. ePCMs should be strong enough to resist shear stress
during fluid flow; otherwise, they may undergo serious damage. Despite
this fact, limited attention has been paid to the measurement of the
mechanical stability of ePCMs. Su et al. [316] investigated the me­
chanical properties of MF encapsulating n-dodecanol by observing
change in the ePCM morphology after pressure application. As show in
Fig. 34, the micro-ePCMs were compressed between two horizontal
plates made of glass. It was found that when the core-to-shell ratio was
3:1, there existed an optimum yield point beyond which the
micro-ePCMs exhibited plastic behavior. This result was attributed to
the shell material reaction and cross-link density. As a result, the me­
chanical behavior of micro-ePCMs was affected by the yield point value.
S.A. Albdour et al.
Fig. 34. Schematic illustration of the mechanical stability measurement of
micro-encapsulated PCMs via the compression of capsules between two hori­
zontal plates made of glass.
Moreover, the mechanical stability of double-shell micro-ePCMs was
shown to be higher than that of single-shell micro-ePCMs. In another
study, Su et al. [317] compared the mechanical properties of
methanol-modified MF shells with unmodified MF shells, both con­
taining paraffin. They revealed that the mechanical properties of the
shell made of methanol-modified MF presented a higher yield-point
value compared to the unmodified MF shell, indicating that methanol
modification can improve the deformation resistance of MF shells.
Borreguero et al. [264] performed a mechanical test for
micro-ePCMs containing paraffin as a PCM and polyethylene-ethylene
vinyl acetate as a shell, with and without carbon nanofibers (CNFs) in
the core. Their results showed that micro-ePCMs with CNFs could
withstand more pressure force compared to micro-ePCMs without CNFs,
as illustrated in Fig. 35. In fact, it was shown that when 2 wt% CNFs
were added to the core, the force required to generate the same micro­
capsule deformation was almost 183% higher. The addition of CNFs
increased the stiffness of the micro-ePCMs, and consequently the
Young’s modulus of the micro-ePCMs was increased. Giro-Paloma et al.
[318] studied the effect of PCM core type (paraffin or palmic acid) on the
mechanical properties of micro-ePCMs encapsulated with PScEA.
Micro-ePCMs with paraffin showed the same mechanical properties at a
temperature range between 25 and 50 ◦ C. However, the micro-ePCMs
with palmic acid presented different mechanical behaviors between 25
and 70 ◦ C. Specifically, the Young’s module was the same, while the
force to deform the micro-ePCMs at 70 ◦ C was found to be ten times
lower compared to the case at 25◦ C. Giro-Paloma et al. [319] examined
the mechanical properties of ePCMs containing tetracosane as a PCM
and PS or PMMA as a shell at different core-to-shell ratios (1:1 and 1:3).
It was found that with a ratio of 1:3, the PS shell was a better option
when the PCM was in its liquid state since the evaluated effective
Young’s modulus was reduced by almost 350%. However, the shell
Fig. 35. Applied force versus deformation of micro-encapsulated PCMs
(paraffin as core and LDPE-EVA as shell) with and without CNFs in the core
[264]. (Reused with permission from Elsevier).
34
Progress in Energy and Combustion Science 93 (2022) 101037
material had no effect on the force required to break the micro-ePCMs.
Moreover, the effective Young’s modulus for the core-to-shell mass ratio
of 1:3 was greater than that of 1:1. Therefore, micro-ePCMs with PS
possessed a higher stiffness. In a number of other studies, different
micro-ePCMs were fabricated with different shell materials, involving
UF and MF with various PCMs [304–306]. The results indicated that for
a given shell thickness and micro-ePCM size, micro-ePCMs with a MF
shell were stronger compared to ePCMs with UF shells. However, they
both ruptured with a larger deformation. The authors concluded that the
deformability and strength of micro-ePCMs were dependent on their
synthesis process and formulation. Hu et al. [320] found that the size of
micro-ePCMs had a considerable impact on the mechanical strength of
microencapsulated dicyclopentadiene with MF, and that large
micro-ePCMs are weaker. It was concluded that the mechanical strength
can be controlled through change in the reaction time for producing
micro-ePCMs with various shell thicknesses.
Yin et al. [321] produced micro-ePCMs with dodecanol as the PCM
and polymer/silica as a hybrid shell. Their results showed that the
addition of silica in the shell or divinylbenzene (DVB) to the PCM
increased the mechanical strength of the shell. However, the addition of
high DVB content led to breakage of micro-ePCMs. Fig. 36 (a) and (b)
depict a typical core@shell structure and a broken micro-ePCM,
respectively. Qiu et al. [322] fabricated micro-ePCMs containing
n-octadecane as a PCM and PETRA-modified poly(lauryl methacrylate)
as a shell. It was found that the modified shell increased the mechanical
strength of the micro-ePCMs. However, ePCMs with a higher PETRA
mass fractions showed lower capsule strength. According to some
research studies [323,310], the mechanical strength of the shell material
is closely related to the PCM content of the polymer shell.
3.3.1.49. Chemical stability. Chemical stability can be described as the
ability of the ePCMs to resist any change due to chemical reactions be­
tween the ePCM and its surrounding environment or between the core
and shell after prolonged periods of time and/or under several repeated
heating/cooling cycles. The chemical stability of ePCMs can be affected
by several factors, including pH value, use of surfactants, synthesis
process, and core-to-shell ratio. The most common techniques for
measuring chemical stability of ePCMs are FTIR and SEM.
Anti-osmosis is a very effective technique to determine the release
rate of micro-ePCMs, and thus, their chemical stability. Zhang et al.
[163] performed anti-osmosis measurements using a spectrophotometer
to evaluate the durability of micro-ePCMs (i.e., the ability of the shell
material to protect the PCM from leakage) produced with n-octadecane
as the PCM and PU as the shell. The micro-ePCMs were synthesized
using different aliphatic amines. The results showed that micro-ePCMs
obtained from the reaction of tolylene 2,4-diisocyanate with ethylene
diamine had the highest release rate, which resulted in leakage of the
PCM, and hence, poor durability. On the other hand, micro-ePCMs
synthesized with Jeffamine demonstrated the best anti-osmosis prop­
erty. Moreover, it was found that the core-to-shell ratio had a substantial
effect on the release rate as micro-ePCMs with a lower core weight
content showed a lower release rate. A similar study was conducted by
Zhang et al. [161] where the micro-ePCMs were obtained at the different
pH values of 2.26, 2.45, and 2.89 while the shell was made of silica. The
findings showed that the fastest release rate was obtained at a pH value
of 2.89, indicating that the release rate was influenced by the shell
thickness, and that micro-ePCMs with compact and thick shells can
exhibit good anti-osmosis properties. Su et al. [324] also performed an
anti-osmosis test of micro-ePCMs with n-octadecane as the PCM, PUR as
the shell, and different weight contents of styrene-maleic anhydride
(SMA) as a surfactant. It was shown that the SMA content significantly
affected the release properties of the micro-ePCMs, as shown in Fig. 37.
Another method to assess the chemical stability of ePCMs is to
observe if they can remain stable when immersed in continuous phases
with different chemical compositions. Wei et al. [159] investigated the
S.A. Albdour et al.
Fig. 36. SEM images of micro-encapsulated PCMs (dodecanol as core and polymer/silica as shell) with a) as-prepared core@shell structure and b) broken capsule
due to the addition of high DVB content in the core [321]. (Reused with permission from Elsevier).
Fig. 37. Release rates of micro-encapsulated PCMs prepared at 1, 2, 3, and 4%
of SMA [324]. (Reused with permission from Elsevier).
chemical stability of micro-ePCMs prepared with polyamide as the shell
and paraffin as the core material using various solvents. Their results
showed that the micro-capsules kept their properties and shapes after
immersion for one hour in a NaOH solution, a H2SO4 solution, ethanol,
ether, acetone, dimethyl sulfoxide, and dimethylformamide. However,
the micro-ePCMs were destroyed when immersed in a ZnCl2 solution.
The superior chemical stability was attributed to the aromatic-molecular
and cross-link structure of the ePCMs. Another common method to test
chemical stability is to observe the chemical structure of ePCMs after
repeated heating/cooling cycles through FTIR analysis. Sarı et al.
[246–248] prepared nano/micro-ePCMs with different PCMs (n-octa­
decane, n-heptadecane, n-eicosane, n-nonadecane, and n-tetracosane)
and different shells (PS and PMMA). The nano/micro-ePCMs were
subjected to 5000 thermal cycles with no effect on the chemical struc­
ture of the nano/micro-ePCMs. Fuensanta et al. [269] investigated the
chemical composition of micro-ePCMs based on paraffin as a PCM and
styrene-butyl acrylate as a shell. It was found that the FTIR absorption
characteristics were unchanged after 220 heating/cooling cycles, which
indicated that the micro-ePCMs exhibited good chemical stability.
Through FTIR analysis, Graham et al. [271] determined the chemical
stability of nano-ePCMs containing salt hydrate as the PCM and PECA
shells. It was observed that the spectrum was almost identical after 100
melting/freezing cycles, indicating high chemical stability during the
release/storage of latent heat. Konuklu et al. [325] evaluated the
chemical stability of CA coated with different shell materials using FTIR
analysis. They showed that the chemical structure of the PCM before and
after encapsulation remained stable. Tahan Latibari et al. [291,292]
35
Progress in Energy and Combustion Science 93 (2022) 101037
conducted a chemical stability test on stearic acid (SA)@titania and
palmic acid@silica microcapsules. They revealed that despite a large
number of repeated heating/cooling cycles, the chemical structure of the
micro-ePCMs was not affected. Wang et al. [270] observed that 1000
heating/cooling cycles had no effect on the chemical structure of
nano-ePCMs containing SA as PCM and PMMA as shell, and that no
chemical degradation occurred. Therefore, the nano-ePCMs were
deemed chemically stable.
3.3.1.50. Thermal stability. Thermal stability is another important fac­
tor to ensure the long-term efficiency of ePCMs before use in solar-
thermal systems. Thermal stability of ePCMs can be defined as the
ability of ePCMs to retain their phase-change properties and the same
decomposition temperature after several heating/cooling cycles at high
or low temperatures, depending on the heat/cold TES application.
Several studies have been performed on the thermal stability of ePCMs
at the nano and microscale mainly using TGA, FTIR, and DSC analyses.
Tahan Latibari et al. [292] evaluated the thermal degradation of
nano-ePCMs based on SA as PCM and titania as shell. It was observed
that the pure PCM exhibited one degradation step at 150− 250 ◦ C, while
the nano-ePCMs showed two thermal degradation steps at 160− 320 ◦ C
and 320− 450 ◦ C. In addition, nano-ePCMs exhibited a maximum release
rate at higher temperatures than the pure PCM. This result indicated that
the titania shell improved thermal stability and prevented leakage of the
melted PCM. Fuensanta et al. [269] investigated the thermal stability of
paraffin nano-encapsulated with PMMA by measuring the melting and
freezing latent heats after 220 melting/freezing cycles. It was shown that
the latent heats of freezing and fusion were respectively is in the range of
15.5− 22.5 J/g and 19.1− 24.4 J/g. These values remained unchanged
after 220 cycles, and the nano-ePCMs were deemed to have high thermal
stability. Moreover, thermal stability was confirmed by measuring the
temperature degradation of both nano-ePCMs and pure PCM. It was
observed that the thermal degradation temperature of nano-ePCMs was
higher than that of the pure PCM. Zhang et al. [326] studied the effects
of the stirring rate and styrene-maleic anhydride and cyclohexane con­
tents on the thermal stability of micro/nano-capsules containing
n-octadecane as PCM and MF as shell. They observed that as the stirring
rate and styrene-maleic anhydride content increased, the ePCMs were
produced with a more uniform shell thickness. A higher thermal stability
was realized when the capsules were synthesized with a stirring rate of
9000 rpm and a styrene-maleic anhydride content of 2.3 wt%. However,
the increase in cyclohexane content had no effect on thermal stability.
Fang et al. [327] determined the thermal stability of nano-ePCMs pre­
pared with UF as a shell and n-tetradecane as a PCM by measuring the
PCM weight release rate under the effect of different concentrations of
NaCl. It was revealed that during the heating process, nano-ePCMs with
1− 3% NaCl presented lower release rates. However, greater release
rates could be observed with NaCl concentrations of 8 and 10%. This
S.A. Albdour et al.
result indicated that NaCl was responsible for stabilizing the reaction
rate of the UF shell. Hu et al. [328] micro-encapsulated methyl laurate
(ML) with a PUR shell at various core-to-shell mass ratios. It was found
that the PUR shell can protect the PCM from volatilization and leakage
and can provide the PCM with high thermal stability. Moreover, it was
observed that higher core-to-shell mass ratios resulted in a faster mass
loss rate and lower thermal stability, indicating that the core-to-shell
ratio was a key parameter governing the thermal stability of
micro-ePCMs, as illustrated in Fig. 38. Lee et al. [294] examined the
thermal stability of binary nitrate molten salt (NaNO3:KNO3 in a 60:40
mass ratio) nano-encapsulated with a silica shells during 50 hea­
ting/cooling cycles over a temperature range of 27− 700 ◦ C. The silica
shell was found to preserve the PCM even far beyond the decomposition
temperature of the PCM, which was advantageous for practical appli­
cations up to 610 ◦ C. Wu et al. [329] prepared micro-ePCMs for a
high-temperature TES system. In their work, they encapsulated Na2SO4
with silica shells at different silica mass ratios. It was observed that
under the heating process from room temperature to 1000◦ C, the PCM
showed a mass loss of roughly 0.4%. However, the PCM mass loss
increased to 4% when the silica mass content increased to 26.8%. It was
concluded that a silica mass content of less than 5.4% kept the PCM mass
loss stable at 1%, ensuring high thermal stability at high temperatures.
Li et al. [330] micro-encapsulated NaNO3 with perhydropolysilazane.
The thermal stability of the capsules was measured under 80 repeated
thermal cycles at higher temperatures. It was found that between 250
and 350◦ C, the latent heat of the nano-ePCMs was reduced by 3.6%, the
melting temperature was reduced by 1◦ C, and the supercooling degree
remained almost constant. Yet, in the temperature range of 350-550◦ C,
the latent heat decreased by 4% at 500◦ C with a sharp decrease of about
20% at 550◦ C. The authors concluded that the encapsulation of PCM
increased their thermal stability by two folds up to 500 ℃, indicating
their high potential for TES systems at high temperatures. Ji et al. [331]
fabricated micro-ePCMs of solar salt with GO-modified silica shells. It
was observed that, compared to the pure PCM, the temperature at which
the PCM started to decompose in the nano-ePCMs increased by 28.1 ◦ C,
while the maximum decomposition temperature increased by 17.5 ◦ C.
This indicated that silica shells can successfully improve the thermal
stability of PCMs.
3.3.2. Stabilization strategies of ePCM slurries/dispersions
The use of ePCM slurries/dispersions in a wide range of thermal
applications appears to be beneficial, with the key drawbacks so far
being their high cost of production, particularly at the nanoscale, and
Fig. 38. a) DTG and b) TGA curves of a pure PCM (ML) and nano-encapsulated PCMs (ML as core and PUR as shell) with core-to-shell mass ratios of 1:1, 1:2, 1:3, and
1:4 [328]. (Reused with permission from Elsevier).
36
Progress in Energy and Combustion Science 93 (2022) 101037
the aforementioned instability issues. The stability of ePCM slurries/
dispersions is crucial for any thermal or solar application, and poor
stability can decrease the heat capacity storage and heat transfer rate. In
addition, the technical viability will be reduced due to the stratification
of the slurry/dispersion [20]. The stability of the slurry/dispersion is
affected by a number of factors, including the use of surfactants, syn­
thesis process of the ePCMs, temperature, pH value, ePCM size/shape,
core-to-shell ratio, PCM content, shell type, and density difference be­
tween the capsules and the carrying fluid. The main stabilization stra­
tegies for ePCM slurries/dispersions are highlighted in the remainder of
this section.
The density difference between ePCM particles and the carrying fluid
induces separation and instability due to gravity, resulting in either
sedimentation or creaming of particles. The most effective strategy to
prevent sedimentation/creaming is by reducing the density difference
between capsules and the carrying fluid, which could also reduce the
viscosity of the slurry/dispersion as a whole, and hence, decrease the
pumping power. Qiu et al. [332] examined the impact of the density
difference between micro-ePCM particles and their carrying fluid, sur­
factant type and concentration, and pH value on the stability of
micro-ePCM slurries at 10 wt%. It was revealed that the density differ­
ence between was the most important parameter affecting stability. A
combination of the appropriate surfactant (in terms of type and con­
centration) and pH value with a zero-density difference was found to
significantly enhance the physical stability of micro-ePCM slurries,
allowing them to be used in TES systems. Wang et al. [333] formulated a
binary mixture as the carrying fluid to match the density of micro-ePCMs
containing resin as the shell and n-hexacosane as the PCM core. Water
was chosen as one component of the binary mixture since it is one of the
most common HTFs. The micro-ePCMs had a density of 900 kg/m3,
which was lower than that of water. Therefore, propanol as a lighter
fluid was chosen as the second mixture component. The authors
observed some sedimentation and creaming in the micro-ePCM slurry
when the fluid density was 900 and 950 kg/m3, respectively. However,
after several tests, it was found that the highest physical stability was
achieved with a carrying fluid density of 941 kg/m3. Wang et al. [334]
studied the stability of micro-ePCM slurries characterized by paraffin as
PCM, MEL as shell, and water/ethanol as the carrying fluid. The slurry
was prepared using a combination of sonication and magnetic stirring,
and to achieve higher stability, an optimal ethanol/water mixing ratio
was determined. The micro-ePCM slurry showed stability for more than
a month without obvious sedimentation or delamination with a
water/ethanol mixing ratio of 1:2. Recently, Fu et al. [335] performed
S.A. Albdour et al.
several measurements on micro-ePCM slurries based on paraffin as PCM
and polymer shells by adjusting the pH value and adding a small amount
of sodium dialkylsulfateas as a surfactant so as to not affect the ther­
mophysical properties of water. Moreover, density of the carrying fluid
was fixed at 941 kg/m3 to keep the density difference between the fluid
and capsules close to zero. These stabilization strategies resulted in
excellent thermal and physical stabilities of the micro-ePCM slurry.
In general, the mixing and pumping processes associated with ePCM
slurries induce shear forces, which may cause breakage of the shell and
leakage of the PCM (when in liquid state) to the surrounding fluid.
Damaged/leaking ePCMs may also occur due to thermal cycling. Drissi
et al. [336] reported that damaged ePCMs can negatively affect their
thermal properties. The drop in specific heat capacity of damaged
ePCMs was reported to be about 28% compared to the non-damaged
ePCMs. Although several studies examined the stability of ePCMs, as
discussed in Section 3.3.1, very limited studies focused on leakage/­
damage prevention strategies. Zhang et al. [337] prepared a novel type
of micro-ePCMs with no mass loss and high encapsulation capacity using
an in-situ polymerization technique. MF and paraffin were used as shell
and PCM, respectively. GO was placed at the core/shell interface to act
as a second protective layer that prevents the leakage of paraffin. It was
found that the micro-ePCMs had better leakage prevention with an
encapsulation ratio of almost 94%, which was a significant improve­
ment. Shi et al. [338] produced leak-proof micro-ePCMs based on
acetylated cellulose nanofibrils (AcCNF) as a shell and paraffin as a
PCM. The AcCNF acted as a supporting material which prevented the
leakage of paraffin during phase-change transitions. The ePCMs showed
reduced supercooling (efficiency of 53% with PCM content of 83%) and
high melting heat. Compared to CNF, higher improvements in thermal
performance and encapsulation efficiency were obtained with the
AcCNF shell due to its compatibility with paraffin. It is worth noting that
leakage measurements are generally made by measuring the weight
change of ePCMs placed in a heated oven on top of filter papers or by
visual observation under repeated heating/cooling cycles [339]. Del­
gado et al. [20] suggested reducing the ePCM size and/or increasing the
shell thickness to prevent damage to the ePCMs.
3.3.3. Stability evaluation techniques of ePCM slurries/dispersions
The stability of ePCM slurries/dispersions can affect their thermal,
optical, and rheological properties, with a direct effect on their appli­
cation and utility. One can notice from the literature that very few
studies have reported on the stability evaluation of ePCM slurries/dis­
persions. The stability of ePCM slurries/dispersions is evaluated using
several techniques, such as the centrifugation method, zeta-potential
measurement, thermal/phase-change properties measurement, and the
turbidity method.
3.3.3.51. Centrifugation method. Centrifugation is the easiest and most
commonly used method to assess the stability of ePCM slurries/disper­
sions. This method is based on sediment formation at the bottom of the
slurry/dispersion due to gravity. Stability is determined by the time it
takes for precipitation to occur. This method has been employed by a
number of researchers to assess the stability of various ePCM slurries.
Karaipekli et al. [340] fabricated nano-ePCMs with n-nonadecane as the
PCM and poly(styrene-co-methacrylic-acid) (P(st-co-MAA)) as the shell.
Centrifugation measurements under 1500 and 3000 rpm and for 1 h
showed the absence of sedimentation at 1500 rpm, while negligible
sedimentation was observed at 3000 rpm. Fu et al. [341] produced
micro-ePCMs with tetradecane as the PCM and silica with/without PS as
the shell. Their results indicated that slurries at 3000 rpm generated
some sediment, while little sediment was observed at 1000 rpm. The R
values (the weight ratio of the solid product acquired by centrifugation
and the one obtained by demulsification) were found to be negligible,
indicating that both slurries possessed excellent physical stability. Fang
et al. [267] prepared nano-ePCMs, using n-tetradecane as the PCM and
37
Progress in Energy and Combustion Science 93 (2022) 101037
PS as the shell, and observed no sedimentation after centrifugation at
1500 rpm. However, the precipitate weight increased as the centrifuge
speed was increased. The R values were found to be almost negligible,
indicating high mechanical stability.
3.3.3.52. Zeta-potential analysis. Zeta potential, also known as electro­
kinetic potential, is another method used to assess the stability of ePCMs
slurries/dispersions. The zeta potential is the electrical potential dif­
ference, measured in millivolts, between the hydrodynamic surface of
shear (the slipping plane) and the bulk fluid. It is known that for purely
or dominantly electrostatically-stabilized colloidal suspensions, a low
zeta potential is a sign of low electrostatic stability, while a high zeta
potential indicates high electrostatic stability. In general, for dominantly
charge-protected dispersions, zeta potential values greater than ± 30
and ± 60 mV indicate good and excellent charge-induced stabilities,
respectively. According to Karaipekli et al. [340], the zeta potential of
their prepared nano-ePCMs slurries at pH of 7 was − 56.8 mV. Joseph
et al. [342] prepared ePCMs using n-octadecane as the PCM and PS as
the shell. They measured the zeta potential of the dispersion at different
concentrations, and observed that for a concentration of 0.7 vol%, the
maximum zeta-potential value was 70 mV. The zeta-potential values
were found to decrease as the concentration increased.
3.3.3.53. Thermal/phase-change properties measurement. Tracking
changes in thermal/phase-change properties over time is another tech­
nique to assess the stability of ePCM slurries/dispersions. In general,
sedimentation may result in thermal conductivity reduction over time or
a change in the phase-change latent heat and melting temperature
during heating/cooling cycles. Liu et al. [343] measured the stability of
their micro-ePCMs slurry using a DSC analysis and thermal conductivity
apparatus. They found that the thermal conductivity, melting temper­
ature, and phase-change latent heat of the micro-ePCMs remained un­
changed under several thermal cycles, indicating good physical stability.
Cingarapu et al. [344] produced nano-ePCMs with tin as the PCM and
silica as the shell. They assessed the stability of the slurry through an
evaluation of the thermal conductivity at 1− 5 vol%. The values were
recorded every 15 min for a period of 15 h. They concluded that all
slurries were stable since no change was observed in thermal conduc­
tivity with time.
3.3.3.54. Turbidity method. The turbidity method is another effective
technique to judge the stability of ePCM slurries/dispersion. In general,
a change in turbidity is a sign of instability in the ePCM slurry. When
light travels through a well-dispersed slurry/dispersion, the radiation
intensity is decreased exponentially along the direction of propagation
due to absorption and scattering by the suspended particles. Since
turbidity is proportional to light extinction (i.e., absorption plus scat­
tering), when light travels through ePCM slurries/dispersions, turbidity
can be quantified by comparing transmitted and incident radiations. Lin
et al. [345] and Zheng et al. [346] measured the stability of ePCM
slurries with different dispersants (PEG and SA) at different concentra­
tions (up to 40% vol) using the turbidity method. They observed that
ePCM slurries without dispersants exhibited a higher stability than those
with dispersants. Similarly, using the turbidity method, Qiu et al. [332]
was able to capture the effects of surfactants, pH value, and the density
difference between capsule and fluid on the stability of ePCM slurries.
3.4. Measurement of thermophysical properties of ePCM slurries
The overall effectiveness of ePCM slurries in solar-thermal applica­
tions depends on their thermal, rheological, and optical properties.
Therefore, an in-depth understanding of these properties is important
for optimal implementation in industrial applications. A summary of the
thermal conductivity and specific heat capacity of ePCM slurries is
presented in Table 8, while a summary of their rheological properties is
 Table 8

S.A. Albdour et al.

Reported data on the thermal conductivity and specific heat capacity of ePCM slurries and dispersions.
Core@shell Temperature ePCM Carrying Concentration Synthesis method Measurementapparatus Main results Ref.
(◦ C) size fluid

N-tetradecane@PS 5− 25 144.5 nm Water 0-15 wt% In-situ miniemulsion - Hot disk method - Thermal conductivity was not affected by the addition of nano-ePCMs [267]
polymerization - DSC at 5 ◦ C. However, a clear increase was observed at 25 ◦ C.
- Specific heat capacity increased rapidly during the phase change,
while it was constant when the PCM was in its solid or liquid state.
N-hexacosane@resin 20− 70 10− 40 Propanol/ 40 wt% Not reported Hot disk method Thermal conductivity dropped with concentration. However, it [333]
μm water increased first and then reduced with temperature.
N-nonadecane@P(St- 25− 34 212 nm Water 0− 2 wt% Mini-emulsion - KD2 Pro analyzer - Thermal conductivity increased with concentration and temperature. [340]
co-MAA) polymerization - DSC - Specific heat capacity increased significantly during the phase
change, while it was constant when the PCM was in its solid or liquid
state.
N-tetradecane@PS/ 5− 20 80− 120 Water 0− 5 wt% Miniemulsion poly- - Hot disk method - Thermal conductivity increased with temperature and decreased with [341]
silica nm merization - DSC mass fraction.
N-tetradecane@PS - Addition of nano-ePCMs improved specific heat capacity.
Paraffin@MF 25− 50 5.392 μm Water/ 0− 40 wt% Not reported Hot disk method Thermal conductivity dropped with concentration and was mainly [343]
ethanol affected by the physical state of the PCM.
Sn@silica Not reported 50− 100 Therminol 0− 5 vol% Modified KD2 Pro analyzer Thermal conductivity of slurries increased linearly with weight [344]
nm polyole wet-chemical fraction following the Maxwell model.
reduction
Paraffin@polymer 20 10− 100 Water 35 wt% Commercial Hot disk method Thermal conductivity dropped with micro-ePCM concentration, while [347]
Paraffin@PMMA μm it was improved with temperature.
n-octadecane@PS 30 209 nm Water 1.5 vol% Miniemulsion polymerization KD2 Pro analyzer No enhancement was observed in thermal conductivity. [342]
Paraffin@polymer 24− 36 1− 20 μm Water 30% Commercial Laser Flash method Thermal conductivity dropped with micro-ePCM concentration, while [348]
it slightly increased with temperature.
Paraffin@PMMA 10− 40 Not Water/PG 0− 43.0 wt% Commercial KD2 Pro analyzer Maximum enhancement was observed at the melting temperature, [349]
reported particularly at higher concentrations.
38

N-eicosane@UF 25− 50 5− 15 μm Water 10 wt% Not reported KD2 Pro analyzer Thermal conductivity dropped with concentration and was mainly [350]
affected by the physical state of the PCM.
N-nonadecane@PUR 25− 35 55− 175 Water 0− 3.36 wt% Interfacial polymerization Transient hot wire Thermal conductivity of slurries with EG were higher than that with [351]
nm EG water.
Paraffin@titania-GO 30− 80 2− 5 μm Water 3 wt% In-situ hydrolysis and - Hot disk method - Thermal conductivity of both slurries increased with temperature and [352]
Paraffin@titania polycondensation - DSC concentration.
- Specific heat capacity increased sharply during the phase-change
transition.
Paraffin@Cu-Cu2O/ 10− 80 688 nm Water 4 wt% In-situ deposition - Hot disk method - Thermal conductivity increased slightly with addition of micro- [353]
CNTs - DSC ePCMs.
- Specific heat capacity depended mainly on the physical state of the
PCM.

Progress in Energy and Combustion Science 93 (2022) 101037

Acid@MWCNTs 25− 85 50− 60 Water 0− 15 wt% Vacuum absorption - Hot disk method - A sharp increase in thermal conductivity was observed during the [354]
nm - DSC phase-change transition. However, after the phase-change transition,
thermal conductivity was slightly reduced.
- Specific heat capacity depended mainly on the physical state of the
PCM.
Paraffin@MF/ 20− 145 Not [BMIM]BF4 0− 20 wt% In-situ polymerization - Hot disk method - Thermal conductivity increased significantly with concentration and [355]
graphitec reported - DSC temperature.
- Specific heat capacity of paraffin@MF/graphite and paraffin@MF
slurries exhibited a maximum value during the phase transition.
Paraffin@SiO2/GO 30− 80 20 μm Water 10 wt% Interfacial - Hot disk method - Thermal conductivity increased with concentration and temperature. [311]
hydrolysis–condensation - DSC - Specific heat capacity of both slurries exhibited a sharp increase
during the phase-change transition.
Paraffin@SnO2/CNTs 30− 80 1− 5 μm Water 5 wt% In-situ precipitation Hot disk method - Thermal conductivity increased with concentration and temperature. [356]
- Specific heat capacity of both slurries exhibited sharp increase during
the phase-change transition.
Paraffin@PMMA 15− 22 1− 5 μm Water 3 wt% Commercial T-history method Addition of micro-ePCMs caused an increase in the specific heat [357]
capacity during the phase change, while a decrease (increase) was
observed for slurries with liquid (solid) PCM.
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

provided in Table 9.

[358]

[341]

[342]

[349]

[353]

[359]

[360]

[361]

[362]
Ref.
3.4.1. Thermal properties

- Viscosity at 14, 20, and 30 wt% was 5, 6, and 18 times higher than

The viscosity of paraffin@Cu-Cu2O/CNTs slurry was lower than that

- Viscosity was not affected by the phase-change transition, and was

- Viscosity decreased with temperature and increased with particle
3.4.1.55. Thermal conductivity. HTFs with higher thermal conductiv­

- Viscosity was higher at higher concentrations, particularly for

ities are strongly desired to develop thermal systems with higher heat

Viscosity of both slurries increased with temperature, while it

concentration until it reached a maximum value at 40 wt%.

- The slurry with surfactant exhibited Newtonian behavior.

transfer rates. The suspension of micro/nano-ePCMs into HTFs may

Viscosity of the slurries increased slowly with increasing

result in higher thermal conductivity values. Therefore, several attempts

- Viscosity was lower at higher temperatures and lower

- Viscosity increased as the concentration increased.

have been made in this research area to give a clear picture of the

- The slurry exhibited a non-Newtonian behavior.

- The slurry exhibited a non-Newtonian behavior.

- The slurry exhibited a non-Newtonian behavior.

- The slurry exhibited a non-Newtonian behavior.

-The slurry exhibited a non-Newtonian behavior.

thermal conductivity of ePCM slurries. In the thermal conductivity

almost 8-14 times greater than that of water.

measurements of ePCM slurries/dispersions, researchers mainly focused
on two different shell materials, namely, polymeric and carbon-modified
shells.
3.4.1.56.0. Polymeric shells. Fang et al. [267] measured the thermal

concentration greater than 30%.

decreases with concentration.
conductivity of nano-ePCM slurries prepared with n-tetradecane as PCM
and PS as shell. They observed that the thermal conductivity was not

size and concentration.

affected by the addition of nano-ePCMs at 5 ◦ C. However, a clear in­

of paraffin@Cu-Cu2O.
crease was observed at 25 ◦ C with a maximum improvement of about

concentrations.
16%. Wang et al. [333] investigated the thermal conductivity of

that of water.
Main results
micro-ePCM slurries at different temperatures and weight fractions. It
was shown that thermal conductivity dropped as the weight fraction
increased. However, thermal conductivity first increased and then
dropped with temperature. In addition, the thermal conductivity values
were found to match well with the Maxwell-Garnett model at 17 ◦ C.

Brookfield viscometer

Brookfield viscometer
Karaipekli et al. [340] found that the thermal conductivity of

Cylindrical Couette
Hot disk method
nano-ePCM slurries increased with weight fraction and temperature,

NDJ-1 rotation
Measurement

Not reported
even though the thermal conductivity was lower than that of the car­

Rheometer

Rheometer

Rheometer
viscometer

viscometer

viscometer
rying fluid. This result was attributed to the interactions between apparatus
surface-functionalized nano-ePCMs as well as their Brownian motion. Fu
et al. [341] showed that, within 5 to 20 ◦ C, the thermal conductivity of
nano-ePCM slurries with and without silica on the PS shell increased

Interfacial polymerization
with temperature and decreased with weight fraction. A higher thermal

Complex coacervation
In-situ polymerization

In-situ polymerization

Coacervation method
In-situ miniemulsion

conductivity was obtained by using silica/PS shells compared to PS

Synthesis method

In-situ deposition
shells. The thermal conductivity of slurries with silica-modified shells
polymerization

was 8.4% higher than slurries without silica. Liu et al. [343] observed Not reported
Commercial

Commercial
that the thermal conductivity of micro-ePCM slurries was enhanced with
temperature before and after the phase-change temperature occurred.
However, there was an abrupt reduction during phase change, indi­
cating that thermal conductivity of the solid PCM was higher than that of
Concentration

the liquid PCM. In addition, it was found that the thermal conductivity

0− 17.7 wt%
0− 40 wt%

0− 35 wt%

0− 30 wt%

0− 44 wt%
of the slurry dropped with weight fraction, which was attributed to the
0− 5 wt%

16 wt%
0− 30%
4 wt%

low thermal conductivity of the shell material. Cingarapu et al. [344]

measured the thermal conductivity of nano-ePCM slurries based on sil­
ica as a shell and tin as a PCM. They observed that thermal conductivity
increased linearly with weight fraction following the Maxwell model. An
Carrying

enhancement of 3% was observed for each 1% increase in the

Water

Water

Water

Water

Water

Water

Water

Water

Water
fluid

nano-ePCM concentration. Zhang and Zhao [347] investigated the

thermal conductivity of two different types of micro-ePCM slurries at 20
Reported data on the rheological properties of ePCM slurries.

◦
C. It was observed that thermal conductivity of the slurries dropped as
2− 260 µm
1− 20 µm

1− 20 µm

3.34 µm
5− 1000
80− 120

1− 5 µm
688 nm

the weight fraction increased. They attributed this to the thermal con­
10 µm
ePCM
size

ductivity of water being higher than that of the PCM cores. Joseph and
nm

µm

Sajith [342] measured the thermal conductivity of nano-ePCM disper­

sions at different fractions. No enhancement in thermal conductivity was
Temperature

observed, which was attributed to the poor thermal conductivity of the

shell material. Delgado et al. [348] demonstrated that the addition of
10− 80

10− 50

17− 70

micro-ePCMs to the carrying fluid actually caused a reduction in thermal

5− 25

5− 25

5− 40

2− 11
(◦ C)

27

25

conductivity. For instance, a reduction of 39% was observed at a weight

fraction of 30% and a temperature of 30 ◦ C. They attributed this to the
fact that the thermal conductivity of water was higher than that of
Ntetradecane@PS-silica

Paraffin@Cu-Cu2O/CNTs

CrodathermTM 60@PU-
n-tetradecane@gelatine

paraffin. Dutkowski and Kruzel [349] presented detailed results on the

Tetradecane@PMMA

thermal conductivity of micro-ePCM slurries containing paraffin as PCM

n-tetradecane@MF
n-dodecane@MF
Ntetradecane@PS

Paraffin@PMM

Paraffin@PMMA
Paraffin@acrylic

and PMMA as shell. It was found that an increase in weight fraction

induced an increase in thermal conductivity during the phase-change
Core@shell

0.1%GNP
Paraffin@p
olymer

transition. A maximum enhancement was observed at the melting

Table 9

temperature of 27 ◦ C, particularly for higher particle concentrations.

39
S.A. Albdour et al.
Moreover, it was observed that the thermal conductivity of slurries with
solid PCMs was lower than that of slurries with liquid PCMs. They also
observed that when the PCM was in the form of a solid or liquid, the
thermal conductivity of the slurry could be evaluated from Maxwell’s
model with good accuracy. The thermal conductivity of the micro-ePCM
slurries at various weight fractions and temperatures is presented in
Fig. 39.
Ho et al. [350] reported that the thermal conductivity of micro-ePCM
slurries was significantly affected by the physical state of the PCM, and
that for temperatures below the melting temperature, thermal conduc­
tivity increased with temperature. However, in vicinity of the melting
temperature, the ascending trend became considerably more pro­
nounced due to the effect of the latent heat of fusion, while during the
phase-change process, thermal conductivity significantly decreased, and
when the PCM completely melted, thermal conductivity began to
gradually increase. Barlak et al. [351] studied the effect of the type of
carrying fluid on the thermal conductivity of nano-ePCM slurries pre­
pared with PUR as the shell and n-nonadecane as the PCM. As base
fluids, water and EG were used. It was revealed that the thermal con­
ductivity of nano-ePCM dispersions with EG or water increased and
decreased, respectively, with increasing the weight fraction. The ther­
mal conductivity of dispersions with water was found to be lower than
that with EG. They reported a maximum enhancement of almost 35%
and 15% with EG and water dispersions, respectively.
3.4.1.57.0. Carbon-modified shells. While several studies have been
performed on the thermal conductivity of ePCM slurries using polymeric
shells, limited studies have been devoted to those with carbon-modified
shells. Ma et al. [352] measured the thermal conductivity of
micro-ePCM slurries with and without GO integrated in the shell ma­
terial. It was observed that the thermal conductivity of both types of
slurries increased with temperature and weight fraction. Compared to
water, the thermal conductivity of slurries with and without GO was
Fig. 39. Thermal conductivity of encapsulated PCM slurries (paraffin as core and PMMA as shell) at different particle concentrations [349].
40
Progress in Energy and Combustion Science 93 (2022) 101037
increased by 4.5 and 3.1%, respectively. This result was attributed to the
higher thermal conductivity of the titania/GO composite compared to
that of only titania. Xu et al. [353] measured the thermal conductivity of
the carrying fluid, a paraffin@Cu-Cu2O slurry, and a paraffin@Cu-­
Cu2O/CNTs slurry. They revealed that the thermal conductivity of the
pure fluid slightly increased with the addition of micro-ePCMs. A
maximum increase of about 2.8% was observed for paraffin@Cu-­
Cu2O/CNTs at 4 wt%. Chen et al. [354] examined the thermal con­
ductivity of nano-ePCM slurries with MWCNTs as shells at particle
fractions of 5, 10, and 15 wt%. Their results showed that the thermal
conductivity of the slurries increased with temperature and particle
fraction, with a sharp increase in thermal conductivity observed during
the phase-change transition between 55 and 75◦ C. When the fraction of
capsules was 15 wt%, thermal conductivity increased by almost 54% at
60 ◦ C, which was attributed to the intense natural convective flow.
However, after the phase-change transition, the thermal conductivity
was slightly reduced. At different concentrations and over a wide tem­
perature range, Liu et al. [355] determined the thermal conductivity of
micro-ePCM slurries containing paraffin as the PCM, MF/graphite as the
shell, and an ionic liquid as the carrying fluid. It was observed that the
thermal conductivity of the paraffin@MF/graphite slurry enhanced by 9
and 13% at 10 and 20 wt%, respectively. The result indicated that the
thermal conductivity increases with weight fraction. Moreover, the
paraffin@MF/graphite slurry showed higher thermal conductivity
compared to that of paraffin@MF at 10 wt%, which was attributed to the
higher thermal conductivity of MF/graphite compared to that of MF. A
similar trend for the thermal conductivity of paraffin@SiO2/GO and
paraffin@SnO2/CNTs slurries was reported by Yuan et al. [363] and Ma
et al. [356], respectively.
3.4.1.58. Specific heat capacity
3.4.1.59.0. Polymeric shells. Specific heat is another important
S.A. Albdour et al.
property that characterizes any HTF. However, the specific heat of ePCM
slurries has received little attention and has only lately been investi­
gated. Fang et al. [267] determined the specific heat capacity of
nano-ePCM slurries and found that when the PCM was in its solid or
liquid states, the specific heat capacity was almost constant and
decreased with nano-ePCM concentration. However, the specific heat
capacity increased rapidly during phase change, in proportion to the
nano-ePCMs concentration. A maximum enhancement of 15% in spe­
cific heat capacity was observed at 15 wt%. Karaipekli et al. [340]
studied the specific heat capacity of nano-ePCM slurries at different
concentrations and temperatures. They revealed that when the PCM was
solid (5− 22◦ C) or liquid (40− 60◦ C), the specific heat capacity was
nearly constant and slightly affected by the addition of nano-ePCMs.
However, during phase change (22− 28◦ C), the specific heat capacity
increased as the temperature and weight fraction increased. The specific
heat capacity was increased by 4.5 and 9.6% at 1.0 and 2.0 wt%,
respectively. They concluded that during the solid-liquid phase change,
the addition of nano-ePCMs significantly improved the specific heat
capacity of the carrying fluid. Fig. 40 illustrates the specific heat ca­
pacity of nano-ePCM slurries at different concentrations and tempera­
tures, as reported in [340]. Fu et al. [341] measured the specific heat
capacity of nano-ePCM slurries with different shell materials, at various
concentrations and temperatures. Their results revealed that the addi­
tion of nano-ePCM particles improved the specific heat capacity of the
carrying fluid within the temperature range of − 20 to 40 ◦ C. The specific
heat capacity values showed a maximum between − 10 and 0 ◦ C due to
the phase-change of water. However, a slight increase in specific heat
capacity was observed in the range of 0 to 10 ◦ C. Furthermore, slurries
with a PS/silica shell were found to have a higher specific heat capacity
compared to slurries with a PS shell. Recently, Dutkowski et al. [357]
examined in detail the effects of both temperature and ePCM concen­
tration on the specific heat capacity of ePCM slurries. They observed that
the addition of ePCMs to the carrying fluid caused an increase in the
specific heat capacity of the slurry during the phase-change process. As
the weight fraction varied between 8.6 and 30.1 wt%, the specific heat
capacity at the melting point increased by almost 266%. Furthermore,
the specific heat capacity of slurries with solid PCMs was higher than
that of slurries with liquid PCMs. When the concentration varied be­
tween 8.6 and 30.1 wt%, the specific heat capacity of slurries with liquid
Fig. 40. Specific heat capacity of nano-encapsulated PCM slurries (n-nonadecane as core and P(St-co-MAA) as shell) at different weight concentrations and tem­
peratures [340]. (Reused with permission from Elsevier).
41
Progress in Energy and Combustion Science 93 (2022) 101037
PCM decreased by 6.7%, whereas the specific heat capacity of slurries
with solid PCM increased by 17.5%.
3.4.1.60.0. Carbon-modified shells. Ma et al. [352] found that the
specific heat of paraffin@TiO2/GO and paraffin@TiO2 slurries, at 3 wt%
and between 40− 50◦ C and 55− 65◦ C, was significantly higher than that
of the carrying fluid. Because of the occurrence of a phase-change
transition, a sharp increase was observed around 60◦ C. Xu et al. [189]
observed different behaviors regarding the specific heat capacity of
paraffin@Cu-Cu2O/CNTs and paraffin@Cu-Cu2O slurries at 4 wt%.
When the PCM was solid, the specific heat capacity of the paraf­
fin@Cu-Cu2O slurry was higher than that of water, while the specific
heat capacity of the paraffin@Cu-Cu2O/CNTs slurry was lower. How­
ever, when the PCM was liquid, both specific heat capacities were lower
than that of water. In addition, during phase change, both specific heat
capacities were greater than that of water, but the paraffin@Cu-Cu2O
slurry had a larger heat capacity compared to paraffin@Cu-Cu2O/CNTs,
which was attributed to the higher encapsulation efficiency of paraf­
fin@Cu-Cu2O. Liu et al. [355] showed that the specific heat capacity of
an ionic liquid increased by 13.4% as the temperature varied from 30 to
25◦ C. The specific heat capacity of paraffin@MF/graphite and paraf­
fin@MF slurries exhibited a maximum value during the phase transition.
The specific heat capacity of the paraffin@MF/graphite slurry at 10 wt%
was enhanced by 70% compared to the pure fluid. Moreover, it was
found that as the weight fraction of paraffin@MF/graphite increased to
20 wt%, the maximum value of the specific heat capacity increased by
two fold compared to the ionic liquid. Yuan et al. [363] compared the
specific heat capacity of the carrying fluid with paraffin@SiO2/GO and
paraffin@SiO2 slurries at 10 wt% within the temperature range of
30− 85◦ C. The specific heat capacity of both slurries exhibited a sharp
increase during the phase-change transition at approximately 60 ◦ C.
However, when temperature was higher than 70 ◦ C, the specific heat
capacity had a lower value compared to that of the carrying fluid. A
similar trend was obtained by Ma et al. [194] for paraffin@SnO2/CNTs.
3.4.2. Rheological properties
3.4.2.61. Polymeric shells. Rheological properties have a significant
impact on pressure drop, pumping power, and heat transfer rate.
Though the benefits of ePCM slurries for thermal applications depend on
S.A. Albdour et al.
the compromise between the viscosity increase and thermal properties
improvement, the viscosity of ePCM slurries as well as their rheological
behavior have received less attention than thermal properties. Yang
et al. [358] prepared four types of micro-ePCM slurries with tetradecane
encapsulated by PEMA, PMMA, PS, or PVAc shells. It was found that
tetradecane could not be encapsulated with PVAc since the phase
change cannot be manifested. They attributed this to the volatile nature
of the monomer, which made polymerization at the surface of tetrade­
cane difficult. However, tetradecane could be encapsulated with PMMA,
PS, and PEMA, resulting in a core@shell structure with good
heat-storage properties. It was revealed that the viscosity of the slurries
increased slowly with an increase in weight fraction until it reached a
maximum value at a weight fraction of 40%. The viscosity at 25 ◦ C and a
particle concentration of 40% was about 20 times the viscosity of water.
Fu et al. [341] investigated the viscosity of nano-ePCM slurries with and
without silica in the shell material. It was observed that the viscosity of
both slurries increased with weight fraction while it decreased with
temperature. At the melting point and 5 wt%, viscosity with and without
silica increased by almost 21 and 16.7%, respectively. Zhang and Zhao
[347] measured the rheological properties of two different micro-ePCM
slurries at different weight fractions, ePCM sizes, and temperatures. It
was found that both slurries showed a Newtonian behavior for shear
rates greater than 200 s− 1, and that viscosity decreased with tempera­
ture while it increased with particle size and concentration. At various
weight fractions and a temperature of 27 ◦ C, Delgado et al. [348]
investigated the rheological properties of micro-ePCM slurries contain­
ing paraffin as the PCM and PMMA as the shell. It was shown that the
viscosity of the slurry at 14, 20, and 30 wt% was 5, 6, and 18 times
higher than that of the carrying fluid. Moreover, when the shear rate
increased, the viscosity dropped until it reached the Newtonian plateau,
where it stayed constant, as illustrated in Fig. 41. It was found that the
viscosity-shear rate profiles could be predicted by the Carreau model
[364]. Yamagishi et al. [359] found that the apparent viscosity of
n-dodecane and n-tetradecane slurries depended on various parameters,
such as temperature, concentration, and micro-ePCM size. The viscosity
of slurries was higher at higher concentrations, particularly at concen­
trations greater than 30 wt%. It was observed that surfactants were
effective in lowering the viscosity, and that the slurry with surfactant
exhibited Newtonian behavior. This behavior was attributed to the fact
that surfactants affected the core-shell or fluid-PCM interactions.
Alvarado et al. [360] presented the relative viscosity of micro-ePCM
slurries based on n-tetradecane as PCM and gelatin as shell. It was
Fig. 41. Viscosity versus shear rate for micro-encapsulated PCM slurries
(paraffin as core and PMMA as shell) at different weight concentrations [348].
(Reused with permission from Elsevier).
42
Progress in Energy and Combustion Science 93 (2022) 101037
observed that the relative viscosity, defined as the ratio of the apparent
viscosity of the micro-ePCM slurry to that of the carrying fluid, was
independent of temperature. Viscosity was lower at higher temperatures
and lower weight fractions. The findings further showed that the slurries
exhibited Newtonian behavior up to 17.7 wt%. At six different ePCM
concentrations, Dutkowski and Fiuk. [361] performed a detailed study
on the rheological properties of micro-ePCM slurries prepared with
Micronal@DS 5039 X–water aqueous solution. It was found that the
aqueous solution had a viscosity of several hundred to several dozen
times that of water in the temperature range of 10-50 ◦ C. Viscosity
increased as the weight fraction of capsules increased. On the other
hand, the rheological behavior study demonstrated that the viscosity of
the slurry dropped with an increase in shear rate until it reached the
Newtonian plateau, where it appeared to be constant, indicating that
there existed a shear rate threshold beyond which the slurry exhibited
Newtonian behavior. Furthermore, when steady-state conditions were
maintained, the phase-change process of the micro-ePCM slurry had no
discernible effect on viscosity near the melting point. However, the
phase-change process influenced viscosity during unsteady-state con­
ditions. It was proposed to measure the melting temperature of PCMs
through viscosity measurements in case PCM properties were unknown
[365]. Latibari et al. [362] examined the rheological properties of
photothermal slurries with CrodathermTM 60 as the PCM and PU as the
shell. Results showed that the viscosity of the slurry increased with
weight fraction and decreased with temperature. It was observed that
viscosity was not affected by the phase-change transition and was almost
8-14 times greater than that of water. Furthermore, increasing the shear
rate caused the viscosity to drop rapidly, and then it became constant,
resulting in non-Newtonian behavior.
3.4.2.62. Carbon-modified shells. To the best of our knowledge, only one
study has been performed on the viscosity of ePCM slurries with a
carbon-modified shell. Xu et al. [353] measured the viscosity of paraf­
fin@Cu-Cu2O/CNTs and paraffin@Cu-Cu2O slurries at 4 wt%, and found
a viscosity enhancement of 33 and 22%, respectively, compared to
water. This indicated that the paraffin@Cu-Cu2O/CNTs slurry was more
viscous than the paraffin@Cu-Cu2O slurry.
3.4.3. Optical properties
Solar-thermal systems based on the direct volumetric absorption of
solar radiation (to be discussed in Section 3.5) are directly dominated by
the optical properties of the HTF. As a result, developing novel HTFs
with outstanding thermophysical characteristics and photothermal
conversion performance is critical. Several attempts were made to
improve the optical properties of pure HTFs by suspending ePCM par­
ticles into the carrying fluid. Wang et al. [334] studied the spectral
transmittance of several colloidal fluids at the wavelength range of
200− 2000 nm, including the carrying fluid (a mixture of ethanol and
water), paraffin@MEL slurry at 1 wt%, a mixture of paraffin@MEL
slurry at 1 wt% and MWCNTs at 0.005 wt%, and a MWCNTs nanofluid at
0.005 wt%. It was observed that transmittance considerably decreased
with the addition of MWCNTs to the carrying fluid, indicating high
optical absorption over the studied wavelength range. However, the
micro-ePCM slurries with and without MWCNTs had almost zero
transmittance, indicating higher optical absorption compared to the
MWCNT nanofluid. Ma et al. [352] prepared a micro-ePCM slurry con­
taining paraffin as PCM and titania/GO as a shell to improve the effi­
ciency of direct solar collectors. The photographs of
paraffin@titania/GO and paraffin@titania slurries at 3 wt% revealed
that the paraffin@titania/GO slurry was darker. Therefore, it exhibited
superior light-absorption properties in the range of visible light
compared to paraffin@titania. This result indicates that the modifica­
tion of a titania shell with GO played a key role in enhancing the optical
properties of the slurry. Xu et al. [353] measured the optical absorption
of paraffin@Cu-Cu2O and paraffin@Cu-Cu2O/CNTs slurries for direct
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

solar collectors. It was found that paraffin@Cu-Cu2O/CNTs exhibited

better light absorption. They attributed this finding to the CNTs struc­
ture, which was similar to hexagonal carbon. Liu et al. [355] prepared
micro-ePCM slurries by suspending paraffin@MF/graphite and paraf­
fin@MF composites into an ionic liquid to examine the effect of
embedding graphite in the shell on the photothermal performance of the
slurry. It was observed that the optical absorption of paraffin@MF/­
graphite was four times higher than that of paraffin@MF. This result was
ascribed to the resonant band-to-band transition and the effect of plas­
mon excitation. Yuan et al. [363] found that the optical absorption
properties of paraffin@SiO2/GO were higher than that of paraf­
fin@SiO2, which indicated that adding GO to the silica shell improved
the solar absorption of micro-ePCM slurries. Ma et al. [356] examined
the optical properties of paraffin@SnO2/CNTs and paraffin@SnO2
slurries. It was shown that paraffin@SnO2/CNTs exhibited a three-fold
increase in optical absorbance within the range of visible light as
compared to paraffin@SnO2, indicating that embedding CNTs within
the shell material can significantly improve optical absorption. Latibari
et al. [362] prepared CrodathermTM 60@PU slurries with the addition of
graphite nanoplatelets (GNPs) to improve optical and thermal proper­
ties. The optical transmittance of the slurries was measured at room
temperature and over a wavelength range of 200− 2500 nm using a
UV-Vis-NIR spectrophotometer. It was found that the GNPs played a
significant role in the absorption of visible light. Gao et al. [366] pro­
posed micro-ePCM slurries with superior magnetic and optical proper­
ties using octadecane@MF composites. MF was modified with GO or
rGO to improve the optical properties and thermal conductivity of the
micro-ePCMs, while octadecane was doped with Fe3O4-OA to enhance
magnetic properties when the micro-ePCMs were recycled under an
external magnetic field. Results showed that the rGO-modified slurry
possessed the highest optical absorbance, followed by the GO-modified
slurry, which had a higher absorbance than the unmodified micro-ePCM
slurry and water, as shown in Fig. 42 (a) and (b). The attributed reasons
for this phenomenon were twofold. First, the optical absorbance was Fig. 42. a) Photographs and b) optical absorbance of magnetic micro-ePCM
improved with GO due to electron conjugation and aromatic character slurries (octadecane doped with Fe3O4-OA as core and MF as shell) with and
effects. Second, a large amount of oxygen-containing functional groups, without modifying the shell with GO or rGO [366]. (Reused with permission
causing damage to the π-π conjugated system of GO, underwent reduc­ from Elsevier).
tion by UV radiation.
absorption of solar radiation using an absorber plate, whereas in DASCs,
3.5. Solar photothermal absorption and storage using ePCM slurries/ solar radiation is volumetrically absorbed within the HTF without the
dispersions need for an absorber plate. The energy efficiency of IASCs can be
improved by increasing the thermal properties of conventional HTFs.
Solar energy appears to be the best choice among other renewable Improvement of the optical properties is not necessary owing to the high
energy technologies because of its abundance, sustainability, and absorptivity of the coated surface. On the other side, due to the low
cleanliness, as well as its ability to be produced at a lower cost and on a absorptivity of conventional HTFs, optical properties are more impor­
larger scale [367,368]. Photothermal, photochemical, and photovoltaic tant in DASCs than thermal properties. In DASCs, the problem of peeling
conversions are all efficient methods for converting solar energy into or oxidation of the absorber plate in IASCs is avoided; yet, the working
other forms of useful energy. However, solar photothermal conversion fluids in DASCs are directly exposed to solar radiation and must be
coupled with TES is one of the most convenient and frequently used durable with cyclic solar radiation.
methods to harvest solar energy due to its high energy conversion and Conventional HTFs, such as ethylene glycol, molten salt, thermal
simplistic operational mechanism. There are numerous applications for oils, and water, possess limited thermal characteristics and are weak
solar photothermal conversion that span a wide temperature range, absorbers over the visible and ultra-violet ranges of the solar spectrum
including solar cookers, solar water heaters, and concentrated solar (absorption of only 13% of solar radiation), resulting in poor thermal
power [369] (refer to Section 2.5). and optical properties, which result in a decrease in the energy effi­
Solar collectors, which collect solar energy and convert it to thermal ciency of solar-thermal collectors. For solar-thermal collectors, nano­
energy, are the cornerstone of photothermal systems. Solar-thermal fluids, which are mixtures of nanoparticles and conventional HTFs, have
collectors can be classified as direct or indirect solar collectors. For been proposed to achieve better performance. Studies on nanofluid-
indirect-absorption solar collectors (IASC), also called surface- based IASCs have shown that the efficiency of IASCs is enhanced
absorption solar collectors, solar radiation is first absorbed and then mainly owing to the increased thermal conductivity of nanofluids.
indirectly transferred to the HTF. However, the high surface tempera­ However, the IASC efficiency is found to drop at higher nanoparticle
ture of the IASC results in significant heat losses and low conversion concentrations due to the increase in viscous forces, which leads to a
efficiencies. Therefore, an alternative type of solar collectors called the decrease in heat transfer rates and an increase in pumping power [215].
direct-absorption solar collector (DASC), also known as a volumetric- On the other hand, studies performed on nanofluid-based DASCs have
absorption solar collector, was developed for further improvement of revealed that the addition of nanoparticles (e.g. plasmonic nano­
the energy efficiency of solar-thermal collectors [6]. There are key dif­ particles) to conventional HTFs can improve optical features even at
ferences between IASCs and DASCs. IASCs are based on the surface

43
S.A. Albdour et al.
very low concentrations as long as long-term radiation stability [370]
and thermal stability [371] are maintained. The reported data indicates
that nanoparticle concentration has a significant impact on the perfor­
mance of DASCs. When nanoparticle volume fraction is above an opti­
mum value, incident radiation is absorbed in the thin top layer of the
nanofluid instead of being volumetrically absorbed, and consequently, a
DASC approaches the surface-absorption limit of IASCs [369]. Relative
to IASCs, nanofluid-based DASCs show an increase in solar-to-thermal
efficiency [372]. Some concerns with nanofluids include their rela­
tively low heat capacity in comparison with conventional HTFs, which
indicates that high receiver efficiency can be obtained at high solar ra­
diation levels [373], and the time mismatch between solar energy
availability and energy demand, which reduces the utility of solar col­
lectors [374].
Other than the limited thermal and optical characteristics of con­
ventional HTFs, the stored energy in solar-thermal collectors based on
conventional HTFs or nanofluids is also a major issue. The stored ther­
mal energy can be released when solar radiation is intermittent (e.g.,
cloudy periods of the day), which may hinder their widespread
commercialization. Recently, ePCM slurries and dispersions were found
to be an appealing option for solar-thermal collectors due to their su­
perior thermal and optical properties, constant temperature during
solid-liquid transition, high latent heat storage capacity, and better
matching between energy supply and demand [31]. ePCM slurries and
dispersions exhibit superior thermal and optical properties compared to
pure fluids and colloidal dispersions. In addition, they can release and
store a considerable amount of latent heat during phase change at
constant temperature. In the following sections, research studies are
reviewed for the application of ePCMs in DASCs and IASCs.
3.5.1. Indirect surface-absorption systems
There are various types of IASCs, among which evacuated-tube col­
lectors and flat-plate collectors are the most common. IASCs consist of
an absorber plate of steel, aluminum, copper, or polymers to which a
wavelength-selective or black coating is applied. The coated plate ab­
sorbs solar radiation and transforms it into thermal energy, resulting in a
significantly high surface temperature. Then, the HTF flowing below the
absorber plate collects heat indirectly via both conduction and convec­
tion. Since the exposed absorber plate has the highest temperature in the
system, a large amount of heat is lost to the environment by both
Fig. 43. Schematic illustration of an indirect-absorption solar collector (IASC) based on an ePCM slurry. Solar radiation is first absorbed by the absorber plate and
then indirectly transferred to the HTF.
44
Progress in Energy and Combustion Science 93 (2022) 101037
convection and radiation and to the other components by conduction.
Moreover, the high temperature of the absorber leads to a decrease in
optical absorption due to peeling and oxidation of the coated surface.
Therefore, IASCs typically exhibit low overall conversion efficiencies,
especially at high operating temperatures. A schematic representation of
an ePCM slurry-based IASC is presented in Fig. 43.
Although reported data have shown that ePCM slurries offer higher
thermal conductivity and specific heat capacity relative to conventional
HTFs, studies on IASCs based ePCM slurries are still largely unexplored.
Dutkowski et al. [375] presented a preliminary research study regarding
the effect of ePCM water slurries (with paraffin as a core and PMMA as a
shell) at 4.3 and 8.6 wt% on the efficiency of flat-plate solar collectors.
The solar irradiance varied between 250 and 950 W/m2. Their results
revealed that at the same solar irradiance, the higher the load fraction of
ePCM, the lower the outlet temperature from the solar collector,
allowing for a reduction in heat loss. At the maximum radiation in­
tensity, the temperature of the ePCM slurry at 8.6 wt% was around 10
degrees lower than that of water. Serale et al. [191] numerically eval­
uated the performance of a flat-plate solar collector based on an ePCM
slurry with n-eicosane as the PCM and glycol-water as the carrying fluid.
It was shown that the total and instantaneous photothermal conversion
efficiencies using the ePCM slurry surpassed that of the glycol-water
mixture, with efficiency enhancements of 4 and 6% reported at vol­
ume concentrations of 30 and 40%, respectively. Huang et al. [376]
characterized the thermal charge/discharge process of a TES system
with a helical coil exchanger under constant heat flux and turbulent flow
conditions. Water was used as the carrying fluid and microencapsulated
paraffin as the heat storage medium. An ePCM slurry with a melting
temperature of 65 ◦ C and various concentrations was tested and
compared to the pure fluid. They observed that slurries with 50 vol%
were not suitable for thermal storage due to the low heat transfer rate.
Moreover, the location and size of the heat exchanger were found to
significantly impact thermal performance of the TES system.
3.5.2. Direct volumetric-absorption systems
The twin design aims of any solar-thermal collector are to minimize
heat loss and maximize solar absorption, consequently maximizing
solar-to-thermal efficiency. Conventional IASCs intrinsically suffer from
high thermal losses due to their hot surface temperatures, hence their
low efficiency. Such drawback is significantly limiting the photothermal
S.A. Albdour et al.
utilization of solar energy. To overcome this limitation, the concept of
DASCs was proposed in 1975 by Minardi and Chuang [377]. In contrast
to IASCs, the incident solar radiation is directly absorbed by the bulk
HTF (i.e., volumetric absorption) rather than by the coated surface.
Therefore, thermal resistance between the absorber plate and HTF is
completely eliminated, and heat losses are minimized due to the lower
surface temperature of the collector. A schematic representation of an
ePCM slurry-based DASC is illustrated in Fig. 44. As the surface tem­
perature of the capsules is expected to be greater than the temperature of
the surrounding fluid (since the shell material is engineered for
maximum solar absorption), ePCMs are considered to behave as heat
sources for the surrounding fluid during the thermal charging and dis­
charging processes (i.e., heat is transferred from capsules to fluid).
Although DASCs can outperform IASCs [6], there are still many attempts
to acquire DASCs with superior photothermal conversion efficiencies.
One of these attempts is by suspending ePCMs in conventional solar
fluids. In contrast to ePCM-based IASCs, studies on ePCM-based DASCs
have received more attention from the scientific community. Fig. 45
presents the photothermal conversion efficiency of micro/nano-ePCM
slurries/dispersions with different core-shell combinations when used
for direct-absorption solar applications. Photothermal efficiencies pro­
vide a strong indicator of the combined optical and thermal function­
ality of ePCMs as solar energy is absorbed, the PCM cores are melted,
and thermal energy is retained while transferring heat to/from the
ePCMs during charging/discharging. The photothermal (solar-­
to-thermal) conversion efficiency in an ePCM-based direct-absorption
system can be defined as [311]:
mΔH
η= , (14)
AIt
where m is the mass of ePCMs, ΔH is the latent heat enthalpy during
phase transition, A is the effective surface area, I is solar intensity, and tis
the irradiation time.
As shown in Fig. 45, for the same core material, modifications to the
shell material result in varying photothermal efficiencies based on the
ability of the shell to absorb one or more spectral bands in the incident
solar radiation. This motivates the synthesis of composite shells made of
multiple martials able to absorb different bands of the solar spectrum.
For example, with TiO2 used in the shell, which is almost exclusively
sensitive to absorbing UV light, and n-eicosane (melting point of 38◦ C)
as a core material, a TiO2/CuS-GO composite shell reaches an efficiency
of 97.1%. CuS and GO were utilized as photothermal fillers, with CuS
nanoparticles loaded into GO nanosheets that served as structural
Fig. 44. Schematic illustration of a direct-absorption solar collector (DASC) based on an ePCM slurry. Solar radiation is volumetrically absorbed within the HTF
without the need for an absorber plate.
45
Progress in Energy and Combustion Science 93 (2022) 101037
supports. CuS has a broad absorption band over the whole spectrum,
with a prominent absorption peak in the near-infrared range. This
combination maximizes the use of solar energy and enhances the pho­
tothermal efficiency. On the other hand, using Crodatherm (melting
point of 60◦ C) as a core material with polyurea as a shell, which is
sensitive to UV light, results in a photothermal efficiency of 30%,
meaning that the potential of solar photothermal conversion is not
efficiently utilized with the polyurea shell (more details are presented in
Sections 3.6.2 and 5.1).
As illustrated in Fig. 46, Wang et al. [334] compared the photo­
thermal conversion performance (during irradiation time of 3000 s) of
MWCNT-ePCM slurries at 5, 10, and 15 wt% with that of water-ethanol
mixture and MWCNT nanofluid at 0.005 wt%. At the charging stage, the
temperature rise of the MWCNT-ePCM slurry was found to be lower than
that of MWCNT nanofluid and higher than that of the pure fluid. The
terminal temperature of the MWCNT nanofluid and slurry with 5 wt%
was increased by 16.3 and 9.5 ◦ C, respectively. Moreover, the terminal
temperature of the slurries was further reduced as the weight concen­
tration was increased from 5 to 15 wt%. This result was attributed to the
heat-absorption and high reflectivity of the slurry at higher concentra­
tions. Moreover, at the discharging stage, the terminal temperature of
the slurry at different concentrations was found to be greater than that of
the MWCNT nanofluid. As compared to the base fluid, an increase of
about 4.6 ◦ C in the terminal temperature of the slurry (at 15 wt%) was
observed, indicating that suspending both nanoparticles and ePCMs into
the base fluid revealed a promising solution for DASCs to overcome the
intermittence of solar radiation.
Ma et al. [352] measured the photothermal conversion performance
of an ePCM slurry and a GO-ePCM slurry under an irradiation time of
4000 s and a weight concentration of 3%. It was found that the tem­
perature of the GO-ePCM slurry increased from 30 to 92◦ C, while the
temperature of the ePCM slurry increased from 30 to 85◦ C. Moreover,
the effective receiver efficiency of both slurries was calculated at the
same temperature and weight fraction, and it was observed that the
effective receiver efficiency of the GO-ePCM slurry was greater than that
of the ePCM slurry. Their result indicated that GO granted the slurry
with superior photothermal conversion properties. Xu et al. [353]
measured the photothermal conversion performance of the base fluid,
CNT nanofluid, paraffin@Cu-Cu2O slurry, and paraffin@Cu-Cu2O/CNT
slurry, at a weight concentration of 4%. The overall results showed that
the CNT nanofluid, paraffin@Cu-Cu2O slurry, and paraffin@Cu-­
Cu2O/CNT slurry had higher temperatures compared to the base fluid
during 3500 s irradiation time. However, before 500 s, the addition of
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 45. Photothermal conversion efficiency of various micro/nano-ePCM slurries/dispersions for volumetric solar-absorption applications

Fig. 46. Temperature variation of MWCNTs-ePCM slurries at 5, 10, and 15 wt% while irradiated for 3000 s at the a) charging and b) discharging stages. Also shown
are the temperature variations for a 1:2 ethanol/water mixture and a 0.005 wt% MWCNTs nanofluid [334]. (Reused with permission from Elsevier).

particles had no significant impact on temperature, while after 500 s, the
temperature of the CNT nanofluid was higher than that of the slurries,
which was ascribed to the heat absorption of ePCMs during the melting
process. After 3000 s, the temperature of the CNT nanofluid, paraf­
fin@Cu-Cu2O slurry, and paraffin@Cu-Cu2O/CNT slurry increased to
99.3, 96.5, and 88.7◦ C, respectively, while the temperature of the base
fluid was only 79.8◦ C. Moreover, the calculated photothermal conver­
sion efficiency showed that the paraffin@Cu-Cu2O/CNT slurry had the
highest efficiency, which makes them favorable for DASCs.
Chen et al. [354] observed that during 7000 s of irradiation, the
temperature of an ePCM slurry at 5 wt% increased to 75 ◦ C, while the
temperature at 10 wt% increased to 80 ◦ C. However, the temperature at
15 wt% increased to 65 ◦ C. The decrease in temperature was attributed
to the reflection of radiation at higher weight concentrations. Moreover,
it was found that the ePCM slurries at 10 and 15 wt% exhibited higher
and lower receiver efficiencies compared to the slurry at 5 wt%,
respectively. Liu et al. [355] examined the photothermal conversion
performance of graphite-ePCM-based DASCs at different weight frac­
tions. Their results indicated that the temperature of the ePCM slurry at
10 wt% was lower than that of the base fluid, resulting in a lower
photothermal conversion performance and thermal storage capacity.
The authors attributed this result to the white color of the ePCM slurry
and the resulting higher light reflection.
Yuan et al. [363] studied the variation in temperature under irradi­
ation for 3000 s for slurries of paraffin@SiO2/GO and paraffin@SiO2 at
10 wt%. It was found that the temperature of the paraffin@SiO2/GO and
paraffin@SiO2 slurries increased to 80 and 67 ◦ C, respectively, with the
paraffin@SiO2/GO slurry having a higher receiver efficiency. Ma et al.
[356] indicated that the temperature of a paraffin@SnO2 slurry and a
paraffin@SnO2/CNT slurry at 5 wt% increased to 90.2 and 82.5 ◦ C,
respectively. In addition, it was shown that the paraffin@SnO2/CNT
slurry had a higher conversion efficiency. Latibari et al. [362] measured

46
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

the photothermal conversion performance of an ePCM slurry containing
water and 0.1% of GNP. It was shown that the temperature of the
GNP-ePCM slurry at 16 wt% and under an irradiation time of 3000 s
increased to 85 ◦ C, while the temperature of the base fluid and ePCM
slurry increased to 55 and 35 ◦ C, respectively. This result was attributed
to the white color of the ePCM slurry and the poor light absorption of the
base fluid. The authors concluded that the required time for the base
fluid and ePCM slurry to achieve 85 ◦ C was greatly reduced in the
presence of GNP.
Gao et al. [366] evaluated the photothermal performance of the base
fluid, ePCM slurry, GO-ePCM slurry, and rGO-ePCM slurry. The ePCMs
were produced with MF as the shell and octadecane modified by OA and
Fe3O4 as the PCM. It was found that the rGO-ePCM slurry attained the
highest thermal storage capacity and temperature in DASCs. They
attributed the photothermal performance enhancement to the superior
absorption property of rGO. A summary of the photothermal conversion
performance and efficiency data of ePCM slurries is presented in
Table 10.
3.6. Functional requirements of ePCM slurries/dispersions in solar
photothermal systems
3.6.1. The solid-liquid PCM core
To date, various core materials, including organic and inorganic,
have been used in ePCM systems. The selection of a PCM as the core
material mainly depends upon the intended application. In solar pho­
tothermal systems, paraffin is the most preferred core material. Non-
encapsulated paraffin has the advantages of little-to-no supercooling,
long-term chemical stability, wide melting temperature range (up to 100
◦
C), non-corrosiveness, and commercial availability. However, the main
drawbacks of paraffin are low thermal conductivity, flammability, and
low latent heat storage density (see Section 2.2.4). To resolve this
problem, paraffin has been encapsulated using a variety of shell mate­
rials, as will be discussed later. The advantages of encapsulating paraffin
are: 1) absence of any reaction between paraffin and its surrounding
environment, 2) ability to resist changes in volume during phase-change
transitions, 3) better leakage prevention, and 4) higher specific heat
capacity, thermal conductivity, and light absorption properties. These
properties have demonstrated that encapsulated paraffin has great po­
tential applications in solar-thermal systems.
3.6.2. The encapsulating solid shell
3.6.2.63. Surface-modified shells. As previously shown, polymer is one
of the most commonly used shell materials for creating ePCMs due to its
appropriate plasticity and outstanding sealing tightness compared with
inorganic shell materials. PMMA, PS, poly(urea-formaldehyde) (PUF),
poly(melamine-formaldehyde) (PMF), and PUR are commonly chosen as
shell materials to encapsulate PCMs. Among the organic shell materials,
MF shells have been widely employed due to their low price, high
strength, good stability, and thermal durability [6].
Since polymer shells have low thermal conductivity, researchers
have suggested inorganic shell materials which have undoubtedly
higher thermal conductivities compared to polymers. The most widely
used inorganic materials for encapsulating PCMs are titania (TiO2)
[292], silica (SiO2) [291], zinc oxide (ZnO) [378], tin dioxide (SnO2)
[365], and calcium carbonate (CaCO3) [379]. However, these shell
materials are usually white-colored with poor optical properties, which
seriously limits their application in DASCs. Consequently, it is impera­
tive to develop ePCMs with superior photothermal conversion capa­
bility. Recently, some researchers have attempted to use
surface-modified shells instead of conventional shells, including
TiO2/GO [352], Cu/Cu2O/CNTs [353], MWCNTs [354], MF/graphite
[355], SiO2/GO [363], SnO2/CNTs [380], PMMA/GNP [362], and
MF/rGO [366]. The proposed shells, due to the introduction of carbon
materials as fillers, were found to exhibit higher thermal conductivity
and solar-absorption capability compared to conventional polymeric
and inorganic shells (refer to Section 3.5.2).
3.6.2.64. Multiple concentric shells. One of the current research hotspots
is producing ePCMs with multi-layered shells for solar volumetric-
absorption applications. Liu et al. [381] fabricated bifunctional
micro-ePCMs for solar-thermal energy storage and solar photocatalysis.
The capsules were produced with n-eicosane as PCM and SiO2/cadmium
sulfide (CdS) as double-layered shell material. It was found that the
micro-ePCMs achieved an energy storage efficiency of 46%, an increase

Table 10
Reported data on the photothermal conversion performance and efficiency of various ePCM slurries/dispersions.
Core@shell Irradiance ePCM Carrying fluid Concentration Main results Ref.
time size

Paraffin@MF 3000 s 10 μm Ethanol/water 5, 10 and 15 wt Hybrid slurries possess lower photothermal conversion compared to [334]
MWCNT % MWCNT-nanofluids at the charging state. However, an inverse trend
nanofluid was observed at the discharging state.
Paraffin@titania-GO 4000 s 2− 5 μm Water 3 wt% Paraffin@titania-GO slurry showed superior photothermal conversion [352]
performance relative to paraffin@titania slurry.
Paraffin@Cu-Cu2O/ 3500 s 688 nm Water 4 wt% Paraffin@Cu-Cu2O/CNTs slurry has higher photothermal conversion [353]
CNTs efficiency compared to CNT nanofluids, paraffin@Cu-Cu2O slurry, and
base fluid.
Acid@MWCNTs 7000 s 50− 60 Water 0-15 wt% Acid@MWCNTs slurry with 10 and 20 wt% showed higher and lower [354]
nm photothermal conversion efficiency compared to the base fluid,
respectively.
Paraffin@MF/graphite 6000 s Not [BMIM]BF4 0-20 wt% - Paraffin@MF/graphite slurry with 10 wt% exhibited higher [355]
reported photothermal conversion performance and thermal storage capacity
compared to paraffin@MF slurry.
- Photothermal conversion performance of paraffin@MF/graphite is
reduced as the weight concentration is increased.
Paraffin@SiO2/GO 3000 s 20 μm Water 10 wt% Paraffin@SiO2/GO slurry revealed higher receiver efficiency and [311]
photothermal conversion performance compared to paraffin@SiO2/
GO slurry.
Paraffin@SnO2/CNTs 3000 s 1− 5 μm Water 5 wt% Paraffin@SnO2/CNTs slurry showed higher photothermal conversion [356]
performance compared to paraffin@SiO2/GO slurry.
CrodathermTM 60@PU 3000 s 3.34 μm Water 16 wt % Slurry with GNP showed higher photothermal conversion performance [362]
-0.1%GNP relative to the slurry without GNP.
Octadecane@MF/rGO 800 s Not Water 15.0 wt% Octadecane@MF/rGO slurry has higher photothermal conversion [366]
reported performance as compared to octadecane@MF/rGO, octadecane@MF/
rGO, and octadecane@MF slurries.

47
S.A. Albdour et al.
in phase-change enthalpy over 70 J/g, and a thermal conductivity in­
crease of 580%. Therefore, the micro-ePCMs exhibited excellent per­
formance in phase-change reliability, thermoregulation, and
solar-thermal performance. The micro-ePCMs also revealed excellent
photocatalytic activity under solar radiation. The capsules led to pho­
todegradation in MB by about 90 wt% under an irradiation time of
14400 s. Furthermore, the capsules showed a fluorescent property due to
the CdS layer. It was concluded that these unique bifunctional properties
can be utilized for sustainable solar photocatalytic and photochemical
systems. Yuan et al. [363] fabricated double-layered micro-ePCMs that
contained n-eicosane as a PCM and PMF/polydopamine (PDA) as a
double-layer shell. They found that with the addition of PDA, the
durability remained unchanged, the latent heat increased to over 190
J/g, and the ePCMs exhibited excellent photothermal conversion fea­
tures, including a quick heating rate and high latent heat. In addition,
the PDA layer decreased the leakage rate and strengthened the shell.
Recently, Pornea and Kim [382] designed and synthesized
micro-ePCMs with a three-layered shell, containing TiO2, SiO2, and PDA
as shell materials and n-eicosane as PCM, as shown in Fig. 47. The au­
thors provided an extensive investigation on the chemical structure and
composition, thermal induction capacity, and crystallinity of the ePCMs,
and it was found that the micro-ePCMs had a phase-change enthalpy of
125.92 J/g. Their study confirmed that the combination TiO2, SiO2, and
PDA not only improved the durability, photocatalytic activity, and
structural stability of the ePCMs, but also promoted localized visible
light absorption and scattering in the shell. Therefore, the designed
micro-ePCMs were deemed promising for solar-thermal conversion
applications.
3.7. The influence of key design parameters on solar ePCM systems
3.7.1. Size of PCM capsules
The size of the PCM capsules is a factor that can greatly affect the
thermal and optical characteristics of the slurry/dispersion as a whole.
In addition, the size distribution of ePCMs in the slurry/dispersion may
be non-uniform, and the ePCM motion may significantly affect the heat
transfer and flow characteristics. However, limited studies have
attempted to capture the effect of this parameter. Lin et al. [383]
numerically analyzed the heat transfer characteristics of ePCM slurries
under various volume concentrations (5-25 vol%) and sizes (5-1000
µm). Their results showed that a smaller capsule size led to higher heat
transfer enhancement, particularly when the size was smaller than 100
μm. Otherwise, the size effect on the heat transfer coefficient was not
Fig. 47. A composite three-layered shell of TiO2, SiO2, and PDA micro-
encapsulating an n-eicosane core (modified from [382]).
48
Progress in Energy and Combustion Science 93 (2022) 101037
noticeable. The mean heat transfer coefficient improved by almost 5.3%
as the size was decreased from 1000 to 100 μm. Furthermore, it was
found that as the volume concentration increased, the average heat
transfer coefficient initially increased, then dropped, reaching a
maximum value of almost 107 W/m2•K at a volume concentration of 20
vol%. The decrease in heat transfer coefficient was attributed to the high
viscosity and low thermal conductivity of the slurry.
Xu et al. [384] also numerically investigated the effect of capsule size
on the heat transfer performance of an ePCM slurry. Their results
showed that for a diameter less than or equal to 10 µm, the capsules were
uniformly distributed throughout the pipe. However, at diameters be­
tween 100 and 1000 µm, the distribution was non-uniform and the
capsules accumulated at the center of the tube. Also, when capsule sizes
were small, relative velocity between the capsules and water was nearly
zero, indicating that the slurry could be considered as a single-phase
fluid (at least from a momentum transfer perspective). However, the
relative velocity increased significantly when the capsule size increased.
In addition, it was revealed that pumping power was reduced with
smaller capsule sizes. The pressure-drop and viscosity dramatically
increased by almost 31 and 85.5% respectively, as the size increased
from 500 to 1000 µm. Ma et al. [385] examined the size effect on the
velocity distribution, pressure drop, and volume fraction distribution of
a slurry in a horizontal pipe subjected to constant heat flux. It was
concluded that as the size decreased from 1000 to 1 µm, the mean heat
transfer coefficient increased by 243%. Furthermore, excellent heat
transfer performance with no penalty in pressure drop was observed for
capsule sizes in the range of 10-100 μm.
3.7.2. Morphology of PCM capsules
As one can notice from the previous sections, most research studies
on ePCMs to date have focused on spherical shapes. To the best of our
knowledge, only one study has taken into account the possibility of
having various ePCM morphologies. Liu et al. [386] aimed to investigate
the morphology effect on thermal storage performance and thermal
response of ePCMs. They designed and fabricated spherical, tubular, and
octahedral ePCMs with n-eicosane as the core and TiO2 as the shell, as
illustrated in Fig. 48. The thermal analysis under non-isothermal con­
ditions indicated that the spherical ePCMs showed the highest amount of
heat charging/discharging due to their highest encapsulation efficiency,
while the tubular ePCMs had the fastest thermal response because of
their specific internal nanostructures. The spherical ePCMs showed the
best energy storage, followed by the octahedral ePCMs, and then the
tubular ePCMs. All the studied ePCMs exhibited excellent photocatalytic
capabilities, temperature regulation, thermal durability, prominent heat
charging/discharging performance, and good shape stability.
3.7.3. The core-to-shell ratio
The core-to-shell ratio is another influencing factor for ePCMs.
However, few studies have examined its impact on the thermal stability
and the core/shell structure of ePCMs. The reported data has shown that
a smaller core-to-shell ratio means having a thicker shell and less PCM
content, and hence, a smaller capacity of latent heat storage. At a higher
core-to-shell ratio, however, the ePCM strength diminishes and the risk
of PCM leakage increases. Zhang et al. [163] microencapsulated
n-octadecane with a PU shell at core-to-shell mass ratios of 75:25 and
70:30. It was shown that as the mass ratio increased, the mean diameter
of the micro-ePCMs increased significantly. Specifically, the mean
diameter at mass ratios of 75:25 and 70:30 was 6.9 and 7.1 µm,
respectively. It is also observed that the latent heat of the ePCM with a
mass ratio of 75:25 is lower than that of 70:30. However, the mass ratio
of 75:25 resulted in better thermal stability.
Roy and Sengupta [387] evaluated the properties of micro­
encapsulated SA and n-eicosane with shell thicknesses of 15 and 30%
when subjected to radiation and thermal cycling tests. It was observed
that for at least 100 heating/cooling cycles, the ePCMs with a thickness
of 30% were thermally and structurally stable. However, the
S.A. Albdour et al.
Fig. 48. SEM image of a) tubular, b) octahedral, and c) spherical micro-ePCMs (n-eicosane as core and TiO2 as shell) [386]. (Reused with permission from Elsevier).
micro-ePCMs with a shell thickness of 15% failed the heating/cooling
cycling tests. Moreover, degradation in thermal properties of the ePCMs
was observed under the radiation test (1 MeV radiation). Hawlader et al.
[158] showed that a lower amount of shell material led to incomplete
encapsulation of the PCM, and that the efficiency of micro-ePCMs
increased as the core-to-shell mass ratio decreased, enabling the rapid
release and storage of thermal energy.
Ohtsubo et al. [388] microencapsulated fenitrothion with a PUR
shell to examine the relationship between mechanical strength and the
mean diameter, shell thickness, and their ratio. The results showed that
the breaking behavior was mainly affected by the mean diameter. The
smaller the pressure required to damage half of the ePCMs, the higher
the mean diameter-to-shell ratio. Su et al. [316] studied the impact of
different core-to-shell ratios (1:1, 3:1, and 4:1) on the performance of
ePCMs. MF and lauryl alcohol were employed as shell and core mate­
rials, respectively. It was proven that higher PCM content was always
required to release/store more thermal energy. However, a reduced shell
thickness can have a negative impact on the mechanical properties of the
capsules. By striking a balance between core content and shell thickness,
it was found that the best performance of the ePCMs was achieved at a
mass ratio of 3:1.
Zou et al. [375] prepared ePCMs with the different core-to-shell ra­
tios of 2:1, 3:2, 1:1, and 1:2. Melamine urea-formaldehyde was used as a
shell and paraffin as a PCM. The shell was doped with Ag, CNT, and
graphene nanomaterials. The authors found that the freezing and
melting latent heats decreased with the reduction of the core-to-shell
ratio. This was mainly attributed to the decrease in the PCM content
as the core-to-shell ratio dropped. Zhang et al. [309] prepared ePCMs,
with poly(2,3,4,5,6-pentafluorostyrene) as the shell and n-octadecane as
the PCM, at six different core-to-shell ratios. It was revealed that ePCMs
with a core-to-shell mass ratio of 2:1 had the highest encapsulation ef­
ficiency, minimum size, and highest thermal storage efficiency, while
ePCMs with a core-to-shell ratio of 3:1 had the lowest latent heat and
encapsulation efficiency. Furthermore, it was observed that the thermal
conductivity of ePCMs was not affected by the core-to-shell ratio.
3.7.4. Loading fraction of PCM capsules
As previously described in Section 3.4, dispersing ePCMs into a fluid
can significantly alter the thermophysical properties of the fluid.
Numerous studies have reported that increasing the loading fraction of
ePCMs leads to an increase in specific heat, in particular during the
phase-change process, an increase in dynamic viscosity, and an increase
or a decrease in thermal conductivity. Moreover, the addition of PCM
capsules to a pure fluid led to a moderate-to-substantial increase in the
absorption property of the fluid, mainly depending on the shell material.
Note that the absorption properties of ePCM slurries have been mostly
examined at only one loading fraction.
While there are several studies that examined the loading fraction
effect on the thermophysical and optical properties of ePCM slurries,
there are limited studies on the impact of loading fraction on the pho­
tothermal performance of ePCM slurries for solar systems. The study by
Liu et al. [355] revealed that, despite the fact that more ePCMs can result
in an improvement in photothermal conversion, a high loading fraction
of ePCMs does not always lead to a higher heat transfer rate. They
observed that an ePCM slurry at 20 wt% had lower photothermal
49
Progress in Energy and Combustion Science 93 (2022) 101037
performance and thermal storage capacity than that at 10 wt%. This
result was attributed to the higher reflectivity of the slurry at 20 wt%.
Fig. 49 illustrates the photothermal conversion performance and ther­
mal storage capacity of slurries at 10 and 20wt%. Dutkowski et al. [375]
observed that the more capsules are in the carrying fluid, the lower the
temperature of the solar collector. The outlet temperature of a solar
collector with an ePCM slurry at 8.6 wt% was 10 K lower than that of the
pure fluid, indicating that ePCM slurries are very effective in reducing
heat loss to the environment. Wang et al. [334] observed that sus­
pending ePCMs in a fluid has an adverse effect. The photothermal per­
formance of slurries was found to decrease with increasing the loading
fraction, which was due to the high reflectivity of micro-ePCMs. They
suggested modifying the shell material with a nanolayer to considerably
improve the optical absorption properties of ePCMs.
3.7.5. Flow rate
Mass/volume flow rate is another parameter that may affect the ef­
ficiency of ePCM slurries in solar systems. However, very limited studies
have taken this parameter into consideration, which may broaden the
possible applications of ePCM slurries in the area of solar systems.
Dutkowski et al. [375] evaluated the photothermal efficiency at the
different mass flow rates of 20, 40, and 80 kg/h, under different irra­
diance values. It was observed that an increase in solar irradiance led to
an increase in the temperature of both the pure fluid and slurry. How­
ever, the temperature of the slurry decreased with increasing the mass
flow rate at the same irradiance, thereby providing a higher energy
conversion efficiency. Fu et al. [335] performed an experimental study
on an ePCM slurry-based PVT system. Their results showed that as the
flow rate increased, the maximum temperature on the surface of the
panel decreased. Moreover, by increasing the flow rate from 200 to 400
ml/min, the average electrical efficiency increased from 12.2 to 12.4%
and the thermal efficiency increased from 58.3 to 68.5%.
3.8. Comparing macro-, micro-, and nano-ePCMs
The encapsulation of PCMs is important to prevent the leakage of
liquid PCMs, improve heat transfer by overcoming the low thermal
conductivity of PCMs, control volume change during solid-liquid tran­
sition, and reduce chemical interaction with the environment. PCM
encapsulation can be classified into three types based on their size;
namely, macroencapsulation (≥ 1 mm), microencapsulation (1− 1000
µm), and nanoencapsulation (≤ 1 µm). Table 11 summarizes the ad­
vantages and disadvantages of PCM encapsulation at different scales.
Macroencapsulation is the most common technique for encapsu­
lating PCMs, in which a considerable amount of PCM, that can range
from a few grams to a kilogram, is encapsulated. PCMs can be macro­
encapsulated in different shapes, such as tubes, rectangular panels, and
spheres. The most cost-effective macro-encapsulants are mild steel, tin-
plated cans, and plastic bottles (made of low/high density poly­
propylene and polyethylene). In general, macro-ePCMs can be easily
fabricated into any desired shape or size to suit various applications.
They can be employed for a wide range of energy storage purposes by
carefully selecting the capsule design and material, which can be
directly used as a heat exchanger or integrated into building materials.
Although macroencapsulation techniques have been known for many
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 49. a) Thermal storage capacity and b) temperature rise as a function of irradiation time for a pure ionic liquid ([BMIM]BF4) and slurries containing different
micro-ePCMs at different weight concentrations [355]. (Reused with permission from Elsevier).

inorganic shell materials using several chemical, physical, and physical-

Table 11
chemical techniques. Microencapsulation is an effective way to prevent
The advantages and disadvantages of ePCM encapsulation at different scales.
PCM leakage in TES systems under several heating/cooling cycles,
Encapsulation Advantages Disadvantages reduce interaction of the PCM with the outside environment, and
technique
enhance heat transfer rate due to the large surface area. Sari et al. [390]
Macroencapsulation (≥ • Can be easily handled • Leakage/perforation observed that micro-ePCMs have higher thermal reliability and chemical
1mm) during production. issues. stability compared to macro-ePCMs. However, micro-ePCMs are more
• Low supercooling • Poor conductivity.
degree. • Non-uniform
difficult to manufacture than macro-ePCMs since their size is less than 1
solidification (PCM mm. Yamagishi et al. [359] showed that the damage rate of
core and boundary). micro-ePCMs decreased as their size was reduced, and that smaller
• Complicated micro-ePCMs (5-10 μm) exhibited higher mechanical strength and could
incorporation into
better withstand shear forces while being pumped. Therefore, the sta­
building materials.
Microencapsulation • Easy to integrate into • Leakage/damage bility of micro-ePCMs was found to be strongly affected by their size.
(1− 1000 µm) building materials. issues. The most recent technique to overcome the drawbacks of uncoated
• Volume change • High viscosity. PCMs is nanoencapsulation, which is similar to microencapsulation,
resistivity during solid- with the exception that it involves ePCMs at the nanoscale. Nano­
liquid transition.
• Various encapsulation
encapsulation is expected to result in higher heat transfer rates due to
techniques are the massive surface area of nano-ePCMs. Nano-ePCMs are also known to
available. be physically more stable than micro-ePCMs. Sukhorukov et al. [391]
• High heat transfer area. demonstrated that the deformation of ePCMs with a size of 10 nm was
Nanoencapsulation (≤ • High mechanical • High supercooling
lower than that of 10-µm capsules when the same force was applied. Yet,
1 µm) stability. degree.
• Volume change • Encapsulation it should be emphasized that nanoencapsulation of PCMs is still in the
resistivity during solid- techniques are limited. infancy stage. Therefore, at present, a clear picture of the characteristics
liquid transition. • High cost. of nano-ePCMs and their benefits over macro- and micro-ePCMs cannot
• Excellent suspension be drawn.
stability.
• High heat transfer area.
• Promising structures to
integrate into building 3.9. Conclusions and future research directions
materials.
Despite the huge potential for micro/nano-ePCM slurries and dis­
persions in photothermal applications, where they perform the com­
years, further work is required to address concerns over corrosion pro­
pound functions of solar absorbers, storage media, and heat carriers,
tection, leakage/perforation issues, and improvement of heat transfer
there is a number of critical challenges that must be resolved before
rates. For example, recently, Vérez et al. [389] experimentally examined
micro/nano-ePCMs may be used in thermal and solar applications in a
the effect of the design of macro-ePCMs on the energy storage perfor­
commercial capacity.
mance using two rectangular slabs with thicknesses of 17 and 35 mm.
Perhaps the most demanding challenge facing ePCMs is related to
Their results revealed that, compared to the thicker slab, the thinner slab
their synthesis and encapsulation method. This is particularly the case
resulted in higher thermal efficiency with reductions of 14 and 30% in
for nano-ePCMs, which have shown superior stability, heat transfer, and
charging and discharging times. One can conclude that the ePCM size
solar absorption characteristics over conventional micro-ePCMs. Phys­
can critically affect the TES performance.
ical and physical-chemical methods have shown their limitation in
Unlike macro-ePCMs, which do not require any predefined proced­
achieving nano-size capsules. However, nano-ePCMs can be produced
ures to encapsulate the PCM, micro-ePCMs require more sophisticated
using chemical methods, particularly polymerization methods, which
techniques. In microencapsulation, PCM capsules, which are mostly
necessitates further research into these methods. Moreover, it was found
spheres, are formed by coating a small amount of PCM with organic or
that the selection of the ePCM preparation method is highly dependent

50
S.A. Albdour et al.
on the core/shell material, capsule size, shell thickness, and desired
thermal, chemical, and mechanical properties. Therefore, the procedure
must often be custom-tailored to produce desirable micro/nano-ePCMs.
This is a costly, complicated, and time-consuming process that results in
techniques limited to the lab scale without any prospects for widescale
production. Therefore, the future direction should be the proposition of
novel cost-effective techniques which combine the simplicity of the
synthesis process with encapsulation of more than one core/shell ma­
terial type.
The use of complementary and orthogonal characterization tech­
niques is highly recommended to adequately identify the structural,
thermophysical, and optical properties of micro/nano-ePCMs. However,
some of these techniques are not recommended as they can be very
costly and complex to use (e.g., SAXS and WAXS), while others may hide
the impurities of ePCMs or even damage them under intense laser ra­
diation (e.g., Raman spectroscopy). Therefore, simpler, faster, and more
efficient techniques for the characterization of micro/nano-ePCMs
should be explored.
Despite its paramount importance for practical deployments, un­
derstanding and evaluating the chemical, mechanical, and thermal
stability of micro/nano-ePCMs is still in its infancy. Clearly, a uniform
standard for the preparation of stable micro/nano-ePCMs needs to be
developed. Although it can change the morphology and structure of
ePCMs, one parameter that has not yet been reported is the long-term
direct exposure to cyclic solar radiation. Stability evaluation of ePCM
slurries/dispersions is still at an early stage, and only a few character­
ization techniques have been reported. However, these techniques
either require extreme dilution of the slurry/dispersion, cannot be per­
formed without capsule damage, or are limited by the centrifuge ca­
pacity. Consequently, the development of non-invasive stability
evaluation techniques is critical to further advance the field of ePCM.
The efficiency of micro/nano-ePCM slurries/dispersions in solar
photothermal applications is determined by their thermal, rheological,
Fig. 50. Multi-scale structures encountered in the analysis of ePCM slurries. This includes molecules/atoms at the molecular scale, PCM molecular assemblies at
mesoscale I, micro/nano-capsules at the microscale, capsule aggregates at mesoscale II, and whole unit operation.
51
Progress in Energy and Combustion Science 93 (2022) 101037
and optical properties. However, studies on these properties for different
capsules sizes and shapes, at different particle loadings, under unsteady-
state conditions, using non-paraffin cores, and during phase change, are
still largely unexplored. The particle loading, in particular, can be a
decisive factor since using too high or low a concentration can severely
reduce photothermal efficiency due to reflection losses or radiation non-
absorption losses, respectively. Moreover, compared to thermal con­
ductivity and optical properties, limited studies have been devoted to
the measurement of heat capacity (before, during, and after phase
transition) and rheological properties of ePCMs.
The presented data revealed that slurries/dispersions with conven­
tional polymeric shells were significantly less promising in the
enhancement of thermal conductivity and solar-weighted absorption
relative to carbon-modified shells. In particular, double-layered shells
were found to increase the photothermal conversion properties, reduce
the leakage rate, and strengthen mechanical properties of the capsule.
Furthermore, nano-sized PCM capsules were found to incur a lower
penalty on viscosity (and pumping requirements) relative to micro-sized
ones, especially at high concentrations. Therefore, it is highly recom­
mended that future development efforts be focused on nano-ePCM sys­
tems with carbon- or metal-modified shells for volumetric direct-
absorption applications.
4. Theory and fundamentals of solar ePCM systems
4.1. Modeling of flow and heat transfer in ePCM slurries/dispersions
From the perspective of thermal and hydrodynamic transport, an
ePCM slurry/dispersion is a two-phase solid-liquid system that exhibits
different behaviors at different scales. By delving into the system, as
shown in Fig. 50, it includes molecules/atoms at the molecular scale,
PCM molecular assemblies at mesoscale I, micro/nano-capsules at the
microscale, capsules aggregated at mesoscale II, and whole unit
S.A. Albdour et al.
operation at the macroscale. Some behaviors, such as molecules/atoms,
discrete entities, and unit operations, have well-established models that
make them relatively simple to identify. However, despite their impor­
tance in understanding and modeling dynamic behaviors, complex be­
haviors at scales such as those for PCM molecular assemblies and ePCM
clusters are not well described. The complexity lies in understanding and
analyzing the material and interfacial structures at mesoscale I, as well
as the heterogeneous flow structures at mesoscale II, before introducing
their effects on neighboring scales (boundary scales and ePCM
particles).
Many researchers have experimentally and numerically investigated
the different scales and physical phenomena in ePCM slurries/disper­
sions to reveal the thermal transport mechanisms associated with the
phase-change process. Because of the problem complexity and building
on the rapid development of computers, numerical methods have
proven to be a powerful tool due to their ability to provide the benefits of
high efficiency and low cost [118]. Therefore, the purpose of this section
is to address the possible models to be used to simulate ePCM slur­
ries/dispersions, including their characteristics and limitations, and
demonstrate their applicability to ePCM systems. While not all of the
models listed below have been applied to the field of ePCMs, they should
be considered as candidate simulation methods in future works.
Fig. 51. illustrates the range of numerical techniques that will be
discussed in the following sections. Micro and mesoscale models are
discrete in nature, capturing comprehensive information about particle
dispersion and trajectory, particle-wall interactions, and particle-
particle interactions. Macroscale models are based on a continuum
approach, in which the ePCM slurry/dispersion is viewed as a homo­
geneous medium with effective properties. Multi-scale models combine
discrete and continuum approaches.
The Knudsen number is commonly used to assess whether a fluid
phase may be deemed continuous or not. Knudsen number can be
expressed as,
λkn
Kn = , (15)
L
where λKn is the molecular mean free path and L is characteristic
physical length scale. Fluid flow can be categorized into four regions
based on the Knudsen number [392]: continuum flow (Kn < 0.001), slip
flow (0.001 < Kn < 0.1), transition flow (0.1 < Kn < 10), and free
molecule flow (Kn > 10).
Fig. 51. Classification of the numerical simulation methods for ePCM slurries/dispersions into microscale, mesoscale, macroscale, and multiscale.
52
Progress in Energy and Combustion Science 93 (2022) 101037
4.1.1. Continuum models
In general, continuum mechanics is a discipline that studies the
behavior of a system while ignoring its particulate nature. As a result, an
area can be divided indefinitely with no individual particles. This
simplification allows us to study fluid movement on scales larger than
particle distances. The flow and heat transfer of ePCM slurries/disper­
sions are simulated using two models under the general umbrella of
continuum mechanics: single-phase and two-phase models.
Single-phase models. To date, the majority of numerical studies on ePCM
slurries/dispersions has been based on a single-phase approach that
assumes the two phases (PCM capsules and the carrying fluid) are well
mixed and travel at equal velocities in thermal equilibrium, i.e., there
are no velocity or temperature slips between them. Other common as­
sumptions in single-phase models include [6,118,191,393,394]:
• Below a threshold of ePCM concentration, the slurry/dispersion is
considered Newtonian (usually less than 30%).
• Thermophysical properties of the slurry that are dependent on tem­
perature include thermal conductivity, specific heat, and density.
• The capsules are rigid and the shell is thin with an appropriate ratio
to the core. This way, the PCM makes up the majority of the capsule
volume.
• The phase-change process is governed by conduction and convec­
tion, with natural convection controlled by the Boussinesq
approximation.
According to the way of handling the phase-change process in the
ePCM slurry/dispersion, the single-phase approach is divided into three
models: the heat source-term model, the effective heat-capacity model,
and the enthalpy model. The finite-difference method (FDM), finite-
element method (FEM), or finite-volume method (FVM) are used to
discretize the governing equations of fluid flow and heat transfer. After
discretizing the equations, the temperature and velocity profiles are
obtained. The previously mentioned single-phase models are commonly
implemented in commercial computational fluid dynamics (CFD)
packages, such as ANSYS Fluent and COMSOL Multiphysics [116].
4.1.1.66.0. Heat source-term model. This methodology assumes that
the phase-change effect—heat absorption or generation—is equivalent
to internal heat source within the fluid, thus serving as a heat source in
the energy equation. As shown in Fig. 52, an ePCM particle consisting of
a core and shell can be considered a standard spherical particle.
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

4.1.1.67.0. Effective heat-capacity model. This approach is regarded

as a simple and effective heat transfer model for ePCM slurries in which
the complicated source term is avoided; thus, it can be easily used in
commercial CFD packages [396]. Effective heat capacity (ceff) includes
both sensible heat (cp) and latent heat (Hs-l). The general energy
equation based on the effective heat-capacity model is written as
follows,
∂T
ρceff = ∇.(k∇T). (25)
∂t
An accurate result is dependent on selecting an appropriate model
that describes actual variation in the specific heat of the slurry [118,397,
398]. In Eq. (25), it can be seen that temperature is the only unknown
variable, where determining the specifications of ceff is key to this
method,
cp,s , T < Ts (solid state)
cp,s + cp,l Hs − l
ceff = { + , Ts ≤ T < Tl (mushy state) . (26)
2 Tl − Ts
cp,l , T ≥ Tl (liquid state)
Fig. 52. Schematic diagram of an ePCM particle consisting of a core with
radius rco and a shell with thickness rpa-rco. It should be noted that the previous empirical equation considers
latent heat, Hs-l, a constant within the phase-change temperature range,
Assuming the slurry is pumped through a circular pipe, the energy i.e., within the mushy zone. An alternative empirical relationship for ceff
equation in cylindrical coordinates is [393,395,396], as a function of temperature can be obtained using data from DSC [399],
( ) as follows,
∂Tb 1 ∂ ∂Tb
ρslcp, slu = ksl r + S. (16) /( )
∂x r ∂r ∂r dHs − l dT
ceff (T) = m , (27)
dt dt
The velocity equation of the fully-developed laminar slurry flow in
the circular pipe is: where the heat flow rate through ePCM particles is represented by dHs-l/
u = 2umax[1 − (r / ro)2]. (17) dt, and the rate of temperature increase or decrease is represented by dT/
dt, which is known from the scanning rate of the DSC test. It is worth
Thermophysical property correlations are used to find the density, noting that theceff(T)profile obtained by DSC is typically non-linear,
thermal conductivity, and specific heat of the ePCM slurry, as will be necessitating piecewise linear interpolation to be used in numerical
detailed in Section 4.2. simulations.
The fluid internal heat source, S, is defined as the product of the Total enthalpy model. In the final single-phase strategy, cp and Hs-l
absorption/generation rate per particle and the number of ePCM parti­ are merged into the total enthalpy, H, as a primary variable for the
cles per unit volume of slurry. The heat absorption/generation rate per energy equation, as shown in Eq. (28) [118,400],
particle is expressed as follows:
∂H
2
Q = − 4π rpa hpa(Tpa − Tf ). (18) ρ = ∇.(k∇T). (28)
∂t
And the number of ePCM particles per unit volume is: The critical step, as with the effective heat-capacity model, is to use
an accurate H(T) relationship, as given in Eq. (29) [401,402],
3C
N= . (19) ⎧
4πrpa
3 ∫T
⎪
⎪
⎪
⎪ Cp, s, T < Ts (solid state)
As a result, the source term in Eq. (16) becomes, ⎪
⎪
⎪
⎪
⎪
⎪ Ti
⎪
⎪
3C ⎪
S = Q.N = − hpa(Tpa − Tf ). (20) ⎪
⎨ ∫Ts T − Ts
rpa H= Cp, sdT + Hs − l , Ts ≤ T < Tl (mushy state) , (29)
⎪
⎪ Tl − Ts
Equivalently, the control energy equation in spherical coordinates is: ⎪
⎪
⎪
⎪
Ti
⎪
⎪
( ) ⎪
⎪ ∫Ts ∫T
∂Tpa ∂ ∂Tpa ⎪
⎪
r2 ρpacp, pa = kpar2 . (21) ⎪
⎪
⎩ Cp, sdT + Hs − l + Cp, ldT, T ≥ Tl (liquid state)
∂t ∂r ∂r
Ti Tl
The thermophysical properties of shell material are calculated as
follows: where Ti is the initial temperature at total enthalpy H = 0 kJ/kg.

rco < r < rsh : cp,pa = cp,sh , kpa = ksh , ρpa = ρsh . (22)
Two-phase models. In most cases, the slip velocity between ePCM par­
The thermophysical properties of core material are calculated as ticles and the carrying fluid is non-zero, especially at high ePCM particle
follows: concentrations [403]. As a result, particle movement causes spatially
and temporally non-uniform distributions of concentration and thermal
0 < r ≤ rco : kpa = kco , ρpa = ρco , (23)
properties through the flow domain. To capture these effects, two-phase
Eulerian–Eulerian models were proposed to describe the flow and heat
− cp,co , Tpa < Tm − ΔTpa
transfer of ePCM slurries and to gain a better understanding of the
( )
cp,pa Tpa = { cp,co +
Hs − l
, Tm − ΔTpa ≤ Tpa ≤ Tm . (24) thermal and hydrodynamic transports in the solid-liquid two-phase
ΔTpa system. Generally, three different Eulerian–Eulerian methods have been
cp,co , Tpa > Tm described in the literature: mixture model, Eulerian, and volume of fluid

53
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

[404]. In numerical investigations of ePCM slurries, the two-phase
Eulerian (TPE) model was used. The TPE model regards the solid and
liquid phases as interpenetrative continua with interphase momentum
and energy exchange. While both phases share the same pressure,
separate continuity, momentum, and energy equations are used for each
phase (i.e., fluid and particles), while using appropriate interaction
terms to represent interphase effects.
The following are assumptions commonly employed in the TPE
model to simplify computations [385]:
• It is assumed that solid particles are smooth and spherical, with a
uniform diameter.
• The slurry/dispersion is considered to be incompressible and
Newtonian.
• Inelasticity of ePCMs is considered, so the energy loss caused by
collisions can be evaluated in the kinetic theory of granular flow.
• The flow of ePCM slurry can be laminar or turbulent.
The mass conservation equations are as follows:
∂ ually. In such methods, each discrete entity can represent a given
(αlρl) + ∇.(αlρlvl) = 0,
∂t
∂
(αsρs) + ∇.(αsρsvs) = 0.
∂t
The momentum conservation equations are as follows:
∂
(αlρlvl) + ∇.(αlρlvlvl) = − αl∇P + αlρlg + ∇.→
τ l + Fsl, l,
∂t
2
→
τ l = αlμl[∇vl + (∇vl)T] − αlμl(∇.vl)I,
3
where Cdr, Clift,Ctdand Cvm are the drag, lift, turbulent dispersion, and
virtual mass force coefficients, respectively. The diameter and volume
fraction of dispersed ePCM particles are dpa and αpa.
The parameters P, μ, and ξ in Eqs. (33) and (35) denote the pressure,
shear viscosity, and bulk viscosity of each phase, which are affected by
the magnitude of velocity fluctuations of the ePCM particles. These three
quantities can be derived from the kinetic theory of granular flow after
solving the conservation equation of solid fluctuating energy to obtain
the granular temperature [385]. As for energy conservation, presently,
there are two approaches for dealing with an ePCM slurry/dispersion
based on the TPE model; namely, the effective specific-heat model [385,
406] and the total enthalpy model [407,408]. Each is adopted for the
energy conservation to describe phase change in the ePCM particle
phase.
4.1.2. Discrete models
The physical meaning of a discrete model is straightforward—it
models discrete entities in the flow domain as the primary elements in
the simulation, with their motions and interactions computed individ­
(30) physical particle. Discrete models, like continuum models, are rarely
solved analytically. Discrete models are discretized at the implementa­
(31) tion level, with the physical models already being discrete. As a result,
discretization is essential to numerically integrate forces between
discrete elements and to update their states (e.g., velocity and position)
[409]. The strength of many discrete models primarily stems from the
(32) well-known molecular dynamics (MD) method at the microscale. As a
result, as the foundation of this approach, molecular dynamic simula­
tions are revised first, followed by Monte Carlo simulations and
(33) smoothed particle hydrodynamics.

∂ → 4.1.2.70. Molecular dynamics. The MD approach considers the in­

(αsρsvs) + ∇.(αsρsvsvs) = ( − αs∇P − ∇Ps ) + αsρsg + ∇.→
τ s − F sl,s ,
∂t teractions of a group of molecules and atoms (system components) as
(34) fluid particles. Over a given time period, the dynamics and interactions
[ ] of molecules and atoms are computed. The calculation period is defined
→ 2
τ s = αsμs ∇vs + (∇vs)T − (∇.vs)I + ( − Ps + ξs∇.vs)I. (35) as the time required to reach a dynamic evaluation between molecules
3 and atoms [410]. MD has a very small time step, usually on the order of
The first term on the right-hand side of Eqs. (32) and (34) shows the fs (10− 15 s) [116].
pressure gradient, the second and third terms are for gravity and stress. MD solves the system of interacting particles using Newton’s equa­
→ tion of motion to specify the trajectories of atoms and molecules.
The last term represents the interfacial forces, F sl , between the two
→ → Therefore, thermophysical properties can be derived. Using interatomic
phases, which are due to the drag force, F dr , lift force, F lift , and tur­ potential force fields, such as the Lennard-Jones potential, the forces
→ between particles are calculated. The calculation of the force field is
bulent dispersion force, F td . This is in addition to the virtual-mass force,
→
F vm , applicable only when the density of the dispersed phase is much regarded as the most critical factor influencing MD accuracy [410].
lower than that of the liquid phase [405]. As a result, the final term of Based on knowledge of the forces acting on molecules, the velocity,
the momentum equation can be expressed as follows (i represents s or l acceleration, and position of particles can be calculated. Thus, statistical
phase), averaging is used to calculate bulk flow domain properties such as ve­
locity, vorticity, stream function, viscosity, density, mass diffusivity, and
→ → → → → pressure [410].
F sl,i = F dr,i + F lift,i + F td,i + F vm,i . (36)
The MD method has been applied in a variety of fields, including
The drag force, lateral lift force, turbulent dispersion force, and physics, biophysics, pharmacophores, and multiphase flow. Despite the
virtual mass force exerted on scattered ePCM particles can be calculated differences in particle characteristics and interaction models between
using the following equations: these fields, they all share common aspects. For instance, the principle of
⃒ ⃒( )
→ 3 ⃒ ⃒ conservation of energy is explicitly used. In other words, there are no
F dr = Cdr ρi αpa ⃒⃒→ v i ⃒⃒ →
v pa − → v pa − →
vi , (37) hidden energy dissipation or energy production during the particle
4d pa
interaction process without addressing a quantitative description. The
random behavior of particles with high motion fluctuations is then
→ tracked. This often takes a long time, and most of the details of such
F lift,i = − Clift ρi αpa →
vi− →
v pa × ∇ × →
v i, (38)
behavior are eventually discarded [410].
→ The most common codes for MD are the large-scale atomic/molec­
F td,i = Ctd ρi ki ∇vpa , (39) ular massively parallel simulator (LAMMPS) package [411,412], mate­
⎛ ⎞ rials studio package [123,413], and condensed-phase optimized
→ di →
v i dpa →
v pa ⎠ molecular potentials for atomistic simulation studies (COMPASS) [414].
F vm,i = Cvm ρi αpa ⎝ − , (40)
dt dt It is reported that MD is suitable for simulating complex fluids and ge­
ometries, as well as non-equilibrium processes at the atomic level [410].

54
S.A. Albdour et al.
However, MD is disadvantaged by difficulties in selecting the most
appropriate force field [413] and being computationally demanding in
terms of the number of particles [116].
A few researchers used MD to study phase-change processes. For
example, Zhang et al. [123] used MD to study the thermophysical
properties of a paraffin-ethylene-vinyl acetate PCM with different con­
centrations of graphene (0.7, 1.5, 3.6, and 7.0 wt%). Results showed that
using graphene at 0.7 wt% provided the highest thermal conductivity
and diffusion coefficient, enhancing molecule mobility and encouraging
phonon transport. Yu et al. [413] employed an optimized MD method to
create a physical model of an NaCl-SiO2-based molten-salt composite
PCM, and to study the effect of adding SiO2 nanoparticles on the ther­
mophysical parameters of the PCM. Results showed that simulated
densities under the chosen force field were 10.8% lower than the
experimental data. Furthermore, 2.4 vol% of SiO2 nanoparticles
increased the thermal conductivity of NaCl by 44% while increasing
viscosity by 23.6%.
Some studies reported that MD is an effective way to describe the
melting behavior of PCM slurries. For example, Rao et al. [414] inves­
tigated the melting behavior of n-nonadecane PCM slurries using MD.
The melting temperatures simulated were very close to the experimental
data. Using the COMPASS force field, Wang et al. [415] investigated the
melting mechanism in a nano-ePCM slurry. The simulated results
revealed that the heat capacity of the nano-ePCM slurry decreased as the
mass fraction of PCM (octadecane) increased. Furthermore, a sharp heat
capacity peak was observed near the melting temperature, indicating
that a large amount of latent heat was absorbed.
4.1.2.71. Monte Carlo models. A Monte Carlo (MC) simulation is based
on calculating the characteristics of a given system by generating
enough stochastic events to catch and record its behavior. It is less
complicated than a MD in that it does not require a force field [416].
Monte Carlo methods make use of the concept of computational parti­
cles, which are significantly larger than actual molecules but behave like
them. In the direct-simulation Monte Carlo method, for example, a
computational particle may represent a set of 106− 1011 molecules [417,
418].
The Monte Carlo method begins with an initial particle configuration
in a given system and then attempts to change this original configura­
tion. The Stokes-Einstein equation [419] is used to select the particles to
be changed. The movement may be accepted or rejected based on an
acceptance criterion. The acceptance standard should ensure that new
configurations sampled in the simulation are drawn from a statistical
mechanics ensemble distribution and are sampled with the appropriate
weight. After the acceptance/rejection step, one value for the property
of interest is obtained, and an accurate average value of the property can
be obtained after many repetitions of the move [416]. The implemented
scheme must be ergodic, which means that every accessible particle in
the configuration space must be able to reach any other particle in the
space with an infinite number of Monte Carlo moves.
4.1.2.72. Smoothed particle hydrodynamics. Smoothed particle hydro­
dynamics (SPH) is a well-known mesh-free method that has received a
lot of attention. SPH represents the entire continuous system as a series
of particles, each with its own set of information and adhering to the
governing equations. The simulation is carried out after marking the
location and specifying all the physical information for each particle. As
such, SPH has the advantage of being able to easily capture the interface
and distribute the particles freely [420]. Using kernel and particle ap­
proximations, approximate numerical solutions are obtained based on
the motion and physical properties of particles. A weight function
known as the smoothing kernel function is used inside the integral
representation of the field function approximation in kernel approxi­
mation. By contrast, the particle approximation substitutes a sum of all
the equivalent values of surrounding particles for the integral
55
Progress in Energy and Combustion Science 93 (2022) 101037
representation of the field function [420].
The requirement for virtual particles in SPH increases the number of
particles inside the domain, making the method computationally
expensive and difficult to implement in available solvers [421]. Far­
rokhpanah et al. [421] focused on using SPH to simulate conduction
heat transfer within a PCM. Modifying heat capacity in the energy
equation took into account the amount of released and absorbed latent
heat during phase transition. The proposed model used five different
methods to improve accuracy, yielding five equations. The robustness of
SPH was demonstrated by comparing the five equations to available
analytical and numerical studies.
4.1.3. Limitations of continuum and discrete models
Notwithstanding their tremendous success, continuum numerical
approaches (macroscale) have their own limitations. Despite the fact
that continuum approaches are more suitable for systems with smoother
spatial and temporal variations, the continuum assumption fails for
problems with length scales of 10 nm or smaller [410]. The single-phase
model, in particular, is limited by the inaccurate/incomplete capture of
the interactions between ePCM particles, particles and the container
wall, and particles and the carrier fluid. Furthermore, the slip velocity
may not be zero due to a variety of factors, such as particle-fluid friction,
gravity, and sedimentation, as well as the non-uniform distribution of
ePCM concentration and thermal properties in the flow domain. More­
over, when an ePCM particle undergoes phase change, a portion of it
becomes liquid. As a result, the carrier liquid, solid phase of the shell,
and liquid phase of the core all coexist. These phases can have different
velocities and temperatures [408]. This necessitates a thorough exami­
nation of each phase without losing the discrete character of the
micro/nano-ePCM particles.
The non-uniform distribution of ePCM particles within flow systems
is expected due to lateral migration, particularly near the entrance re­
gion and boundary layers, which violates the homogeneous assumption
of the single-phase model. Additionally, because Brownian motion and
thermophoresis can have a large effect on nano-ePCM particle disper­
sions, temperature and velocity slips between fluid and particles can be
significant. As a result, it appears that using a two-phase model is
preferable to using a single-phase one. Ma et al. [385] demonstrated that
the two-phase Eulerian model could predict the variation of solid par­
ticle concentration and provide high accuracy in energy transport per­
formance, particularly for particles larger than 100 μm in diameter.
The concept of interpenetrative continua in the energy equations of
the two-phase Eulerian model, on the other hand, ignores the develop­
ment of the phase-change process within ePCM particles. As a result, the
thermophysical properties of ePCM particles are assumed to be the
same, as is the temperature distribution within the particles. As a result,
the energy exchange would be linear during phase change based on the
heat transfer and temperature difference between particles and the
carrying fluid, which requires ad hoc assumptions. Thus, errors in the
simulation results are unavoidable. Many studies reported that the
phase-change process within spherical capsules was reduced non­
linearly, resulting in nonlinear energy exchange between particles and
the carrier fluid [406,422,423]. Moreover, because of the existence of
particle shells, the phase-change process of each particle is independent,
and the temperature distribution of the particles is discrete rather than
continuous, according to Lin et al. [383]. Despite the benefits of discrete
approaches (at the micro and mesoscales) in revealing the details of a
complex process, discrete methods require a large amount of computer
memory and computational time, severely limiting the size of their
computational domain.
4.1.4. Multi-scale models
Multi-scale problems encompass any system or process that spans
multiple geometric or temporal scales. For example, fluid flow can be
classified into three scales: macroscale, mesoscale, and microscale. The
continuity and Navier-Stokes equations are the governing equations for
S.A. Albdour et al.
fluid at the macroscale, as they reliably predict velocity, density, and
pressure. At the mesoscale level, sometimes referred to as the mean-free-
path scale, the kinetic theory based on the well-known Boltzmann’s
equation is utilized to describe the one-particle phase-space distribution
function. Additionally, Newton’s law [424] is applied at the microscale
level to establish the real position and velocity of fluid particles (mole­
cules/atoms). The inherent time scale at each level is also different. For
example, the typical time scale in the macroscale is about one second;
however, at the microscale, it drops down to around 10− 12− 10− 14 s
[425]. Thus, to faithfully comprehend a multi-scale phenomenon,
coupled analysis on multiple scales rather than an individual one is
required. It should be noted that, despite the notable multi-scale char­
acteristics, multiphase flow computer simulations have traditionally
followed two approaches: fully continuum or fully discrete, with no
explicit consideration of multi-scale structures.
The main principle behind multi-scale models is that the various
scales are regulated by distinct equations and solved numerically in
distinct ways. Then, they exchange the needed data by coupling at the
interface (i.e., solving regionally and coupling at the interface) [425].
The information exchange at the interface can be expressed mathe­
matically as [425,426],
U = Cu, (41)
u = RU, (42)
where U and u are the macroscopic and microscopic variables, respec­
tively, and C and R denote the compression and reconstruction opera­
tors, respectively. Using various averaging methods, the compression
operator C is easily defined. It compresses massive amounts of data
obtained from nano/micro-scale numerical solutions. The reconstruc­
tion operator R, on the other hand, is difficult to create. However, both
operators are based on fundamental physical principles such as mass and
energy conservation, as well as being physically meaningful, mathe­
matically stable, computationally efficient, and easily implementable.
The main idea behind the coupled solution method is to divide the
domain into three regions; namely, the particle region (discrete), the
continuum region, and the hybrid region. The exchange happens at the
interface of the particle and continuum regions within the hybrid region.
The information exchange process should be repeated indefinitely until
the convergence criterion is met. Different coupling pairs have been
investigated, such as FVM with LBM, FVM with MD, FVM with MC, and
LBM with MD. Using FVM and LBM as an example, the coupling pro­
cedure can be summarized as follows:
1- Assume the initial conditions at the interfaces.
2- The FVM numerical simulation is performed in the continuum
region.
3- The FVM numerical solution yields the temporary solution; thus, the
proposed reconstruction operator is used to transform data at the
interface with the hybrid area.
4- The LBM numerical simulation is performed in the discrete region.
5- In the same manner as in Step 3, the temporary solution obtained
from the LBM numerical simulation is transformed at the interface
with the hybrid region to be used in the FVM simulation using the
proposed compression operator.
6- Steps 2 to 5 are repeated until the solutions achieve convergence
standards.
It should be noted that the numerical data obtained from the micro/
nanoscale solution is significantly larger than the data obtained from the
macroscale solution. As a result, numerical solutions are transferred
from one with fewer data points to one with more data points. The
following subsections introduce the fully-discrete coarse-grained and
hybrid continuum-discrete methods as specific implementations of the
multi-scale approach.
56
Progress in Energy and Combustion Science 93 (2022) 101037
4.1.4.73. Fully-discrete coarse-grained methods. Coarse graining is the
process of converting a microscopic description to a simpler macro­
scopic one by removing degrees of freedom and shrinking the di­
mensions of the state space, making a large system computationally
tractable. Coarse graining is a technique that aggregates clusters of
atoms into a single bigger unit [427]. The larger unit is more restricted
in its degrees of freedom than the atoms. The coarse-graining process has
the disadvantage of causing information loss in the system. Further­
more, determining which degree of coarse-graining is optimal in some
ways, as well as identifying microstates that can be reliably
coarse-grained, are both significant challenges in this procedure [428].
Dissipative particle dynamics (DPD), as an example of fully-discrete
coarse-grained methods, bears a strong resemblance to MD and can be
thought of as a coarse-grained version of it. DPD tackles a cluster of
atoms or molecules (coarse-grained) rather than an individual atom or
molecule as in MD [429]. DPD evolved as a result of an
application-driven need to simulate molecular systems for which the
current space and time constraints of MD are insufficient. DPD’s accu­
rate representation of thermal fluctuations distinguishes it from con­
ventional continuum methods, enabling accurate representation of
critical physical phenomena occurring at the micro and nanoscales, such
as heat and mass diffusion [430]. Additionally, its spatial scales vary
considerably across the physical domain and encompass a wide range of
sizes, from macro to nanoscales. Abu-Nada [431,432] investigated
steady-state 2-D conduction heat transfer with a variety of boundary
conditions, including those with and without internal heat generation.
Analytical solutions and finite-difference techniques were benchmarked
against the DPD simulations. Temperature distributions in the conduc­
tion domain were found to be accurately predicted by DPD. In addition,
Abu-Nada [433,434] also implemented the DPD technique for natural
convection applications, including heat transfer enhancement of nano­
particles [435]. Ng and Sheu [436] established the DPD model with
energy conservation to accurately simulate the speed of the solid-liquid
interface in the mushy zone, particularly in the case of a high thermal
conductivity ratio. The effective thermal diffusivities of mushy particles
were linearly interpolated using the estimated solid percentage. When
numerical solutions to one- and two-dimensional solidification problems
were compared to analytical solutions and/or experimental results,
there was a high degree of agreement.
4.1.4.74. Hybrid continuum-discrete methods. The analysis of ePCM flow
systems has traditionally been conducted using Eulerian–Eulerian
methods [393,396,397]. These techniques begin by solving conserva­
tion equations on a set grid and then adding suitable source terms to
account for mass, momentum, and energy transfer between phases [397,
408]. Recent attention has focused on a hybrid continuum-discrete
approach that can account for the continuum nature of the carrying
fluid using the Eulerain description and the discrete nature of ePCM
particles using the Lagrangian description. Rather than depending on
semi-empirical correlations to determine interfacial forces and fluxes,
hybrid Eulerian-Lagrangian methods directly acquire these variables via
direct coupling at the two-phase interface. The carrying fluid and ePCM
particles can be solved in two different frames of reference by applying
Eulerian-Lagrangian models to ePCM slurries/dispersions.
The physical phenomena captured using Eulerian-Lagrangian
models include temperature and velocity slips between fluid and parti­
cles [437], colloidal and collisional interactions between particles
[438], non-homogeneities in the particle spatial distribution [439],
particle agglomeration [440], and particle-wall interactions [441].
Eulerian-Lagrangian methods would use the continuum technique
wherever possible while incorporating the preceding physical processes
via the particle approach. As a result, Eulerian-Lagrangian methods can
accurately capture physical phenomena at a much lower computational
cost. However, the degree to which a model is coupled determines its
accuracy, which can be classified into four categories. Only the
S.A. Albdour et al.
continuous phase can influence the particle phase in one-way coupling.
In two-way coupling, both phases can influence the other. When a
particle disrupts the fluid phase and interacts with another particle, this
is referred to as three-way coupling. Finally, four-way coupling accounts
for particle interactions as well as particle-wall interactions [442].
The mass, momentum, and energy conservation equations for the
continuous phase can be written as follows [404],
∇.(ρb vb ) = 0, (43)
∇.(ρb vb vb ) = − ∇P + ∇.(μb ∇vb ) + Sp,m , (44)
( )
∇. ρb cp,b vb Tb = ∇.(kb ∇Tb ) + Sp,e , (45)
where Sp,m in Eq. (44) is a source term that represent momentum transfer
between the carrying fluid and ePCM particles. This can be determined
by finding the change in the momentum of particles as they move
through a control volume. The source term, Sp,e in Eq. (45) denotes
energy transfer between the fluid and particles. It can be determined by
calculating energy variations of the particles as they traverse the fluid
phase. Sp,m and Sp,e can be expressed as follows,
∑ mpa
Sp,m = npa F, (46)
δV
∑ mpa dTpa
Sp,e = npa cp,pa , (47)
δV dt
where δV denotes the cell volume and npa is the number of solid particles
contained within a cell volume. The mass and total specific force acting
on an ePCM particle are denoted bympaand F, respectively.
In Eq. (46), the total specific force, F, is made up of body and hy­
drodynamic forces, such as gravity, drag, thermophoresis, Saffman’s lift,
magnetic, Brownian, and virtual mass forces [404].
The energy equation of a particle is as follows:
dTpa ( )
mpa cp,pa = Nupa πdpa kb Tb − Tpa , (48)
dt
where Nupa can be calculated as follows,
Nupa = 2.0 + 0.6Re0.5 0.3
pa Pr , (49)
where Re and Pr are the Reynolds and Prandtl numbers, respectively.
Thus, in hybrid Eulerian-Lagrangian methods, the carrying fluid is
treated as a continuum and the computational speed is determined by
how the computational domain is discretized while treating PCM cap­
sules as particles with distinct properties. Newton’s second law is used to
predict the positions and velocities of N particles in linear motion given
external and interparticle forces. The deterministic forces operating on
the carrying fluid can be mathematically replaced by random fluctuating
forces when it comes to the mobility of ePCM particles in the carrying
fluid. These random forces have a zero mean over time, and their
amplitude is determined by the dissipation fluctuation theorem.
The equations that regulate phenomena in the Eulerain reference
frame can be solved using different numerical techniques, such as FDM
[443], FEM [444], FVM [445], and LBM [446]. Similarly, phenomena in
the Lagrangian reference frame are governed by approaches such as
Langevin-dynamics [447], Brownian dynamics [448], Stokesian dy­
namics [449], and particle-in-cell.
Rostami [450] used the Eulerian-Lagrangian approach in two-way
coupling to investigate the heat transfer characteristics of a paraffin
wax micro-ePCM slurry in a mini-channel. A thin layer of Fe3O4 was
used to coat the particles, with volumetric concentrations ranging from
0 to 10%. Drag, buoyancy, and weight were the forces acting on the
particle phase. The control volume and SIMPLE methods were used to
solve the velocity and temperature fields for the carrying fluid. The
fourth-order Runge-Kutta method was used to solve for the velocity of
particles. The temperature of the particles was determined by solving
57
Progress in Energy and Combustion Science 93 (2022) 101037
the transient conduction equation. The results indicated that when
Reynolds number was 1000, volumetric concentration was 10%, and
there was no supercooling, the Nusselt number increases by 13%.
Shabgard et al. [451] simulated the settling of a PCM slurry in a
vertical tube with heated wall surfaces. The arbitrar­
y–Lagrangian–Eulerian (ALE) approach was adopted and implemented
in a finite-volume formulation using two coupling methods. A
body-conformal mesh was used to account for particle sedimentation
and interface morphological changes. The average Nusselt number at
the particle surfaces was obtained, which could be utilized as an input to
mixture-based Eulerian–Eulerian models (that are less computationally
expensive) for simulating slurry flows.
4.2. Thermophysical property correlations for ePCM slurries/dispersions
The governing equations presented in Section 4.1 show that the
required slurry thermophysical properties are specific heat capacity,
thermal conductivity, viscosity, and density. Therefore, this section aims
to present the experimental and theoretical correlations that represent
each property.
4.2.1. Specific heat capacity
The effective specific heat of an ePCM slurry cp, sl is made up of the
specific heats of the ePCM particles cp, pa and base fluid cp, b. The first
step in calculating the effective specific heat capacity of an ePCM slurry
is to assume that the specific heat of the PCM is the same in both solid
and liquid phases (i.e. cp, pa= cp, s= cp, l), so it is calculated as follows in
the absence of phase-change processes [452],
( )
cp, sl = mf cp, pa + 1 − mf cp, b, (50)
wheremfrepresent the mass fraction of PCM.
Based on available parameters, there are two methods for calculating
cp, pa. Chen et al. [453] proposed calculating cp, pa by treating an ePCM
particle as a core and shell, as shown below,
cp, pa =
(cp, co + ycp, sh)ρcoρsh
, (51)
(yρco + ρsh)ρpa
where ρpa is calculated as following,
(1 + y)ρcoρsh
ρpa = . (52)
ρsh + yρco
The models above do not consider the phase-change process inside
the ePCM particles. However, if the latent heat of the ePCM particles is
known and the phase-change process is taken into account when esti­
mating heat transfer performance, the effective specific heat of the
ePCM slurry will be a function of temperature during the phase transi­
tion, cp,pa = cp,pa(T), which can be related to the latent heat of fusion as
follows [396,454],
∫Tl
Hs − l = cp, pa(T) dT. (53)
Ts
As shown in Fig. 53, the variation of effective specific heat of ePCM
particles with temperature within the phase-change temperature range
can be represented by five different profiles. Rectangles, middle tri­
angles, and sinusoidal curves are used to represent symmetric profiles,
while the two oppositely oriented triangles are used to represent
asymmetric profiles. The effective specific heat for each case is described
next [396,398,452].
For the right triangle profile:
( )
cp, pa(T) = cp, s + 2
Hs − l cp, s
− (T − Ts). (54)
2
Tmr Tmr
For the left triangle profile:
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

⎧
⎪
⎪ co = 4.047
⎪
⎪
⎪
⎨ A = 3.86 × 10− 3 + 3.944 × 10− 2 ∅
T < 30∘ C : ,
⎪
⎪ B = 9.698 × 10− 2 − 0.56568∅ + 0.16672∅2
⎪
⎪
⎪
⎩
Tc = 25.35
⎧
⎪
⎪ (62)
⎪
⎪
⎪
⎪
⎪
⎪ co = 4.054
⎨
∘
T ≥ 30 C : A = − 6.667 × 10− 3 + 0.2555∅
⎪
⎪
⎪
⎪ B = − 0.25721 − 0.2252∅ + 9.708 × 10− 2 ∅2
⎪
⎪
⎪
⎪
⎩
Tc = 36.24
It is worth highlighting that the majority of authors extend the use of
correlations for micro-ePCM slurries in their numerical simulations to
nano-ePCM dispersions [454,456,457].

Fig. 53. Sine curve, left triangle, right triangle, rectangle, and middle triangle 4.2.2. Thermal conductivity
profiles for the variation of specific heat capacity of ePCM particles with As a starting point, calculating the thermal conductivity of a slurry is
temperature. possible using the Maxwell model [458]. Because it assumes no slip
( ) between the base fluid and particles, it is known as a static model. The
− Hs − l cp, s formula obtained can be written as follows:
cp, pa(T) = cp, s + 2 2
+ (T − Tl). (55)
Tmr Tmr
2 + kpa/kf + 2∅(kpa/kf − 1)
ksl = kf . (63)
For the middle triangle profile: 2 + kpa/kf − ∅(kpa/kf − 1)
[ ]
cp,l − cp,s 4Hs − l
(
Ts + Tl
) And the thermal conductivity of the core-and-shell particles is
cp,s +
Tl − Ts
+
(Tl − Ts )2
(T − Ts ), Ts ≤ T ≤
2 calculated from [453],
cp,pa (T)= { [ ] ( ) . 1 1 dpa − dco
4Hs − l cp,l − cp,s Ts + Tl = + , (64)
cp,l + − (Tl − T), < T ≤ Tl kpadpa kcodco ksh dpa dco
(Tl − Ts )2 Tl − Ts 2
( )2
(56) dco ρsh
= . (65)
For the rectangular profile: dpa ρsh + yρco

Hs− l This model typically produces accurate results for spherical ePCMs.
cp, pa(T) = . (57) However, as the shape of suspended particles deviates from spherical,
Tmr
the accuracy of the model degrades. Furthermore, the predicted thermal
For the sine curve profile: conductivity values for the slurry are less than the experimentally re­
( ) [ ( )]
π Hs − l T − T1 ported ones due to the enhancement caused by particle-carrier fluid
cp, pa(T) = cp, s + − cp, s sin π . (58) interactions [394]. Hamilton and Crosser [459] considered this effect
2 Tmr Tmr
and modified Maxwell’s model by introducing the shape factor of sus­
Thus, Eq. (50) can be rewritten to represent the effective specific heat pension particles as follows:
of the ePCM slurry undergoing phase change, as follows [452],
kpa + (w − 1)kf + (w − 1)(kpa − kf )∅
( )
cp, eff , sl = mf cp, pa(T) + 1 − mf cp, b. (59) ksl = kf , (66)
kpa + (w − 1)kf − (kpa − kf )∅
In an important study [452], the right triangle, left triangle, rect­
where w represents the shape factor of suspension particles and it varies
angular, and sine curve models were compared for microcapsules con­
within the range of 3-3.13 [394]. The model is reduced to Maxwell’s
taining 20− 25% PCM. The results revealed that the difference between
model by substituting w = 3, which is the shape factor of a spherical
the four models was less than 4%.
capsule. However, this modified model failed in several aspects,
Another correlation based on experimental data for nano-ePCM
including underestimating the thermal conductivity enhancement
dispersions is written as follows [340],
caused by dispersing nanoparticles and considering the temperature
(1 − ∅)ρb cp, b + ∅ρpacp, pa dependence of nanoparticle size [454].
cp, sl = . (60)
(1 − ∅)ρb + ∅ρpa Several authors explored the augmentation of thermal conductivity
caused by particle-particle, particle-liquid, and particle-wall in­
Based on the experimental results of Karaipekli et al. [340], Haddad
teractions while the ePCM slurry passes through channels. They used
et al. [455] derived the following correlation for nano-ePCM dispersions
particles and fluids with the same thermal conductivity at different
(n-nonadecane as a core and styrene/methacrylic acid copolymer as
particle Péclet numbers and found the following relationships
shell):
[460–463],
cp, sl = co + AeB(T− Tc )2
, (61) keff = f .ksl,
Where for, kf = 0.020833Tf − 0.0275,

rpa
kpa = rpa r − r ,
kco
+ paksh co

58
S.A. Albdour et al.
( )
2+
kpa k
+ 2∅ kpaf − 1
kf
ksl = kf ( ),
k k
2 + kpaf − ∅ kpaf − 1
⎧
⎨ A = 3.0, m = 1.5, Pe < 0.67
f = 1 + A∅Pem, A = 1.8, m = 0.18, 0.67 ≤ Pe ≤ 250 . (67)
⎩
A = 3.0, m = 1/11, Pe > 250
It is worth mentioning that Eqs. (63) and (67) are the most frequently
used correlations for numerical simulations of nano/micro-ePCM slur­
ries/dispersions. On the other hand, inspired by the linear relationship
between thermal conductivity and the volume concentration of nano­
particles in a nanofluid, many researchers employed the following
equation to calculate the effective thermal conductivity [454],
ksl
= 1 + Nc∅, (68)
kf
where Nc is a constant referred to as the number of thermal conductivity,
which can be altered by changing parameters such as the size, shape,
and concentration of nanoparticles, as well as the type of base fluid. It
can also be affected by the preparation method, suspension temperature,
ultrasonication time, and other factors. It is important to note that Eq.
(68) is limited to dilute suspensions and a low volume fraction of nano-
ePCMs (5%) [454]. For a suspension of nano-ePCMs in water that in the
temperature range of 25 − − 34◦ C, Haddad et al. [455] derived another
correlation based on the available experimental data of Karaipekli et al.
[340],
( ) (
ksl = 0.63456 + 2.5 × 10− 2 ∅ +
) statistical thermodynamic analysis of such nano-systems and theoretical
− 1.39 + 10.99∅ + 10.59∅2 + 3.3466∅3 10− 11 T 6.37 (69)
The thermal conductivity obtained in [455] was compared to the
thermal conductivity of nanofluids at the same concentrations. For both
of them, thermal conductivity increased as the particle volume fraction
and temperature increased. Additionally, the results were consistent
with some experimental data published in the literature.
4.3. Viscosity
The most common models for predicting the effective viscosity of an
ePCM slurry, applicable to Newtonian fluids (∅ < 30%), are Einstein’s
[464], Batchelor’s [465], and Vand’s [466] models, which are respec­
tively expressed as:
μsl = μf (1 + 2.5∅), (70)
( )
μsl = μf 1 + 2.5∅ + 6.2∅2 , (71)
( )
μsl = μf 1 − ∅ − A∅2 − 2.5. (72)
In Vand’s model, A is a parameter that varies between 1.16 and 4.5
for different materials and sizes [455]. It is worth noting that Vand’s
model is most frequently used by researchers because it is relatively
insensitive to particle size in the range of 3 to 300 μm and valid for
volume ratios of less than 37%. Chai et al. [394] compared the previ­
ously mentioned correlations at various PCM volume concentrations. A
was 1.16, 3.4, and 4.45 in Eq. (72) when the volume fraction was less
than 10%. The viscosity predictions from all correlations were quite low
and showed little difference from the base fluid. When the volume
concentration exceeded 10%, the predictions showed a significantly
larger difference from the base fluid, and they increased drastically as
concentrations increased, except for the Einstein model. The most
notable increase was in Eq. (72) when A was equal to 4.45. It is worth
noting that Eq. (72) is also the most frequently used correlation for
numerical simulations of nano/micro-ePCMs in mini/microchannels,
with A = 1.16 [467].
Another correlation was established using the linear relationship
59
Progress in Energy and Combustion Science 93 (2022) 101037
between viscosity and nanoparticle volume fraction [454], as follows:
μsl
(73)
= 1 + Nv∅.
μf
It is worth mentioning that Eq. (73) is valid only for a low volume
fraction of nano-ePCMs (5%).
Another correlation was developed [455] for a suspension of
nano-ePCMs operating in the temperature range of 25 − − 34◦ C, as
shown below,
( )
μsl = 2.838 + 0.3753∅1.79 (1 + T)− 0.355 . (74)
4.3.1. Density
ρsl = (1 − ∅)ρf + ∅ρpa, (75)
The most widely used equation for calculating the density of a nano/
micro-ePCM slurry/dispersion is as follows [394,468]: where ρpa is
computed as shown in Eq. (52). Based on experimental results, another
relationship was derived for a suspension of nano-ePCMs, valid in the
temperature range of 25− 34◦ C, as follows:
( ) (
ρsl = 1.0008 + 2.03 × 10− 3 ∅ +
)
− 10.79 + 8.84∅ − 11.53∅2 + 4.063∅3 10− 8 T 3.18 . (76)
Correlations such as those mentioned above are derived using strict
assumptions regarding temperature and PCM concentration values.
However, a thorough theoretical understanding of energy transport at
the nanoscale is required, especially for thermal conductivity and spe­
cific heat. This includes both fundamental knowledge gained through
modeling of nanoscale energy transport mechanisms. As a result, the
following two sections will discuss the theoretical foundations for
analyzing energy transport at the nanoscale in PCMs.
4.4. Theoretical background of thermal conductivity in PCMs
Thermal conductivity is similar to the majority of non-equilibrium
transport quantities that cannot be solved in closed form without
imposing certain assumptions. A thorough theoretical investigation of
the thermal conductivity of solid and liquid PCMs that is consistent with
experimental data is required for further development and enhancement
of the performance of PCMs in latent TES systems. Thermal conductivity
in solids is fundamentally based on the kinetic theory of thermal con­
duction in gases, which provides a framework for analyzing the micro­
scopic processes governing heat conduction. Therefore, in the current
section, gas thermal conductivity is revisited first, followed by solid and
liquid thermal conductivity.
4.4.1. Gas thermal conductivity
Thermal conductivity in gases is caused by energy transfer between
gas molecules, which is highly dependent on the average distance
traveled by a phonon between collisions. This is known as the mean free
path of molecules, λ. High-temperature gas molecules diffuse among
low-temperature gas molecules, collide with them, and release kinetic
energy. The mean free path, λ, is related to the mean free path compo­
nents in the x-, y-, and z-directions, as shown in Fig. 54, via the following
relationship:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
λ = (Δx)2 + (Δy)2 + (Δz)2 . (77)
If an isotropic substance is assumed, then phonons can travel in all
three directions in space equally well. Therefore, Δx = Δy = Δz and Eq.
(77) can be rewritten as follows,
1
(Δx)2 = λ2 . (78)
3
The total heat flow rate is expressed as follows,
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 54. Relationship between the mean free path in three dimensions and the
mean free path in the heat flow direction.
Fig. 55. Sketches of a) mass-spring system of lattice material, b) non-vibrating
Q = cv mΔT, (79) atom, and c) atom vibration associated with phonon generation.

where cv and m are the isochoric specific heat capacity and mass of the temperature increases, its vibrations deviate from the equilibrium state.
material, respectively, and ΔT is the temperature change across Δx. The Following that, high-energy phonons are created and diffuse, resulting
mass of the material can be expressed as follows, in the formation of a temperature gradient [470]. As a consequence, in
the presence of a temperature gradient, heat will flow from the hot end
m = ρV = ρAΔx, (80)
to the cold end, as shown in Fig. 56.
where ρ, V, and A are the density, volume, and area of the material, Each phonon carries an amount of energy equal to hv instead of the
respectively. Thus, Eq. (79) can be rewritten as follows: kinetic energy equal to 1/2mv2 since a phonon is massless. Phonon
transport is modeled like that of gas molecules, which is known as the
Q = cv ρAΔxΔT. (81) phonon gas model (FGM) [471]. By analogy, to describe the thermal
By defining the mean time interval between two phonon collisions as conductivity of a crystal lattice, the phonon gas model considers pho­
τ, we obtain the heat transferred within the time τ as follows, nons in crystalline solids to be gas particles. This approach has been
shown to be effective for understanding heat transport in solids at
Q cv ρAΔxΔT various scales. According to the model, each phonon contributes the
Q̇ = = . (82)
τ τ following to the heat flux [471]:
From Fourier’s law, the thermal conductivity coefficient is expressed vg
as follows, Q = hω ∼ (86)
V,
Q̇Δx
k= . (83) where ω is the phonon frequency, h is the reduced Planck’s constant, vgis
AΔT
phonon velocity, and Ṽ is the volume per mode of vibration. The
By substituting Eqs. (78) and (82) into Eq. (83), we obtain,
1 2
Δx2 λ 1 λ
k = cv ρ = cv ρ 3 = cv ρ λ. (84)
τ τ 3 ⏟⏞⏞⏟τ
v

Therefore, the gas thermal conductivity coefficient is expressed as

follows,
1 1
k = cv ρvλ = Cv vλ, (85)
3 3

where Cv is the heat capacity per unit volume obtained from the product
ofcvandρ.

4.4.2. Solid thermal conductivity

For solids, heat can be conducted via excitations caused by electrical
carriers (electrons or holes) or lattice waves (phonons). In metallic
materials, the majority of heat transfer occurs via electrical carriers
[469]. However, in crystalline dielectric materials, lattice waves are the
dominant heat transporters [469]. When heat energy reaches the surface
of crystalline PCMs, it is transferred to the atoms located on the surface.
Each atom vibrates as it receives heat, which is then transferred at the
same rate to neighboring atoms. Thus, a quasi-particle exists as a result
of the vibrational waves called phonons. For this reason, the lattice
structure of the crystalline PCM can be assumed as a coupled mass and
spring system, as illustrated in Fig. 55. At low temperatures, atoms in the
crystal lattice vibrate close to their equilibrium positions, working to
Fig. 56. Phonon energy variation with temperature and distance. In the pres­
prevent the phonon from being excited. However, when crystal ence of a temperature gradient, heat will flow from the hot end to the cold end.

60
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

problem with this model is mainly encountered with materials that do conductivity model is given as follows:
not have well-defined phonon dispersion and therefore do not have well- ∫∞
defined velocities. According to Eq. (86), knowing the phonon velocity 1
k= cv (ω)v(ω)λ(ω) dω. (87)
determines the rate at which the energy of a phonon moves through the 3
material (from the hot end to the cold end).
0

Thermal energy does not flow directly through the crystal but rather
diffuses through it according to the type of phonon scattering. Phonon
scattering can be classified into three types: phonon-phonon scattering,
phonon-defect scattering, and phonon-interface scattering [470].
Phonon-phonon collisions (also known as three-phonon scattering)
are further classified into two types [472]: normal processes (N pro­
cesses) and Umklapp processes (U processes). As illustrated in Fig. 57,
energy and momentum are conserved in N processes, whereas U pro­
cesses conserve only energy. When only a few phonons are present in the
crystalline PCM, the probability of a phonon collision is extremely small,
resulting in a long mean free path. However, as the number of phonons
increases, the collision probability increases, the mean free path be­
comes shorter, and the thermal conductivity increases as well. Thus, the
greater the degree of phonon collision in a PCM, the greater its thermal
conductivity and ability to conduct heat. Defects in the PCM lattice in­
crease the likelihood of phonon scattering, such as reflection and
diffraction, which has a detrimental effect on phonon transport. Small
impurities in the PCM lattice increase thermal resistance and decrease
thermal conductivity [490]. Point defects, dislocations, vacancy defects,
and impurities are the most frequent types of lattice defects [473].
On the other hand, the effect of phonon-boundary scattering is
greatest at low temperatures, where the mean free path of the phonon is
the longest. In composite PCMs, the interface between the filler matrix
and the PCM is the primary barrier to thermal transport. Interfacial
resistance impedes heat flow within composite PCMs, minimizing the
advantage of using a highly thermally conductive filler. As a result,
composite materials have a lower thermal conductivity than thermal
conductivity fillers [474].
The thermal conductivity of solids is similar to that of kinetic gases,
taking into account the direct factors affecting thermal conductivity,
including heat capacity per unit volume, Cv, phonon velocity, v, and
phonon mean free path, λ. This is in addition to the three phonon po­
larizations in solids: one longitudinal and two transverse branches. The
Debye formulation can be used to estimate the lattice thermal conduc­
tivity of crystalline materials with respect to the lattice vibration fre­
quency, assuming that the dispersion relation and bulk mean free
pathways are well approximated as isotropic [475]. The thermal
By assuming a spring connecting two types of atoms with masses M1
and M2, the bonds between the atoms are described by a spring constant,
and then the solution of the lattice vibration frequency, ω, is given as a
function of wavevector, k, as follows [476],
( ) (( )2 )1/2
2
ω(k ) = SC
1
+
1
+ SC
1
+
1
−
4
sin2k a
, (88)
M1 M2 M1 M2 M1 M2 2
where a is the distance between two atoms at equilbrium, i.e., the lattice
constant, and SC is the spring constant. Then, the dispersion relation can
be used to calculate the phonon velocity, as follows [477],
dωk
v= . (89)
dk
The phonon dispersion relationship is considered critical for thermal
transport research since it establishes a link between statistical atomic
behavior and macroscopic heat transfer [477].
The basic assumption in Eq. (87) is that, as previously stated, the
dispersion relation and bulk mean free paths are isotropic. This holds
true for gases (such as molecules, photons, and free electrons), as well as
electrons and phonons in amorphous materials. Yet, the dispersion
relation of electrons and phonons in crystalline materials is direction-
dependent, necessitating a more generic form of Eq. (87) [478]. Thus,
introducing the mean free path into Eq. (87), to acquire better knowl­
edge of the internal heat transport mechanisms of crystalline materials,
will produce more accurate results [479].
The mean free path is affected by three forms of phonon scattering.
Whichever of the three factors produces the shortest mean free path has
a real influence over the other scattering processes. Matthiessen’s rule
defines the effective mean free path, λeff, as follows [2, 24],
1 1 1 1
= + + , (90)
λeff λph λd λb
where λph, λd, and λb denote the mean free path as determined by the
phonon-phonon, phonon-defect, and phonon-boundary scatterings,
respectively. Fig. 58 shows a representation of phonon mean free
pathways due to different scattering types.
Therefore, to focus on the bulk mean free path, λ, and reflect its
contribution on thermal conductivity, the integral variables in Eq. (87)
are changed from ωto λ, with an exchange of the order of integration and
summation [478]:

∑∫ 1
∞ ( )− 1
dλbulk
kbulk = − Cv λbulk dλbulk . (91)
s
3 dω
0

The negative sign is introduced since the dominant trend of dλbulk/

dω is negative, therefore, the resultant value of kbulk is positive [478].
By applying Fubini’s theorem, we can exchange the summation and
integration in Eq. (91) and rewrite it as follows:
∫∞
kbulk = kλ dλbulk , (92)
0

where,
∑1 ( )− 1
dλbulk
kλ = − Cv λbulk , (93)
s
3 dω

Fig. 57. Phonon-phonon collisions are classified into a) normal (N) and b) wherekλis the thermal conductivity per mean free path.
Umklapp (U) processes. Energy and momentum are conserved in N processes, Holland [480] provided another analytical model of crystal thermal
whereas U processes conserve only energy.

61
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

follow the model of kinetic gas conduction, which assumes that the gas
particles are dilute and non-interacting [475].
The majority of the theoretical expressions for liquid thermal con­
ductivity are based on Bridgman’s model. It assumes a liquid as a cubic
lattice with side lengths of d. Each corner contains a molecule with 2KBof
energy transferred at the speed of sound from the water molecule to
other neighboring molecules through the cross-sectional area d2 [483],
yielding,
2kB vsound
kBridgman = = 2kB vsound n2/3 , (98)
d2

where vsound is the longitudinal sound speed in the liquid, and d is the
mean distance between the centers of molecules, which can be expressed
in terms of the molecular density of the liquid as d=n− 1/3.
Prior to proceeding, it is worth noting that amorphous solids and
liquids exhibit a similar degree of short-range order in their structure, as
evidenced by the similarity of the theories used to describe their thermal
conductivity. A clear similarity can be seen between Eqs. (97) and (98).
Xi et al. [484] recently proposed a unified formula for calculating the
thermal conductivity of liquids and amorphous solids at room temper­
ature based on their structural similarity.
Bridgman’s model was shown to agree well with the experimental
thermal conductivity results of polar liquids, such as ethanol, hydrogen
sulfide, and methanol [475]. However, it deviated from the experi­
Fig. 58. Phonon mean free paths due to a) phonon-phonon, b) phonon-defect, mental results of other liquids, such as water and molten salts [475].
and c) phonon-boundary scattering. Bridgman’s model was developed based on a reinterpretation of the
rigid spheres assumption in the kinetic theory of gases, as follows [485],
conductivity that completely accounts for the effect of longitudinal and k = 2.8kB Usn2/3 . (99)
transverse phonons on heat conduction. The formula, as indicated in Eq.
(94), is made up of two parts: thermal conductivity of transverse kTraand In Eq. (99), the numerical coefficient of 2.8 was initially 3 [484].
longitudinal phonons kLon, However, it has been modified to obtain better agreement with the
experimental data. Due to uncertainty around the sound velocity in
k = kTra + kLon , (94) many liquids, a semi-empirical relationship for sound speed in liquids
based on more certain physical characteristics gained acceptance [486],
where, as follows:
θ∫T /T ( )1/2
2 CTra T 3 x4 ex (ex − 1)− 2 dx 1
kTra = , (95) Us = , (100)
3 τ−Tra1 ρks
0

where ks is the adiabatic compressibility. Thus, Eq. (99) is rewritten as

θ∫L /T
2 CLon T 3 x4 ex (ex − 1)− 2 dx follows,
kLon = , (96)
3 τ−Lon1 ( )1/2
1
(101)
0
k = 2.8kB n2/3 .
ρks
where x = KhBωT, and by considering i = Tra or Lon, θi = KBhωi and Ci =
( )( )3 However, due to difficulty in obtaining adiabatic compressibility, the
KB KB
2π 2 vi h . isothermal compressibility kTis used instead, which is much simpler to
At this point, it is worth mentioning that amorphous solids have obtain [486], yielding,
vibrational modes that can conduct heat. However, since they do not ( )1/2
1
have long-range order like crystalline material, heat is transferred via k = 2.8kB n− 2/3
. (102)
collective vibrations distinct from phonons, referred to as locons, dif­ ρkT
fusions, and propagons [481]. The Cahill–Pohl model was proposed for Overall, consistency between Bridgman’s model and experimental
the minimum thermal conductivity of the amorphous solid, assuming data is insufficient. This difference in ionic liquids and ionanofluids is
that the mean free path of each vibrational mode is half its wavelength. typically between 5 and 15%, and it can reach up to 50% [486].
Later on, their model was simplified to [482], On the other hand, Chapman and Enskog [475] revised the kinetic
1.21 gas theory to integrate the comparatively high density of liquids into a
(97)
2
k=
3
kB (2vTra + vLon )n3 , new kinetic theory of liquids. Their concept is based on the observation
that liquid molecules collide more frequently than gas molecules. Their
where KB is Boltizmann’s constant, vTra is the transverse speed of sound, assumption is backed by the effective scattering diameter of liquid
vLon is the longitudinal speed of sound, n is the number density of atoms. molecules, D, which can be computed using viscosity measurements:
[ ]2
4.4.3. Liquid thermal conductivity ko 2 3kB ∏
kChapman− Enskog = 1 + πρD3 g(D) + , (103)
Thermal conduction processes in liquids are based on the movement g(D) 5 2m
and vibration of molecules as a response to the temperature gradient. [ ]2
However, because of the strength of the density and intermolecular μo 4 3∏
μChapman− Enskog = 1+ πρD3 g(D) + , (104)
contacts in liquid molecules, thermal conduction in liquids does not g(D) 15 5

62
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

√̅̅̅̅̅̅̅̅̅̅̅̅̅̅ equilibrium. This theorem is represented by the so-called "Green-Kubo"

25 πmkB T 3kB
ko = , (105) relations [489]. This avoids some of the complexities associated with
32 D2 π 2m
non-equilibrium approaches due to the large temperature gradients. The
25
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅
πmkB T general form of Green-Kubo relations used in MD calculations is:
μo = , (106)
32 D2 π ∫∞
∏ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅ Y=β 〈Ao (t)Ao (0)〉eq dt, (114)
4
= ρ2 D4 g(D) πmkB T , (107) 0
9
( ) where Y is the transport coefficient of interest (in our case, thermal
1 − 119ρb
g= , (108) conductivity), Ao is an observable, and β is a constant. The expressions
1 − 2ρb
for Ao and β depend on the considered coefficient. Depending on the
macroscopic quantity of interest, the derivation of Green-Kubo formulas
2
b = πD3 , (109) can be quite different. In the case of thermal transport, the Green-Kubo
3
formula establishes a relationship between thermal conductivity and
where ko is the dilute-gas thermal conductivity, μo is viscosity, D is the heat flux spontaneous fluctuations as follows [490],
effective molecule diameter,ρis liquid density, mis the mass of a liquid ∫∞
molecule, and T is absolute temperature. Unfortunately, the Chap­ k=
V
〈J(t).J(0)〉dt, (115)
man–Enskog kinetic theory of liquids failed to account for the temper­ kB T 2
0
ature dependence of liquid thermal conductivity [475].
Another well-known model for liquid thermal conductivity was where J(t) is the heat flux vector at time t, V and T are system volume
established by Horrocks and McLaughlin [487]. It was based on the fact and temperature, respectively.
that liquids have a lattice structure through which excess energy caused The total heat flux is the summation of the convective term, Jc,
by a temperature gradient is transferred in two ways. The first is by the arising primarily from the diffusion of particles, and the virial term, Jv,
movement of molecules between cells, expressed as follows: arising primarily from atomic interactions. Each term can be expressed
( ) as follows [490]:
( )1 √̅̅̅
n h k B T 2 Cv 2 ( nh ) kB T
− eo

kconv = 1− e , (110) J(t) = Jc (t) + Jv (t), (116)

N 2πm vf a N
[ ]
1 ∑
where vfis the free volume of the liquid, eo is the height of the boundary Jc = ei vi , (117)
V i
potential barrier restricting a molecule to its cell, nhis the number of
vacancies, N is Avogadro’s number, m is the mass of a molecule, and Cv is [ ]
the specific heat per molecule. The second way is via a vibrational 1 ∑( ( ))
Jv = Fij . vi + vj rij , (118)
mechanism in which the molecule vibrates inside its cell, as follows: 2V i<j
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
[ { (r )14 (r )8 }]1/2 m ( 1 − nh )
ε where ei and vi are the per-atom energy and velocity, Fij is the force
(111)
o o N
kvib = P 2 2 11C14 − 5C8 Cv 2 ,
π Ro m a a a between atoms i and j, viand vj are their velocities, and rij is the sepa­
ration distance between them. Therefore,
where P represents the probability that energy is transferred when two
∫∞
vibrating molecules collide and ε is the depth of the potential well at the V
k= ((Jc (t) + Jv (t)).(Jc (0) + Jv (0)))dt. (119)
equilibrium diameter ro. C14and C8 are lattice summation constants of kB T 2
values 12.05899 and 12.80194. Therefore, 0

k = kvib + kconv . (112)
However, it is reported that the thermal conductivity of simple liq­
uids up to their boiling points is almost entirely due to the vibrational
contribution and that convective contributions can be ignored [487].
Thus,
k ≈ kvib . (113)
By comparing Horrocks and McLaughlin’s and Bridgman’s models
with experimental data, values from the Horrocks and McLaughlin
model agree on average within 20% of experimental values, as opposed
to values from Bridgman’s model, which are within about 35% [487].
Another approach to determining the thermal conductivity of liquids
is grounded in MD simulations, where the central premise is to consider
that every substance is composed of elementary particles at the most
fundamental level (atoms or molecules). Once the fundamental dy­
namics parameters of these molecules are determined (i.e., position,
velocity, and interaction force), macroscopic physical properties of the
substance, such as volume, temperature, and pressure, can be deter­
mined using statistical methods [488].
Transport coefficients, such as thermal conductivity, viscosity, and
diffusion, are determined from MD by utilizing the fluctuation-
dissipation theorem, which establishes a relationship between non-
equilibrium coefficients and spontaneous fluctuations occurring at
4.5. Theoretical background of specific heat capacity in PCMs
In the early nineteenth century, the French physicists Pierre-Louis
Dulong and Alexis-Thérèse Petit demonstrated that the gram-atomic
heat capacity (specific heat multiplied by its atomic weight) of an
element is constant; that is, approximately six calories per gram atom for
all solid elements. They accounted for the molar specific heat of the solid
at high temperatures using the energy equipartition theorem of classical
statistical mechanics. They assumed that at high temperatures, solid
atoms behaved like simple harmonic oscillators, with all vibrational
degrees of freedom fully excited. Their model is known as the
Dulong–Petit law, which is defined as follows [491]:
cp = 3R = 3NA kB, (120)
where R and Na are the gas constant in kJ/kmol•K and Avogadro’s
number, respectively.
The weaknesses of the model lie in the overestimation of the cp of
many materials, such as graphite and diamond, and an inability to
predict material behavior at low temperatures [492]. Additionally, it has
been observed experimentally that the cp of certain solids decreases as
the temperature decreases, which contradicts the Dulong–Petit law
[492]. Later on, and under the umbrella of the quantum harmonic
oscillator, Einstein used new assumptions to overcome the previously

63
S.A. Albdour et al.
mentioned shortfalls. He believed that all atoms vibrated at the same
frequency, leading to:
( )
TE
cp,E = 3NA kB fE , (121)
T
where fE
(T )
is the Einstein heat capacity function and TE =
k .
E hωE
T
B By knowing the values of thermal conductivity and specific heat
worth mentioning that when T ≫ TE, cp in the Einstein model can
expressed as cp,E = 3NAkB, which is consistent with the Dulong–Petit law.
Debye offered another model based on the concept of collective
lattice vibrations. He made the assumption that the crystal is an isotropic
continuum and that elastic waves accurately described the thermal
motion of atoms. Each mode of elastic wave vibration has a harmonic
oscillator analogy. Additionally, he took into account all vibrations
below the Debye frequency (upper limit of the specified elastic wave
frequency). His model is expressed as follows:
( )3 ∫TD
cp = 9NA kB
T x4 ex
dx, (122)
TDe (ex − 1)2
0
where x =
kB T . When T ≫ TDe,the model showed good agreement with
hωE
the Dulong–Petit law and the Einstein model. However, when T ≪ TDe,
the low frequancy modes are excited by thermal excitation. The cp of
Debye model becomes,
( )3
12 T dispersions, in addition to analytically and numerically evaluating their
cp = NA kB . (123)
5 TDe
Eq. (123) is referred to as Debye-T3 law.
Although the Einstein and Debye models provide an excellent bal­
ance of precision and applicability in describing the heat capacity of
solid states, it is difficult to predict melting, which is a significant
shortcoming in crystal thermodynamics theory. This is due to the diffi­
culties in controlling anharmonicity around the melting point, which is
believed to produce instability that drives the discontinuity in the free
energy curve. The underlying mechanisms responsible for the lattice
instability that drives the transition to the liquid state are currently
unknown, and no self-consistent solid-state model can predict it. The
reason behind this is that the interactions in a liquid are both strong and
system-specific, suggesting that energy greatly depends on the liquid
type, leading to a statement that liquid energy cannot be calculated in
general form. Computational methods like MD and density functional
theory are often needed to understand the transition from solid to liquid
[493]. Modern MD approaches, such as the instantaneous normal mode
theory [494] and the two-phase thermodynamic model [495], are
helpful for deriving thermodynamic properties for MD simulations, but
their implementation is rather complicated. Consequently, scientists and
engineers have relied primarily on empirical criteria to estimate ther­
modynamic properties of liquids.
Bolmatov et al. [496] developed a phonon theory of liquid thermo­
dynamics that encompasses both classical and quantum regimes. They
hypothesized that the phonon states of a liquid are only impacted by its
relaxation time, τ, which is the average time between two successive
atomic jumps at a single place in space. They were able to obtain liquid
energy in the following way:
( )( ( ) ( )3 ( ))
αT hωD ωF hωF
E = NT 1 + 3D − D , (124)
2 T ωD T where the total attenuation of waves by both absorption and scattering is
where α is the coefficient of thermal expansion, ωD is Debye’s frequency,
and ωF = 2τπ is Frenkel’s frequency. Then, for each temperature, they
utilized Eq. (124) to evaluate the isochoric heat capacity of a liquid, as
follows:
Progress in Energy and Combustion Science 93 (2022) 101037
1 dE
Cv = , (125)
N dT
where N is the number of phonon longitudinal modes. The results
revealed that the obtained liquid energy described the experimental
behavior of an extensive variety of simple and complicated liquids.
It is
capacity of a PCM, the rate of heat transfer from a heat source to the
innermost part of a PCM can be determined using thermal diffusivity, as
follows:
k
α= . (126)
ρcp
4.6. Optical properties and radiation transfer in ePCM slurries/
dispersions
Understanding the fundamentals of radiation transfer and optical
properties of ePCM slurries/dispersions is key in DASCs that rely on the
dual functionality of ePCMs for solar absorption and storage. For
instance, in the DASC system that was discussed in Section 3.5.2, part of
the incident solar radiation was directly absorbed by the carrying fluid
and the other part by the ePCM particles, which is highly dependent on
their optical properties and the nature of their interactions with the
electromagnetic waves. Therefore, the following sections are dedicated
to presenting the foundation of radiation transfer in ePCM slurries and
optical properties.
4.6.1. Radiation transfer in ePCM slurries/dispersions
The interactions of electromagnetic waves with an ePCM slurry are
somewhat different from their interactions with a homogeneous me­
dium such as a liquid or gas. In general, electromagnetic waves traveling
through a homogeneous medium can be reflected, absorbed, or trans­
mitted [497], as illustrated in Fig. 59 (a).
When photons reach a participating radiative medium (solid, liquid,
or gas), their energy is attenuated exponentially throughout the medium
due to absorption and scattering. The absorbed energy is converted into
internal energy, the amount of which is proportional to intensity of the
incoming electromagnetic waves and traveled distance through the
medium. However, due to scattering, radiation is redirected from the
direction of propagation to be augmented in another direction.
Assuming that the incident waves, Iη, are traveling within an infini­
tesimal volume in the direction ̂s through a medium with a constant
refractive index, i.e., waves traveling in a straight line, as shown in
Fig. 59 (a), we obtain,
(dIη )abs = − σ η,a Iη ds, (127)
(dIη )sca = − σ η,s Iη ds, (128)
where ση,sand ση,a are the scattering and absorption coefficients,
respectively. By summing up Eqs. (127) and (128), then integrating the
resultant equation over a geometric path ̂s , we obtain,
⎛
∫s
⎞
⎝
Iη (s) = Iη (0)exp − (σaη + σ sη )ds⎠ = Iη (0)e− τη , (129)
0
quantified using the extinction coefficient,ση,ex, defined as,
σ η,ex = ση,a + σ η,s . (130)
The optical path length, τη, is a dimensionless quantity that aids in
determining the phase of light and controlling interference and
diffraction as it travels. It is defined based on the extinction coefficient,
as follows:
64
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Fig. 59. Electromagnetic radiation interactions with a) a homogeneous medium and b) a small particle. This includes transmission, absorption, reflection, refraction,
and diffraction.

∫s
dIη (τη , ̂s )
τη = ση,ex ds. (131) ̂s = ση,a Ibη (τη , ̂s ) − ση,a Iη (τη , ̂s ) − ση,s Iη (τη , ̂s )
d τη
0
∫
σ η,s
As for interacting with a small individual particle, the direction of + Iη (τη , ̂s i )ϕη (̂s i , ̂s )dΩ i , (133)
4π
incident photons may change, as seen in Fig. 59 (b). This directional 4π
change can take place through one of three methods [497]:
where Iη is radiation intensity, τη is optical path length, Ibη is Planck’s
• Diffraction: The photon may change its direction without ever function, and Ω is solid angle. ϕη (̂s i , ̂s ) denotes the scattering phase
colliding with the particle. function which describes the likelihood that a ray from one direction, ̂s i ,
• Reflection: The photon may be reflected from the particle. will be scattered in another direction, ̂s . The right-hand side of Eq. (133)
• Refraction: The photon may change its direction after penetrating shows that intensity increases by emission (ση,aIbη) and in-scattering
the particle. (σ ∫ )
from other directions 4ηπ,s 4π Iη (τη , ̂s i )ϕη (̂s i , ̂s )dΩi while decreasing by
absorption (σ η,a Iη (τη , ̂s )) and out-scattering away from the incident di­
These three mechanisms are collectively known as the scattering of
radiation. rection (ση,s Iη (τη ,̂s )). All quantities in Eq. (133) are a function of location,
The mechanism of interaction between electromagnetic waves and time, and wavenumber. Since the intensity and scattering phase function
particles is determined by the relative size of the particle in comparison are both functions of ̂s i and ̂s , Eq. (133) can also be written as follows:
to the characteristic wavelength of incident radiation, λ. This is quan­ dIη (τη , ̂s ) ωη
∫
tified using the size parameter of the particle, defined as follows, ̂s + Iη (τη , ̂s ) = (1 − ωη )Ibη (τη , ̂s ) + Iη (τη , ̂s i )ϕη (̂s i , ̂s )dΩi ,
d τη 4π
4π
2π rpa
χη = , (132) (134)
λ

where rpa is effective radius of the particle. where ωηis the single scattering albedo, which indicates the relative
When electromagnetic waves interact with an ePCM slurry, they are importance of scattering to absorption. When ωη = 0, the medium does
partially absorbed by the liquid and partially absorbed and scattered by not scatter at all, whereas ω = 1 indicates pure scattering. The single
the ePCM particles. As a result, an ePCM slurry can be optically viewed scattering albedo is formulated as follows,
as a participating radiative medium. The radiative transfer equation ση,s σ η,s
ωη ≡ = . (135)
(RTE) can then be used to evaluate radiative transfer within the ePCM ση,a + σ η,s σ η,ex
slurry in the presence of absorption, emission, and/or scattering. The
The last two terms in Eq. (134) are frequently combined, and this is
RTE describes the radiative intensity field within an enclosure as a
known as the source function for radiative intensity, defined as follows:
function of radiation direction (unit vector, ̂s ), location, → r , and a
∫
spectral variable, e.g., wavenumber, η. ωη
Sη (τη , ̂s ) = (1 − ωη )Ibη (τη , ̂s ) + Iη (τη , ̂s i )∅η (̂s i , ̂s )dΩi . (136)
To compute the net radiative heat flux across a surface element, it is 4π
necessary to evaluate radiative energy contributions from all possible 4π

directions and wavenumbers. When an electromagnetic wave travels in
the direction of ̂s through an ePCM slurry, it loses energy by absorption
and scattering away from the direction of travel, while acquiring energy
through emission and scattering in the direction of travel ̂s from other
directions. As a result, the RTE depicts the intensity change by adding
the contributions from absorption, emission, in-scattering, and out-
scattering along the direction of ̂s . Consequently, the RTE in its full
form is given by (computations detail can be found elsewhere, e.g.,
[497]),
Therefore, Eq. (134) can be written in the deceptively simple form of,
dIη
̂s + Iη = Sη . (137)
d τη
The RTE is generally difficult to solve due to several factors,
including geometry as problems are often multi-dimensional while the
majority of exact solutions are for one-dimensional geometries. Another
factor is that the temperature field is unknown and uncoupled from
conduction and convection, so it must be determined through the

65
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

directional and spectral integration of the RTE. It is also common to where D and H are the electric and magnetic field vectors, respectively,
assume that there is no scattering or that scattering is isotropic as and E and μ0 are electric field intensity and magnetic permeability,
anisotropic scattering is difficult to model and is rarely reported. respectively. The charge density owing to free electrons is denoted by ρf,
Furthermore, most calculations are restricted to situations involving the and it is considered to be related to the electric field vector as follows:
domain with constant properties [497]. Some solution methods for the
RTE are reported in the literature to be used in complex situations with ∂ρf
= − ∇.(σ e E). (144)
the aforementioned difficulties, such as the spherical harmonics method ∂t
[498], the discrete ordinates method [499], the zonal method [500], As previously mentioned, whenever an electromagnetic wave or
and the Monte Carlo method [501]. photon interacts with a medium that includes small particles, the radi­
In [502], the authors investigated the influence of radiation heat ative intensity of the photon or wave may be changed by absorption
transfer during the melting of a PCM inside a spherical shell. The RTE and/or scattering. If scattering by one particle is unaffected by the
was expressed under the assumption of isotropic scattering in a spheri­ presence of other particles, we have independent scattering; otherwise,
cally symmetric medium, as follows: we have dependent scattering. The scattering regime of a particle system
μ ∂[r2 I(r, μ)] 1 ∂[(1 − μ2 )I(r, μ)] ( ) is determined by three parameters: the size parameter, χη, volume
r2 ∂r
+
r ∂μ
+ σ η,a + σ η,s I(r, μ) fraction, αp, and the interparticle distance to wavelength [505].
For suspension systems (nanofluid or ePCM dispersion), the inde­
∫1
σ η,s pendent scattering region is widely used since it enables the determi­
= σ aη Ibη (T) + I(r, μ′ )dμ′ , (138)
2 nation of the optical properties and radiation extinction of a particle
cloud via a first-order summation of the optical properties and radiation
− 1

where μ is cosine of the angle formed by the beam’s direction, Ω, and the
radial vector’s extension, r. The last term in Eq. (138) specifies fluctu­
ation in the intensity of radiation inside a medium as a result of scat­
tering from the incoming direction μ . Therefore, the authors solved the
′
RTE using the discrete ordinate method. This entailed discretizing the
full incidence solid angle with a finite number of ordinate directions and
weight factors. Thus, the integral term in the integro-differential Eq.
(138) is substituted for a quadrature calculated over each ordinate. This
resulted in the transformation of the problem into a discrete system of
differential equations, which can be used to calculate the radiation in­
tensity Ii at any point within the medium:
μi ∂[r2 Ii ] 1 ∂[(1 − μ2 )I]μ=μi ( ) σ sη ∑
n
+ + σ η,a + σ η,s Ii = σaη Ibη + wi Ii .
r ∂r
2 r ∂μ 2 i=1
The subscript i represents quadrature points (ordinate directions),
and a weighting factor for each ordinate direction is represented by wi.
After the radiation intensity is known, the local radiative heat flow, qr,
which contributes to the energy equation, can be estimated using the
following expression:
∫1 ∑
n rating a scaling factor based on the solid volume percentage [6,508],
qr = 2π I(r, μ)μdμ = 2π μi wi Ii .
− 1
i=1
The discrete ordinates method was also used to solve the RTE in its
form as written in Eq. (134) to analyze the melting process of a fatty
acid-filled glass brick wall [502]. The melting process was linked to the
discretized energy equation based on the enthalpy method to compute
the temperature field, while the LBM was used to compute the velocity
field. The main conclusions were that convection had a significant effect
on the heat transfer process, whereas long-wave radiation could be
ignored when studying the melting process.
4.6.2. Evaluation of the optical properties of ePCM slurries/dispersions
Maxwell’s equations serve as the foundation for all scattering the­
ories. Based on electrical experiments with very coarse temporal and
spatial resolutions, Maxwell proposed a set of equations that fully
describe electromagnetic waves, i.e., the interactions of electric and
magnetic fields. The equations are presented as follows [503,504],
→ Maxwell’s equations and impose rather strict conditions. Both basic
∂D ̅→
= ∇ × H,
∂t
D(ω) = ε(ω)E(ω),
→ scattering approximation. First, the ePCM suspension should be dilute
∂D 1 →
=− × E,
∂t μ0
extinction of individual particles. Siegel and Howell [506] proposed the
following condition for the interparticle distance that should be satisfied
for the independent scattering region:
λ
ID + 0.1D > , (145)
2
where D is equivalent diameter of the particle. According to [507], the
interparticle distance can be expressed in terms of the volume fraction
as,
ID = 2.77Dαpa− 3.081
. (146)
To sum up, if the solid volume fraction, αpa,is less than 10% and a
particle meets the independent scattering condition, the extinction co­
(139)
efficient can be determined using the independent scattering theory [6],
as follows [497,508],
3αpaQ η,ex
σ η,ex = . (147)
2dpa
However, if αpa is greater than 10% and less than 70%, the modified
independent scattering theory can be applied, which involves incorpo­
(140) 3αpaQ η,ex
σ η,ex = Sr, (148)
2dpa
where Sr is the Singh-Kaviany scaling factor, which introduces the effect
of the solid volume percentage of ePCM slurries/dispersions in the
calculation of the extinction coefficient. It can be stated as follows:
Sr = 1 + 1.84αpa − 3.15α2pa + 7.20α3pa . (149)
Qη,ex in Eq. (147) represents the extinction efficiency, which is equal
to the summation of the absorption and scattering efficiencies. These
three quantities can be determined using a variety of analytical and
computational methods. The optimal technique is determined by the
geometry, composition, and concentration of the particles, as outlined in
the following sections.
Analytical approaches. Rayleigh’s and Mie’s scattering theories are two
general optical theories that have been widely used. Both are based on
theories, as well as Mie’s theory for encapsulated spheres, will be dis­
(141)
cussed in the following subsections.
Rayleigh’s theory. Two conditions must be satisfied if the optical
(142)
properties of an individual particle are to be derived using the Rayleigh
(143) enough so that the dependent scattering effects are negligible. Second,

66
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

the particle size should be smaller than the wavelength of incident ra­ where an and bn are the Mie coefficients, which can be computed by
diation. Strictly speaking, the Rayleigh scattering approximation is valid applying Maxwell’s boundary conditions at the surface of the particle
under the assumptions of χη << 1 and |m|χη << 1 [497,509], where m = after expanding the electromagnetic waves. Ultimately, they can be
n + ik is the ratio of the complex refractive indices of the ePCM particle expressed as follows [511],
to the surrounding fluid medium. The Refractive index and the ab­
sorption index are denoted by n and k, respectively. an =
ψ n(x)ψ ′n (mx) − mψ ′n (x)ψ n(mx)
(157)
By meeting these conditions, the absorption and scattering effi­
′
ξn(x)ψ ′n (mx) − mξn (x)ψ n(mx)
ciencies can be calculated using the following equations,
mψ n(x)ψ ′n (mx) − ψ ′n (x)ψ n(mx)
{ 2
m − 1
[ ( )
χ 2η m2 − 1 m4 + 27m2 + 38
]} bn = (158)
Qη,a = 4χ η Im 2 1+ , (150) mξn(x)ψ ′n (mx) − ξ′n (x)ψ n(mx)
m +1 2
15 m + 2 2
2m + 3
ψ n and ξn are the Riccati-Bessel functions, which must be solved in a
8
⃒( 2 )⃒
⃒ m − 1 ⃒2 step-by-step manner. To derive these functions, the following mathe­
Qη,s = χ 4η Re⃒⃒ 2 ⃒. (151) matical computations based on the recursive technique are used [509,
3 m +2 ⃒
512],
As a result, the extinction efficiency of a single particle is calculated
2n − 1
as follows: ψ n (z) = ψ n− 1 (z) − ψ n− 2 (z), (159)
z
{ 2 [ ( ) ]}
m − 1 χ 2η m2 − 1 m4 + 27m2 + 38
Qη,ex = 4χ η Im 2 1+ n
m +1 2
15 m + 2 2
2m + 3 ξ′n (z) = − ψ (z) + ψ n− 1 (z), (160)
⃒( )⃒2 z n
8 4 ⃒⃒ m2 − 1 ⃒⃒
+ χ η Re⃒ 2 . (152)
3 m +2 ⃒ ξn (z) =
2n − 1
ξn− 1 (z) − ξn− 2 (z), (161)
z
It is important to note that there is a lack of experimental in­
vestigations into the absorption index of PCMs. Additionally, the ab­ n
ξ′n (z) = − ξ (z) + ξn− 1 (z) (162)
sorption of a PCM is changed by the addition of nanoparticles or the z n
encapsulation of the PCM by a shell [6], further emphasizing the As initial conditions, the recursive relationships listed below are
importance of conducting systematic investigations to reveal the optical applied,
properties of ePCMs and NE-PCMs.
The scattering efficiency varies with the fourth power of particle size, ψ − 1 (z) = cos(z), (163)
as seen in Eq. (152). However, the absorption efficiency varies almost
ψ o (z) = sin(z), (164)
linearly with particle size, even though there is a χ 2η term inside the
imaginary part of Eq. (150) [374], which does not have a significant ξ− 1 (z) = exp(− iz), (165)
impact. By substituting Eq. (152) into Eq. (148), the extinction coeffi­
cient can be defined as follows: ξo (z) = i exp(− iz). (166)
12παpa
{ 2
m − 1
[ ( )
χ 2η m2 − 1 m4 + 27m2 + 38
]} Mie’s theory for encapsulated spheres. Mie’s theory, which is fasci­
σ η,ex =
λ
Im 2
m +1
1+
15 m2 + 2 2m2 + 3 nating when applied to a single spherical particle, can be extended to a
⃒( 2 )⃒2 coated/encapsulated sphere. Mie’s theory is based on the expansion of
4 3 ⃒
8π D αp⃒ m − 1 ⃒ ⃒
+ . (153) incident electromagnetic waves, scattered waves, and waves inside the
λ4 ⃒ m2 + 2 ⃒ particle in terms of spherical vector harmonics. When it comes to coated
In some circumstances, the conditions of χη ≪ 1 and |m|χη ≪ 1 are no particles, the expansion of these waves applies to the core and each shell.
longer met in a system after some time due to particle clustering. As a Therefore, the electromagnetic fields must meet Maxwell’s boundary
result, the size and shape of the original particles can be greatly altered.
The produced clusters are always large and irregular since clustering (i.
e., aggregation and/or agglomeration) is categorized as a random pro­
cess [505].
Mie’s theory. The Rayleigh scattering approximation is applicable to
small particle sizes. But as the particle diameter and incident wavelength
become of the same order of magnitude, Rayleigh’s theory no longer
applies. As a result, Mie’s theory can be used, which takes into account
the effect of various scattering directions by the expansion of incident
electromagnetic waves, scattered waves, and waves inside the particle in
terms of spherical vector harmonics [505], allowing it to describe
scattering for large particles. The literature can be consulted for more
information on the calculation procedure (e.g., [510]).
In Mie’s scattering theory, the scattering Qη,s and absorption Qη,a
efficiencies can be obtained as follows,

2 ∑ ∞ ( )
Qη,s = 2 2
(2n + 1) |an | + |bn | , (154)
x2 n=1

2 ∑ ∞
Qη,ex = (2n + 1)Re(an + bn ), (155)
x2 n=1 Fig. 60. Schematic view of a spherical particle with r − 1 concentric shells (or r
concentric spheres) and s materials (where s = r) embedded in a non-absorbing
Qη,a = Qη,ex − Qη,s , (156) medium. The 1st boundary is between the core and the innermost shell, the 2nd
boundary is between any two consecutive shells, and the 3rd boundary is be­
tween the outermost shell and the embedding medium.

67
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

conditions at three different boundary levels, as indicated in Fig. 60.
Namely, the boundary between the core and the innermost shell, the
boundary between two consecutive shells, and the boundary between
the outermost shell and the embedding medium. From the first bound­
ary to the third, the solution is worked out step by step [497]. To the best
of the authors’ knowledge, no works have utilized Mie’s theory for
encapsulated spheres in ePCM slurries.
Fig. 60 depicts a multilayered spherical particle (i.e., r concentric
spheres). The core sphere of radius R is represented by material s = 1 and
refractive index n1. Concentric with the core sphere is a multi-shell of r
− 1of various materials, s = 2, …., r, different thicknessesds, and the
refractive indices of each material are denoted byns. It is assumed that
the coated particle is embedded in a non-absorbing medium with a
refractive index of nM. The relative complex refractive index, m, is
defined as the relative refractive indices from shell sto shell s + 1. For s
= r, the refractive index nr + 1 corresponds to the refractive index nM of
the embedding medium. The wavenumber for each medium is defined as
follows [497],
2πns
ηs = . (167)
λ
And the corresponding size parameter, χs, is defined as follows,
(
∑s
) =
χ s = ηs+1 R + dj , (168)
j=2
The T matrix in Eq. (171) is a transition matrix that converts the
coefficients of the incident field to the coefficients of the scattered field.
This technique is mostly used for axisymmetric particles, such as finite
circular cylinders and spheroids.
Finite-difference time-domain (FDTD). Finite-difference time-domain
(FDTD) is a method for obtaining the optical coefficients of an object
with complicated geometry and/or composition by directly solving
Maxwell’s time-dependent curl equations. The equations are discretized
in time and space using finite-difference approximations. As a result,
when electromagnetic waves interact with particles, the discretized
Maxwell equations are employed to describe their propagation and
scattering. Based on the source of the electromagnetic wave, conver­
gence information for the scattered field can be obtained. For example,
when the sinusoidal source is used, the scattering information is ac­
quired by establishing a steady-state field at each grid. However, when a
pulse source is utilized, information is extracted when the scattered field
decreases significantly to a small value. This approach can be used on a
variety of materials as well as full-wave bands. It can also be used for any
shape or defect that can be found in the particles [509].
For a 1D system, the discrete form of the electric flux-dependent form
of Maxwell’s equations in Eq. (141) is written as follows,
Ej+1/2 (i) − Ej− 1/2
(i) H j (i + 1/2) − H j (i − 1/2)
, (172)
Δt Δx
where i and j are space and time coordinates, respectively. It is important

to note that the time step must be small enough to ensure that this in­
where η, R, and d are the wavenumber, core radius, and shell thickness,
formation does not travel from one grid cell to the next faster than the
respectively. Index j varies from 2 to the number of shell materials used,
speed of light in the medium [514].
s. Calculations details for the extended Mie coefficients for coated
Discrete dipole approximation (DDA). The discrete dipole approxi­
spheres and their initial conditions can be found in [497].
mation (DDA) method solves the integral volume equation discretized
Basic optical theories such as Rayleigh’s and Mie’s theories have
from Maxwell’s equations for an array of virtual N-point dipoles instead
clear physical implications and are simple to solve. However, they
of the particles. As a result, this approach is ideal for irregular and
necessitate extremely strict conditions, and in some cases, they are
complex geometries. It solves the electrodynamic interaction of elec­
inapplicable. For example, only certain geometries have perfect solu­
tromagnetic waves and dipoles based on fast Fourier transform (FFT)
tions to Maxwell’s equations, such as spheres, spheroids, or infinite
iterations [515]. If the array spacing is narrow enough in comparison to
cylinders. In addition, the small size of particles increases the collision
the wavelength of electromagnetic waves in the target material, and N is
rate while decreasing interparticle distance. Therefore, particle clus­
large enough to correctly characterize the target shape, the approach is
tering often occurs. Rayleigh’s scattering theory in this case cannot be
valid [516]. DDSCAT [517] and OpenDDA [518] are two well-known
used to describe the scattering process because the particle size has
codes for performing DDA calculations to determine the absorption
increased (i.e., χη ≫ 1). Hence, computational/approximate methods are
and scattering properties of particles. Ref. [516] provides a full account
required, as presented next.
of the DDA procedure.
Generalized multi-particle Mie (GMM) theory. The generalized multi-
Computational approaches
particle Mie (GMM) theory is an extension of Mie’s theory in which the
T-matrix method. The T-matrix method, also known as the extended
incident and scattering electromagnetic fields are expanded in terms of
boundary condition method, begins the same as Mie’s theory by
vector spherical wave functions [519]. Using this method requires full
expanding the incident, scattered, and internal electromagnetic waves
geometric description of particles or their clusters (aggregates or ag­
into the corresponding vector spherical harmonics [509]. This is fol­
glomerates). All sorts of materials and full-wave bands can be used in
lowed by finding the internal field expansion coefficients, cn and dn,
this process, but the particles must be homogeneous. In this method, the
through solving a set of linear equations, as follows [509],
incident and scattered electromagnetic fields are expanded as a
( )
(
Kqn + mJqn Lqn + mIqn
)( )
cn eTM third-kind vector spherical harmonic expansion, as shown in Eqs. (173)
n
= (− i) TM . (169) and (174) [520,521],
Iqn + mLqn Jqn + mKqn dn en
∞ ∑
∑ n ∑
2
K,J, L, and I are area integrals evaluated numerically across the i
Einc = p(1) (1)
mnp Nmnp (ηri ), (173)
particle’s surface area. eTM n and eTM
n are the incident beam coefficients.
n=1 m=− n p=1

The coefficients of scattered field expansion, an and bn, are obtained

in the same way [513], ∑
∞ ∑
n ∑
2
i
Esca = aimnp Nmnp
(3)
(ηri ), (174)
( )( ) ( ) n=1 m=− n p=1
̃ qn + m̃
K J qn ̃Lqn + m̃I qn − icn an
= . (170)
̃I qn + m̃
Lqn ̃ ̃ qn
J qn + mK − idn bn
where η is the wavenumber, ri is the position vector, n is a multi-index
By designating the matrix in Eq. (169) as A and the matrix in Eq. that subsumes the polarization p = 1, 2 and the multipole indices m
(170) as B, we have [513], = − n,..., n. The vector spherical wave functions for incoming and out­
going waves are denoted by Nmnp and Nmnp .
( ) ( ) (1) (3)
( )
an eTM eTM
= BA− 1 nTM = T nTM . (171) Evaluation of the scattered field of each particle is needed to solve
bn en en
multi-particle scattering problems. Therefore, aimnp is determined
through applying boundary conditions on the surface of a single particle.

68
S.A. Albdour et al.
Assuming that the total incident electromagnetic field for each particle is
Eiinc , which consists of the original incident wave Eio and the scattered
field
∑N i
=i Es (j) from all other particles in the simulation area, the
j∕
following relations are obtained [519],
aimnp = aimn pimnp , (175)
∑
N Understanding and analyzing the material and interfacial structures of
i
Einc = Eoi + Esi (j), (176)
j∕
=i
where aimn is the Mie coefficient of single spherical particle i and pimnp is
the expansion coefficient of the total incident electromagnetic field.
4.7. Energy analysis of ePCM-based direct-absorption solar collectors
(DASCs)
Generally, the energy efficiency of a latent TES system can be
determined, using the first law of thermodynamics, as the ratio of useful
output energy to input energy. Due to energy loss, the useful energy
output is always less than the energy input in a practical TES system.
Thus, understanding the energy efficiency of TES can help in increasing
the amount of stored/released energy by minimizing losses.
Mosaffa et al. [522] conducted an energy analysis of a latent TES
system for free cooling applications to demonstrate the advantages of
cascading PCMs over a single PCM system. Their findings indicated that
by employing multiple PCMs, decreasing the temperature difference
between the HTF and PCM over time increased the energy efficiency. Yu
et al. [523] investigated the energy performance of a PV/T system based
on a micro-ePCM slurry. Results showed that, when compared to pure
water, the slurry provided a maximum improvement in energy effi­
ciency at a lower inlet velocity. Eisapour et al. [524] investigated the
energy efficiency of a PV/T system with a sinusoidal wavy tube based on
a micro-ePCM slurry enhanced with nanoparticles as the coolant fluid.
The electrical and thermal efficiencies of a typical PV/T module were
increased from 10.73% for the former and 58.56% for the latter, to
11.33% and 63.74%, respectively, when using a micro-ePCM slurry
enhanced with nanoparticles instead of pure water.
For the energy analysis of a DASC based on an ePCM slurry/disper­
sion, the main idea is that solar radiation is absorbed by both the car­
rying fluid and ePCM particles. Thus, the overall energy efficiency is
given as:
Quse,slurry
ηtotal = . (177)
Qsun
The following expression is used to find the amount of useful heat
carried by the ePCM slurry,
Quse,slurry = ṁslurry cp,eff (Tout − Tinlet ). (178)
The received energy from the sun is written as follows:
∫∞
Qsun = A.αg . I(λ)dλ. (179)
0
4.8. Conclusions and future research directions
A sound understanding of the theory and fundamentals that govern
the performance of ePCM systems can be realized through a variety of
tools. As inherently multi-phase and multi-scale systems, it is unfortu­
nate that the majority of published research on ePCM slurries and dis­
persions is based on continuum, single-phase models. In continuum
models, intraparticle, interparticle, particles-wall, and particle-fluid in­
teractions are inaccurately or incompletely captured. Furthermore, if
friction or gravity forces are important, the assumption of no-slip ve­
locity clearly fails. Discrete approaches, on the other hand, where the
69
Progress in Energy and Combustion Science 93 (2022) 101037
motion and interactions of discrete entities in the flow domain are
individually computed, are constrained by the computer’s memory and
computational time. Multi-scale models (e.g., coarse-grained and
continuum-discrete models) have the potential to overcome the limita­
tions of continuum and discrete models and accurately describe ePCM
slurries/dispersions where coupled analysis on multiple scales is
required. Studies on the mesoscale, in particular, are poorly explored.
PCM molecular assemblies, as well as the heterogeneous flow structures
of ePCM clusters, are the main challenges at this scale.
For a better description of slurry behavior, empirical/semi-empirical
thermophysical property correlations for the density, heat capacity, and
thermal conductivity of ePCMs are needed over a broad range of tem­
peratures and concentrations. Parallel to experimental data, a funda­
mental understanding of the thermal conductivity and heat capacity of
PCMs will expedite progress toward the design of advanced PCM sys­
tems capable of storing and releasing latent heat more efficiently.
Computational methods like molecular dynamics and density functional
theory can allow us to better understand the transition from solid to
liquid.
In the design for direct-absorption solar applications, optical prop­
erties of the micro/nano-ePCMs and radiation transfer in their slurries/
dispersions ought to be properly evaluated. Although both Mie’s and
Rayleigh’s theories are based on Maxwell’s equations, only Mie’s theory
should be used to evaluate the optical properties of most ePCM systems
as dependent scattering often cannot be ignored. Of particular interest to
ePCMs is the Mie theory for encapsulated spheres where incident elec­
tromagnetic waves, scattered waves, and waves inside the particle are
expanded at each shell. However, both Rayleigh’s and Mie’s theories are
no longer applicable if the particles cluster. In such cases, it is recom­
mended to use computational approaches such as the T-matrix method,
finite-difference time-domain, discrete dipole approximation, or the
generalized multi-particle Mie theory.
5. Recent advances in solar photothermal conversion using
micro/nano-ePCMs
In light of this comprehensive review on PCMs and the dual func­
tionality of micro/nano-ePCMs for solar photothermal absorption and
storage, it is critical to highlight present knowledge gaps and future
research objectives. As such, the following sections will highlight a
number of topics that the authors believe represent potential or realized
breakthroughs that should guide future research directions.
5.1. Custom engineering of multi-functional PCM shells
The degree of success of any solar conversion and storage system is
dependent on the solar photothermal capture, transfer, and storage
processes. By employing ePCM slurries/dispersions in volumetric ab­
sorption systems, the processes of radiation extinction, thermal storage,
and heat transport are seamlessly and synergistically combined. The
majority of research advances in the field of solar TES systems based on
ePCMs have focused on the storage process, which has been extensively
discussed in the preceding sections. As such, the current section will
highlight some of the most interesting advancements in the field of
ePCMs that have been made to optimize the integration of the processes
of solar capture, conversion, and storage, with a particular emphasis on
capsule shell optimization.
The shell encapsulating a PCM plays a critical and multi-functional
role that determines the efficiency and longevity of a photothermal
conversion and storage system. This is particularly true for direct
volumetric absorption systems with the dual functionality of solar
photothermal absorption and storage. As shown in Fig. 61, the shell has
multi-functional roles in a direct-absorption system, including optical,
thermal, and structural roles. The optical role of the shell entails solar
energy absorption and conversion to cause the PCM cores to melt and
S.A. Albdour et al.
Fig. 61. The multi-functional roles of the shell encapsulating a PCM in a direct-absorption photothermal conversion and storage system.
retain thermal energy. The broadband or selective extinction of solar
radiation is a critical function assumed by the shell in volumetric ab­
sorption systems. To improve heat transfer in both the PCM core and the
carrying fluid, the thermal role of the shell entails having high thermal
conductivity. Structurally, the shell is responsible for preventing leakage
and degradation of the PCM core during charging and discharging
processes. Traditionally, shell materials are synthesized from polymer,
organic, or inorganic materials such as polymethyl methacrylate
(PMMA) [525], melamine formaldehyde resin [526], polystyrene (PS)
[527], polyurethane [528], urea formaldehyde [160], silica [529], ti­
tanium dioxide [386], calcium carbonate (CaCO3) [379], cuprous oxide
(Cu2O) [530], zirconia (ZrO2) [531], and aluminum hydroxide oxide
Al2O3•xH2O [532].
The infinite potential of solar radiation in direct-absorption ePCM
slurries and dispersions is limited mainly by the inability of conventional
shell materials to harvest a significant portion of sunlight. This is despite
the PCM core and carrying fluid being able to absorb a small part of
incident radiation, mainly in the infrared range. As shown in Fig. 62,
infrared radiation accounts for 49% of the solar spectrum, visible light
Fig. 62. Extraterrestrial (yellow) and terrestrial (red) solar spectra. Also shown
is the spectrum of blackbody radiation (black).
70
Progress in Energy and Combustion Science 93 (2022) 101037
accounts for 44%, and UV light accounts for about 7% of the spectrum.
However, the majority of the aforementioned shell materials are strong
absorbers only in the UV band. This indicates that the majority of solar
radiation would be unused by the shell and slurry/dispersion as a whole.
In light of these considerations, extensive research is being conducted
along a variety of pathways to design and synthesize new PCM shells
that maximize solar radiation absorption while simultaneously main­
taining the aforementioned structural and thermal functionalities.
For instance, TiO2 is a popular inorganic shell material since it out­
performs polymer materials in terms of mechanical strength and thermal
conductivity, which improves the operational reliability of the ePCM
and the heat transfer performance of the slurry/dispersion as a whole.
However, because of its poor optical absorption properties in the visible
light range (TiO2 is in the form of a white powder), it is unable to
effectively absorb solar radiation. Nonetheless, in a recent important
development, Zhao et al. [533] reported that by reducing the oxygen
content of TiO2 to form TiO2-x, the ability to absorb visible light was
enhanced as a result of narrowing the bandgap. Thus, by modification of
conventional shell materials for ePCM particles, it is possible to meet
their multifunctional needs by combining the intrinsic properties of the
component materials to boost their light-harvesting capacity.
Pornea and Kim [382] designed an innovative ePCM with a hierar­
chical SiO2/TiO2/polydopamine (PDA) compound shell and n-eicosane
as the core. The traditional interfacial polycondensation method was
used to prepare silica-coated n-eicosane. The TiO2 white particles were
then deposited in varying amounts on the SiO2 layer to create different
samples, and then a PDA surface modifier was deposited on top of the
TiO2 layer. SiO2 functions as a refracting channel that extends the op­
tical path of incoming light by exciting electrons, thereby increasing
localized surface heating at the outer surface of n-eicosane without the
need of a thermal conductivity initiator. The deposition of the PDA film
on the TiO2 surface was dictated by how PDA, due to its π-system,
mimics organic semiconductors, which was previously exploited as a
photosensitizer for visible light absorption [534]. Because of the
increased localized surface photothermal heating at the outer surface of
the core, an absorption shift was induced over a wider wavelength
range, allowing for more photon usage. The proposed triple-layer
structure was shown to surpass existing shell designs in terms of latent
heat, mechanical strength, thermal conductivity, capsule leakage, and
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

solar energy absorption.

Modification efforts of conventional TiO2 shells were not limited to
absorption augmentation in the visible light range but included the
entire light spectrum. For example, Fan et al. [535] synthesized
n-eicosane/TiO2/CuS-GO microcapsules capable of capturing and
absorbing radiation across the entire solar spectrum. The combination of
CuS and GO was used as a photothermal filler, where CuS nanoparticles
were loaded into GO nanosheets that acted as structural supports. CuS
has a broad absorption band across the entire spectrum, with a strong
near-infrared (NIR) absorption peak, as shown in Fig. 63(a). This is
mostly due to the influence of the surface plasmon resonance of CuS,
which occurs when a collective oscillation of conduction electrons on
the surface of nanoparticles is excited by light with a wavelength longer
than the size of the particle, resulting in unusual absorption and scat­
tering properties. GO, on the other hand, operated synergistically with
CuS due to its high surface area, mechanical strength, and abundance of
oxygen-containing groups, avoiding severe aggregation of GO flakes and
CuS nanoparticles. This uniformly localized CuS nanoparticles on the
flakes, leading to hot-carrier transfer and easier electron transport. The
photothermal storage efficiency was up to 97.1% under simulated sun­
light irradiation, outperforming existing solar-driven microcapsules by
91.8% [536]. The absorbance spectra of the microcapsule samples are
shown in Fig. 63 (b). Because of the brookite-phase TiO2 shells with
wide bandgaps, all of the microcapsule samples were strongly respon­
sive to UV light. The n-eicosane/TiO2/CuS-GO microcapsules were
found to display significant broadened absorption across the full solar
spectrum.
SiO2 is another inorganic shell material that is commonly chosen due
to its non-toxicity, structural stability, and well-defined surface char­
acteristics. Unfortunately, in addition to having poor optical properties,
SiO2 has low mechanical strength and can be easily damaged. To address
these issues, Zhang et al. [537] developed and synthesized new paraf­
fin/SiO2/Ti4O7 microcapsules with paraffin cores and Ti4O7
nanoparticle-modified SiO2 shells through the sol-gel technique. The
TES capacity of the synthesized microcapsules was high (122.4− 169.5
kJ/kg). The thermal conductivity of the new microcapsules increased
from 0.304 to 1.322 W/m•K as compared to paraffin due to the high
thermal conductivity of the SiO2 shells enhanced by Ti4O7 nanoparticles.
Additionally, as illustrated in Fig. 64, Ti4O7 nanoparticles exhibited an
exceptional optical absorption capacity across the wavelength range of
200− 2500 nm, indicating that they are excellent photo-capturing ma­
terials. As a result, the optical absorption of paraffin/SiO2/Ti4O7
increased as the Ti4O7 nanoparticle concentration increased. The pho­
tothermal storing efficiency of the paraffin/ SiO2/Ti4O7 microcapsules
Fig. 64. Absorption spectra of Ti4O7, paraffin, paraffin/SiO2 microcapsules,
and paraffin/SiO2/Ti4O7 microcapsules with different percentages of Ti4O7
[537]. (Reused with permission from Elsevier).
reached up to 85.36%, whereas pure paraffin was limited to only
24.14%.
Another shell enhancement technique to simultaneously increase
solar-absorption and thermal conductivity is based on using graphite
and its derivatives, which have high thermal conductivity, ultra-light
weight, and intrinsic blackbody-like optical absorption. For example,
GO nanosheets have the advantage of being extremely thin, with a
monolayer thickness of around 1 nm [538], while exhibiting a high
degree of elasticity [539], making them ideal for barrier applications
[540]. Furthermore, the presence of a variety of hydrophilic oxygen
functional groups, such as epoxy, carboxylic, and carbonyl, on the hy­
drophobic carbon layers results in the formation of amphiphilic GO,
which facilitates its assembly at the oil-water interface [541]. Therefore,
GO has been used to encapsulate PCMs and serve as a leak-proof seal
[337,542].
Ma et al. [352] created a novel heat transfer slurry incorporating
paraffin/TiO2/GO microcapsules to improve the receiver efficiency of a
DASC system. By in-situ hydrolysis and polycondensation of tetrabutyl
titanate, the microcapsule with paraffin as a core and TiO2 as a shell was
developed. GO was self-assembled onto the TiO2 shell to improve visible
light absorption and thermal transfer performance. The color of paraf­
fin/TiO2/GO was darker than that of paraffin/TiO2, indicating a greater
capacity for visible light absorption. Furthermore, thermal conductivity

Fig. 63. Absorption spectra of a) CuS and GO and b) different microcapsule samples (n-eicosane as a PCM core with different shells) [535]. (Reused with permission
from Elsevier).

71
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

rose from 0.25 to 0.95 W/m•K upon encapsulating paraffin with this
composite shell material.
Reduced graphene oxide (rGO) is a modified version of GO in which
the oxygen content is reduced chemically, thermally, or using other
reduction techniques. rGO cannot have the original structure of gra­
phene because some oxygen functional groups remain within or on its
surface. Gao et al. [366] synthesized magnetic phase-change micro­
capsules modified with rGO. The core material was octadecan doped
with oleic acid (OA) and covered with Fe3O4 magnetic nanoparticles,
while the MF shell was modified with rGO. The authors produced
GO-modified micro-ePCMs, which were darker in color than the
micro-ePCMs without GO, and then converted them into rGO-modified
micro-ePCMs using a UV-assisted reduction method. When compared
to the GO-modified micro-ePCMs, the thermal conductivity of
rGO-modified micro-ePCMs rose from 0.31 to 0.41 W/m•K. The increase
in thermal conductivity was attributed to the reduction of oxygen con­
tent, which led to a decrease in GO defects. In turn, this limited the
scattering of phonons, ultimately resulting in an increase in thermal
conductivity. During the UV-assisted reduction to form rGO, several
oxygen-containing functional groups were removed. These groups were
the reason for destroying the π − π conjugated structure of GO. Due to
partial recovery of the conjugated network and the delocalized electron
configuration in graphene, the rGO-modified ePCMs exhibited superior
optical absorbance relative to the GO-modified ones. By effectively
doping magnetic nanoparticles into the microcapsules, the
rGO-modified capsules demonstrated a strong magnetic response,
excellent controllability, and recyclability. Despite this, the latent heat
of the GO-modified ePCM slurry decreased from 183.43 to 178.73 J/g
due to the presence of a small number of faulty microcapsules after the
addition of GO, resulting in octadecane leakage. Furthermore, a few
GO-modified capsules with inherent structural flaws were easily broken
during the UV-assisted reduction process, leading to a minor decrease in
latent heat capacity.
the top surface continually rose as the extinction coefficient grew and
the temperature of the top layer of the collector increased.
Ma and Zhang [6] extended their work to compare the performance
of direct- and indirect-absorption solar collectors (IASCs) based on an
ePCM slurry at a volume fraction of 10% and an absorption index of 1 ×
10− 4. The results indicated that the DASC had a higher photothermal
conversion efficiency than the IASC because the ePCM slurry could
absorb incident radiation directly. Additionally, they demonstrated that
the optical properties of a phase-change slurry with a fixed particle size
are largely determined by the absorption index and solid volume frac­
tion of the capsules.
The authors also studied the temperature distribution in DASCs and
IASCs using a slurry without phase change (SWPC) and polyalphaolefin,
respectively. According to their findings (shown in Fig. 65), the tem­
perature of the working fluid inside the DASC was higher than that
within the IASC. On the other hand, the temperature of the working fluid
near the top surface of the DASC was substantially lower than that of the
IASC since incident radiation was absorbed by the top plate of the IASC.
As a result, it was deemed almost unavoidable that the maximum tem­
perature of the solar collector appeared on the top surface of an IASC,
causing increased heat losses to the environment via convection and
radiation. Furthermore, the temperature of the working fluid inside the
DASC for both the PCM slurry and the SWPC was found to be higher than
the top surface temperature. The temperature of the working fluid rose
vertically from top to middle before gradually decreasing as the incident
depth increases. The optical characteristics of the slurry, as well as heat
loss from the top surface, influenced the location of the highest
temperature.
Wang et al. [334] experimentally investigated the transmittances of
a micro-ePCM slurry, a water/ethanol MWCNT nanofluid, and a mixture
of the slurry and nanofluid for DASCs. The results showed that adding
MWCNTs to the base fluid dramatically enhanced absorption across the
whole wavelength range. Without MWCNTs, the micro-ePCM slurry

5.2. ePCMs or nanofluids in direct-absorption solar collectors

Numerous studies on DASCs have been conducted using nanofluids

[543]. Zain et al. [544] investigated the dispersion of different nano­
structured materials in water, such as CuO, GO, and ZnO, for a DASC
application under the weather conditions of Lahore over a year. The
outcomes revealed that, when compared to pure water, the GO, ZnO,
and CuO nanofluids improved the rate of heat transfer by 23.5, 21.1, and
15.1%, respectively. According to the findings, GO nanofluids have
considerable potential for solar thermal applications. Sharaf et al. [545]
proposed a novel Eulerian-Lagrangian hybrid modeling approach to
capture the discrete nature of dispersed nanoparticles in a DASC. Results
showed that by increasing the loading of nanoparticles from 0.001 to
0.05%, a significant increase in the nanofluid absorption efficiency was
observed.
Alternatively, it is believed that by employing ePCM slurries and
dispersions into DASCs, the efficiency of the solar collector can be
further increased, building on the high latent TES capacity and nearly
constant-temperature characteristics of ePCMs [546]. However,
research into ePCM-based DASCs is still at its infancy.
Ma and Zhang [406] numerically investigated the heat transfer
properties of a volumetric-absorption solar collector based on
nano-ePCM dispersions using a two-dimensional model of a parallel
plate. The results of the nano-ePCM dispersion were compared to those
of a conventional nanofluid devoid of phase change. Due to the spatially
uniform slurry temperature caused by phase change in the cores, the
efficiency of the collector using nano-ePCM dispersions was found to be
greater than that based on conventional nanofluids. The results indi­
cated that the DASC based on nano-ePCM dispersions was sensitive to Fig. 65. Temperature distribution in DASCs based on an ePCM slurry a) with
the extinction coefficient of the particles. The collector efficiency and b) without phase change as opposed to IASCs operating with c) an ePCM
initially increased as the extinction coefficient increased, but then slurry with phase change and d) a pure HTF [6]. (Reused with permission
dropped as the extinction coefficient further increased. Heat loss from from Elsevier).

72
S.A. Albdour et al.
exhibited extremely low (near-zero) transmittances in the desired
wavelength range. Mixing ePCMs with the nanofluid resulted in nearly
the same transmittance as the nanofluid alone. As a result, it was pre­
dicted that combining micro-ePCMs with MWCNTs may enable
combining their photothermal conversion and TES capabilities to be
employed in solar-thermal energy harvesting.
Xu et al. [353] prepared a slurry of spherical microcapsules with
paraffin cores and a shell layer of irregularly shaped copper and cuprous
oxide (Cu2O) nanoparticles covered with a large number of CNTs for use
in a DASC system. This combination was motivated by the high thermal
conductivity of copper (401 W/m•K), the excellent absorption ability of
Cu2O in the visible range, and the ability of CNTs to absorb 99.97% of
incident sunlight. The results indicated that adding CNTs substantially
increased the thermal conductivity of the paraffin/Cu-Cu2O/CNTs
slurry, expedited heat transfer, and increased the rate of heat storage. As
a result, the slurry of paraffin/Cu-Cu2O/CNTs displayed considerable
improvements in thermal conductivity, light absorption performance,
specific heat capacity, and rate of heat storage.
5.3. Optical filtration using ePCMs for direct-absorption PV/T collectors
A PV/T collector can utilize the same solar input to simultaneously
generate both electrical and thermal outputs. Additionally, optical
concentrators may be used to reduce the required area of PV cells.
However, increasing the optical concentration may cause the tempera­
ture of PV cells to rise, which is undesirable since it decreases the con­
version efficiency of the cells. To maintain reasonable efficiencies, PV
cells must be cooled. At the same time, heat collected from the solar cells
can be utilized.
In general, the photothermal conversion process turns solar energy
into heat with a very constant efficiency across the solar spectrum, with
the only variable being the optical characteristics of the absorber ma­
terial utilized. The PV conversion process, on the other hand, is
extremely wavelength-dependent and most efficient when photons with
energies close to the bandgap energy of the PV cell are utilized. Because
of these concerns, an efficient way to employ solar cells is to focus only
the section of the solar spectrum that is most efficiently converted into
electricity (typically, visible light) onto the cells and divert the rest of the
solar spectrum to a thermal receiver (usually, UV and infrared lights).
This is the fundamental concept behind spectral splitting or optical
filtration in hybrid PV/T systems, as illustrated in Fig. 66 in which the
Fig. 66. Working principle of an ideal concentrating spectral-splitting PVT
collector. Incident radiation is concentrated then split into photoelectric (PV
cell) and photothermal (thermal absorber) spectral components.
73
Progress in Energy and Combustion Science 93 (2022) 101037
incident beam is divided into PV and thermal spectral components
[547].
Recently, it has been suggested that using spectral splitters/filters
enhances the performance of a PV/T system by thermally decoupling the
PV and thermal components, allowing them to operate at significantly
different temperatures. As a result, the PV component can deliver high-
quality heat without significantly increasing the PV cell temperature.
Liquid absorptive filters, such as nanofluids, are frequently utilized as
coolant fluids and spectral splitters. In the coolant case, the nanofluid
flows beneath the PV cells to collect their heat and cool them down.
While acting as a spectral filter, the nanofluid divides the light spectrum
so that visible light is delivered to PV cells, while infrared and ultraviolet
lights are absorbed to increase nanofluid temperature [548]. An et al.
[549] used a customized experimental system to investigate the per­
formance of a concentrating PV/T collector equipped with a Cu9S5
nanofluid as a spectral splitting filter. Their findings indicate that when
Cu9S5 nanofluid was used as an optical filter, the efficiency of the PV
module increased from 16.3 to 34.2%. Crisostomo et al. [550] sus­
pended core-shell Ag-SiO2 nanoparticles in water to filter out the
optimal spectrum for silicon PV cells. The results indicated that when
exposed to the same illumination, the proposed PV/T prototype with the
nanofluid produced 12% more energy than a stand-alone PV system.
On the other hand, benefiting from their ability to store energy and
work at an almost constant temperature, PCMs have been employed to
regulate the temperature of PV panels. Su et al. [551] integrated a PCM
layer into the heat transfer tubes of an air-based PV/T collector. Ac­
cording to their findings, the overall PV/T efficiency with a 3-cm PCM
layer above the PV panel was 10.7% higher than when no PCM was used.
Sharma et al. [7] investigated the effect of using a micro-fin (surfaces
that have been expanded in one or more micro-scaled dimensions) with
a PCM enhanced with Cu nanoparticles on the thermal management of
building-integrated photovoltaics. When compared to standard PCMs,
the proposed micro-fins reduced the temperature of the PV panel, while
the nano-enhanced PCM increased heat release, resulting in an overall
lower PV temperature.
Numerous studies have reported that PCMs in their liquid state may
be useful for solar spectrum transmission. For example, Buddhi and
Sharma [8] measured the transmittance of commercial-grade stearic
acid and discovered that it has a higher transmittance than glass at the
same thickness. Consequently, they recommended using it as trans­
parent insulation due to its high transmittance and low thermal con­
ductivity. Goia et al. [552] found that paraffin wax exhibited nearly
constant transmittance in the visible range and more preferential
selectivity in the NIR range when it is liquid. Additionally, Manz et al.
[553] investigated the transmittance of CaCl2.6H2O in a solar space
heating and daylighting external wall system. The result indicated that
visible light was primarily transmitted, whereas invisible radiation was
primarily absorbed and converted to heat, resulting in a phase-change
process. Based on these findings, it is possible to conclude that PCMs
can be used as optical filters in concentrated PV/T systems.
Motivated by this, Yazdanifard et al. [554] developed a dynamic
numerical model to examine the energetic and exergetic efficiencies of a
concentrated PV/T collector integrated with a hybrid PCM-nanofluid
spectral splitter. As spectral filter components, they used two PCMs
(paraffin RT25 and salt hydrate S27) as well as an Ag/water nanofluid.
In their investigation, the PCM was positioned once above and once
below the nanofluid channel. In both situations, the salt hydrate pro­
duced a greater fluid temperature and a higher overall exergy efficiency
than paraffin, suggesting that choosing the suitable PCM can have a
substantial effect on system performance. However, when the PCM was
placed beneath the nanofluid channel, relatively higher temperatures
and higher total energy and exergy efficiencies were obtained. Addi­
tionally, relative to the nanofluid-based PV/T collector, exergy effi­
ciency was raised by 14.9% and fluid temperature was increased by 54%
to of 111◦ C. As a result of the greater absorptivity of PCMs of infrared
radiation, they claimed that the suggested system may exploit a broader
S.A. Albdour et al.
area of the solar spectrum.
Yazdanifard et al. [512] took this a step further by employing a
NE-PCM layer as the optical filter rather than bulk PCM. The researchers
used 32-carbon paraffin (C32H66) as a base PCM and glycerol as a base
fluid. Both the base PCM and fluid were doped with gold and/or silver
nanoparticles. Five distinct configurations of the spectral splitter were
examined in terms of energy, exergy, and energy storage. The results
indicated that placing the nanofluid on top of the NE-PCM layer resulted
in the maximum output temperature and energy and exergy efficiencies.
However, placing the NE-PCM layer at the bottom of the nanofluid
resulted in the highest energy storage performance. Overall, energy ef­
ficiency was more dependent on the Ag volume fraction, whereas exergy
efficiency was found more sensitive to the Au volume fraction.
The aforementioned studies pave the way for further research in this
area, including enhancing the optical and thermal properties of PCMs.
Therefore, utilizing micro/nano-ePCM slurries and dispersions as spec­
tral filters for PV/T collectors is an unexplored future route. Fig. 67
shows a schematic of the proposed spectral-splitting PV/T system using
an ePCM slurry for optical filtration.
5.4. Encapsulation of molten salts for high-temperature solar applications
A variety of organic PCMs have been used for TES. However, because
organic PCMs operate at low phase-change temperatures, they are
limited to temperatures below 100◦ C in most cases. As a result, to sup­
plement CSP plants with suitable high-energy-density PCMs, molten
salts have been investigated. Molten salts outperform organic PCMs in
terms of volumetric melting enthalpy and operating (melting) temper­
atures, increasing the energy density for storage by up to 50% and
lowering the cost by more than 40% [155]. Unfortunately, they are
corrosive at elevated temperatures, which complicates their handling
[555].
Encapsulation strategies have been proposed to address this concern
by encapsulating core components within macro, micro, and nanoscale
capsules to avoid chemical interactions between molten salts and the
surrounding environment [556,190]. Micro-ePCMs offer the benefit of
increasing the available surface area for heat transmission as compared
to macro-ePCMs. Thus, effective thermal conductivity of the TES system
may be enhanced [557]. Nano-ePCMs, on the other hand, are more
durable and have a lower breakage rate than micro-ePCMs [558]. As a
result, micro and nanoscale applications of molten salt encapsulation are
being considered.
However, due to the high water-solubility of molten salts, the
encapsulation process is disturbed when using conventional techniques
such as the sol-gel method. Therefore, a limited-water sol-gel method is
required. Lee and Jo [155] proposed a surfactant-free
Fig. 67. Schematic of the proposed spectral-splitting concentrated PV/T system using an ePCM slurry/dispersion for optical filtration. The ePCM slurry/dispersion
flowing through the upper channel functions as a spectrum splitter (optical filter) that absorbs specific wavelength bands while transmitting other bands.
74
Progress in Energy and Combustion Science 93 (2022) 101037
microencapsulation method in which sodium nitrate (NaNO3) was
enclosed by protective silica. The results revealed the suitability of
NaNO3/SiO2 microcapsules for storing thermal energy in various
high-temperature applications with a high encapsulation efficiency of
89% on average. In another study, Lee and Jo [559] devised a
surfactant-free encapsulation methodology for the synthesis of
NaNO3/SiO2 microcapsules for solar-thermal energy storage. They
evaluated the influence of precursor and catalyst concentrations on the
NaNO3/SiO2 microcapsules, as well as the synthesis time. Microcapsules
can retain 2.1 times more thermal energy than solar salts, according to
the study. The microcapsules retained their high performance after 50
thermal cycles and 12 hours of high-temperature heating.
Zhang et al. [560] synthesized microcapsules using a complex ma­
terial system composed of a binary salt of LiNa as the core and silica as
the shell. Results indicated that the proposed binary carbonate salts
were suitable for CSP applications because they had a latent heat ca­
pacity of over 220 J/g at 498 ◦ C with a 134.4% increase in effective heat
capacity over the best-commercialized product. Additionally, it was
demonstrated that the micro-ePCMs were thermally stable up to 540 ◦ C
without any change to their latent heat capacity.
Li et al. [561] used sodium nitrate (NaNO3) as the core material and
titanium dioxide as the shell to fabricate a micro-ePCM. The
micro-ePCM had a melting point of 306.5◦ C and a solidification point of
296.7◦ C, which indicated that it could be used in CSP TES systems. The
resultant micro-ePCM maintained thermal stability after 200 thermal
cycles with a latent heat of 135.3 J/g. Furthermore, when the
NaNO3/TiO2 micro-capsules were suspended in thermal oil, thermal
conductivity and specific heat were enhanced by 18.4 and 131.7%,
respectively, compared to thermal oil.
On the other hand, to our best knowledge, there is only one study on
the nanoencapsulation of molten salts published by Lee and Jo [294]. In
this study, the authors developed the nanoencapsulation technique by
taking advantage of the high solubility of molten salt in water and
employing emulsification and sol-gel processes. The results revealed
that nanoencapsulation in silica shells boosted thermal stability of the
solar salt, with the breakdown temperature of the nano-encapsulated
solar salt increasing to 596.5◦ C. Through the repetition of 50 thermal
cycles, excellent thermal dependability was established as the morpho­
logical appearance and thermal performance of the nano-ePCM were not
degraded.
5.5. New physical insights into ePCM slurries/dispersion using multi-scale
modeling
As mentioned earlier in Section 4.1.4, the phase-change rate inside
spherical capsules is reduced nonlinearly during the phase-change
S.A. Albdour et al.
process, which naturally results in non-linear energy exchange between
the capsule and the carrying fluid [422]. Additionally, due to existence
of the shell, the phase-change process of each particle is independent.
Consequently, the temperature distribution of the particles is discrete
rather than continuous [383]. Nonetheless, using a purely continuum or
discrete approach is insufficient to fully understand the heat transfer
phenomena in an ePCM slurry/dispersion. To gain a better under­
standing of ePCM slurries/dispersions, multi-scale approaches are
required that take into account the disparity of behaviors and the in­
teractions between different scales [426].
In micro/nano-ePCM slurries/dispersions, multi-scale modeling has
not been extensively employed. However, multi-scale models have been
utilized in different thermal and fluidic systems between the atomistic
and continuum scales, which could be used to establish the groundwork
for the multi-scale modeling of micro/nano-ePCM slurries/dispersions.
Under the umbrella of multi-scale modeling, many coupling pairs have
been implemented, including MD/SPH [562], MD/FVM [563,564],
MD/FEM [565], and MD/LBM [566,556] (details are presented in Sec­
tion 4.4.1).
To the best of the authors’ knowledge, only one recently published
study employed a multi-scale approach for an ePCM slurry [383]. The
authors attempted to bring a new perspective on understanding the
practical thermal energy transport of the ePCM slurry by implementing a
hybrid continuum-discrete approach. As a result, they created a
multi-scale mathematical model to predict the flow and heat transfer of
the micro-ePCM slurry during phase transition. The macroscale flow and
heat transfer model was coupled with heat transfer during phase change
at the microscale. Then, in the confined microscale simulation, a
sequence of constrained simulations were performed at each point when
macroscale data was required. The constraints included ambient tem­
perature of the microcapsule shell and the heat transfer coefficient. The
results indicated that when nonlinear latent energy release was
considered, numerical results from the multi-scale model were the
closest to experimental data of any known model. Additionally, when
the microcapsule size was decreased from 1000 to 100 µm, the average
heat transfer coefficient rose from 97.03 to 102.11 W/m2•K. However,
when the microcapsule size was smaller than 100 µm, the microcapsule
size had a negligible effect on the heat transfer coefficient.
6. Concluding remarks: Prospects and recommendations
The encapsulation and suspension of solid-liquid PCMs using
custom-engineered shells for solar photothermal conversion and storage
is a highly promising concept that paves the way for smart, multi-
functional solar fluids. The resulting ePCM slurries and dispersions
elegantly combine the functions of solar absorbers, heat carriers, and
storage media, thus circumventing the need for absorber plates and
separate TES systems. This promotes ePCM-based direct-absorption
systems as the next-generation of solar-thermal collectors.
Relative to nano-enhanced and shape-stabilized PCMs (considered,
along with ePCMs, to be the most advanced and promising PCM-based
solutions), ePCMs offer the often-overlooked advantage of continuous
fluidity regardless of the working temperature and phase-change ac­
tivity (charging or discharging, solid or liquid). This translates into
seamless integration into active-cooling systems and solar-thermal col­
lectors that require a continuously flowing fluid. Other advantages of
ePCMs over alternatives at the forefront of the PCM scene include leak-
proof operation over numerous thermal cycles, complete prevention of
chemical interactions between the PCM and its surroundings, and
effective suppression of phase separation (incongruent melting). This is
in addition to inherently overcoming the low-thermal-conductivity issue
that long plagued PCMs by significantly increasing the available surface
area for heat transfer.
There has been a number of interesting developments in recent years
in the field of solar ePCMs, including the synthesis of broadband-
absorbing composite and multi-layered shells, the expansion of
75
Progress in Energy and Combustion Science 93 (2022) 101037
polymerization methods to nano-encapsulation, and reducing the de­
gree of supercooling in confinement by using nucleation additives. Yet,
there remains a long road ahead for solar ePCMs to become an available
and affordable industrial commodity. Throughout this work, a number
of new research directions have been identified to lift the application
limitations of ePCM systems.
As the suspensions of PCM capsules simultaneously perform the
functions of solar absorption, storage, and transport, equal attention
must be given to their optical, thermal, rheological, and structural
properties at a wide range of working temperatures, particle loadings,
and flow rates. Compared to thermal conductivity and optical proper­
ties, limited studies have been devoted to the measurement of heat ca­
pacity and rheological properties of ePCMs before, during, and after
phase transition. But perhaps more pressingly, the introduction of
ePCMs to high-temperature applications has been disadvantaged.
It was observed that the majority of studies have been limited to the
use of water as the carrying fluid, paraffin as the core material, and/or
polymers as the shell material. This has narrowly restricted the use of the
resulting ePCM slurries and dispersions to low-temperature applica­
tions. Therefore, it is important for future studies to focus on improving
the encapsulation of non-paraffin core materials that possess high phase-
change temperatures (e.g., salt hydrates and metal alloys) using inor­
ganic and solar-active shells (e.g., carbon-based and plasmonic metals),
along with their suspension in carrier fluids with high boiling points (e.
g., thermal oils) to open the room for high-temperature applications.
Relative to conventional micro-ePCMs, nano-ePCMs have shown
superior structural stability, heat transfer, cyclic reliability, and solar
absorption characteristics. Moreover, nano-ePCMs incur a much lower
penalty on viscosity (and pumping power) with no clogging or abrasion
issues in the pumping and piping system. These characteristics make
nano-ePCMs more promising for both solar and thermal applications,
which should give a strong thrust for future research efforts to be
directed on investigating nano-ePCMs rather than micro-ePCMs. For
instance, one poorly understood area is the effect of nanoconfinement on
the phase-change properties and behavior of PCMs relative to their bulk
properties. Another area that requires special attention is the develop­
ment of non-invasive stability evaluation techniques for nano-ePCMs.
From a system-level perspective, ePCM slurries and dispersions are a
natural fit for PV/T collectors in which they can simultaneously perform
the functions of optical filtration and thermal regulation, thus maxi­
mizing thermal and electrical outputs from the same solar input. This is
possible by using ePCMs to selectively absorb the non-PV-useful bands
of the solar spectrum before reaching the PV receiver while removing
excess heat from below the PV cells at a semi-constant temperature.
Therefore, a huge capacity for future research, on the material and
system levels, is available for ePCM-based PV/T collectors. Another
completely unexplored and highly interesting system-level concept is
the mixing of PCM capsules with different core and/or shell materials in
the same suspension. This is expected to lead to significant improve­
ments in the thermal (due to the initiation of multiple phase-change
processes that can span a wide temperate range) and optical (due to
the possibility of maximizing broadband/selective solar absorption over
multiple spectral bands) properties of the suspension as a whole.
In parallel with experimental campaigns, a better understanding of
the multi-scale and multi-phase nature of ePCM slurries and dispersions
is pivotal. Adopting purely continuum or discrete approaches was found
to be insufficient to completely comprehend the heat and mass transfer
phenomena in an ePCM slurry or dispersion. Multi-scale models have the
potential to overcome the limitations of continuum and discrete models
by effectively representing an ePCM system with coupled analysis on
various scales. This enables multi-scale models to describe the nonlinear
latent heat release of PCMs in agreement with experimental results.
Therefore, to capture the key physical phenomena in solar ePCMs, it is
recommended that hybrid continuum-discrete methods (which do not
rely on any property correlations) be used in conjunction with Mie’s
theory for encapsulated spheres.
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Building on the maturity of PCMs and particulate systems as [19] Zayed ME, et al. Performance augmentation of flat plate solar water collector
using phase change materials and nanocomposite phase change materials: a
commercialized products, the industrial uptake of micro/nano-ePCMs is
review. Process Saf. Environ. Prot. 2019;128:135–57. https://doi.org/10.1016/j.
closer than ever. A niche market for suspensions of micro/nano-ePCMs is psep.2019.06.002.
in synergizing the absorption, transfer, and storage of solar energy in a [20] Delgado M, Lázaro A, Mazo J, Zalba B. Review on phase change material
single process. By critically surveying the most promising advances, emulsions and microencapsulated phase change material slurries: materials, heat
transfer studies and applications. Renew. Sustain. Energy Rev. 2012;16(1):
identifying the most pressing technical gaps, and sketching a research 253–73. https://doi.org/10.1016/j.rser.2011.07.152.
roadmap to address these issues, this work is a leap forward to establish [21] Qiu Z, Ma X, Li P, Zhao X, Wright A. Micro-encapsulated phase change material
a foothold for micro/nano-ePCM slurries and dispersions in the solar- (MPCM) slurries: Characterization and building applications. Renew. Sustain.
Energy Rev. 2017;77(June 2016):246–62. https://doi.org/10.1016/j.
thermal industry. rser.2017.04.001.
[22] Abutayeh M, Alazzam A, El-Khasawneh B. Optimizing thermal energy storage
Declaration of Competing Interest operation. Sol. Energy 2015;120:318–29. https://doi.org/10.1016/j.
solener.2015.06.027.
[23] Medrano M, Gil A, Martorell I, Potau X, Cabeza LF. State of the art on high-
The authors declare that they have no known competing financial temperature thermal energy storage for power generation. Part 2-Case studies.
interests or personal relationships that could have appeared to influence Renew. Sustain. Energy Rev. 2010;14(1):56–72. https://doi.org/10.1016/j.
rser.2009.07.036.
the work reported in this paper. [24] J. D. Webb and R. W. Burrows, “Materials research for passive solar systems:
solid-state phase-change materials,” SERI Rep. TR-255-1828, vol. No. DE8500,
References 1985.
[25] Wang K, Qin Z, Tong W, Ji C. Thermal energy storage for solar energy utilization:
fundamentals and applications. Renew. Energy - Resour. Challenges Appl. 2020;
[1] Yang L, nan Huang J, Zhou F. Thermophysical properties and applications of
(September). https://doi.org/10.5772/intechopen.91804.
nano-enhanced PCMs: an update review. Energy Convers. Manag. 2020;214
[26] Ghoneim AA. Comparison of theoretical models of phase-change and sensible
(March):112876. https://doi.org/10.1016/j.enconman.2020.112876.
heat storage for air and water-based solar heating systems. Sol. Energy 1989;42
[2] Salunkhe PB, Shembekar PS. A review on effect of phase change material
(3):209–20. https://doi.org/10.1016/0038-092X(89)90013-3.
encapsulation on the thermal performance of a system. Renew. Sustain. Energy
[27] Morrison DJ, Abdel-Khalik SI. Effects of phase-change energy storage on the
Rev. 2012;16(8):5603–16. https://doi.org/10.1016/j.rser.2012.05.037.
performance of air-based and liquid-based solar heating systems. Sol. Energy
[3] Cabeza LF, Castellón C, Nogués M, Medrano M, Leppers R, Zubillaga O. Use of
1978;20(1):57–67. https://doi.org/10.1016/0038-092X(78)90141-X.
microencapsulated PCM in concrete walls for energy savings. Energy Build 2007;
[28] Mohamed SA, et al. A review on current status and challenges of inorganic phase
39(2):113–9. https://doi.org/10.1016/j.enbuild.2006.03.030.
change materials for thermal energy storage systems. Renew. Sustain. Energy
[4] Ran F, Chen Y, Cong R, Fang G. Flow and heat transfer characteristics of
Rev. 2017;70(December 2016):1072–89. https://doi.org/10.1016/j.
microencapsulated phase change slurry in thermal energy systems: a review.
rser.2016.12.012.
Renew. Sustain. Energy Rev. 2020;134(August):110101. https://doi.org/
[29] Wang F, Maidment G, Missenden J, Tozer R. A review of research concerning the
10.1016/j.rser.2020.110101.
use of PCMS in air conditioning and refrigeration engineering. Adv. Build.
[5] Iachachene F, Haddad Z, Arıcı M, Abu-Nada E, Sheremet MA. The effect of nano
Technol. 2002;2(Kulkami 1994):1273–80. https://doi.org/10.1016/b978-
encapsulated phase change materials and nanoparticles on turbulent heat
008044100-9/50158-3.
transport: a conical diffuser scenario. J. Energy Storage 2022;52(PA):104703.
[30] Kenisarin M, Mahkamov K. Passive thermal control in residential buildings using
https://doi.org/10.1016/j.est.2022.104703.
phase change materials. Renew. Sustain. Energy Rev. 2016;55:371–98. https://
[6] Ma F, Zhang P. Performance investigation of the direct absorption solar collector
doi.org/10.1016/j.rser.2015.10.128.
based on phase change slurry. Appl. Therm. Eng. 2019;162(January):114244.
[31] Kalidasan B, Pandey AK, Shahabuddin S, Samykano M,
https://doi.org/10.1016/j.applthermaleng.2019.114244.
Thirugnanasambandam M, Saidur R. Phase change materials integrated solar
[7] Sharma S, Micheli L, Chang W, Tahir AA, Reddy KS, Mallick TK. Nano-enhanced
thermal energy systems: global trends and current practices in experimental
Phase Change Material for thermal management of BICPV. Appl. Energy 2017;
approaches. J. Energy Storage 2020;27(August 2019):101118. https://doi.org/
208(September):719–33. https://doi.org/10.1016/j.apenergy.2017.09.076.
10.1016/j.est.2019.101118.
[8] Buddhi D, Sharma SD. Measurements of transmittance of solar radiation through
[32] Mahian O, Ghafarian S, Sarrafha H, Kasaeian A, Yousefi H, Yan W. Phase change
stearic acid: a latent heat storage material. Energy Convers. Manag. 1999;40(18):
materials in solar photovoltaics applied in buildings : an overview. Sol. Energy
1979–84. https://doi.org/10.1016/S0196-8904(99)00077-1.
2021;224(May):569–92. https://doi.org/10.1016/j.solener.2021.06.010.
[9] Hassan F, et al. Recent advancements in latent heat phase change materials and
[33] Lu Y, et al. Novel smart textile with phase change materials encapsulated core-
their applications for thermal energy storage and buildings: a state of the art
sheath structure fabricated by coaxial electrospinning. Chem. Eng. J. 2019;355
review. Sustain. Energy Technol. Assessments 2022;49(September 2021):101646.
(July 2018):532–9. https://doi.org/10.1016/j.cej.2018.08.189.
https://doi.org/10.1016/j.seta.2021.101646.
[34] Wang C, Hossain M, Ma L, Ma Z, Hickman JJ, Su M. Highly sensitive thermal
[10] Jacob R, Bruno F. Review on shell materials used in the encapsulation of phase
detection of thrombin using aptamer-functionalized phase change nanoparticles.
change materials for high temperature thermal energy storage. Renew. Sustain.
Biosens. Bioelectron. 2010;26(2):437–43. https://doi.org/10.1016/j.
Energy Rev. 2015;48:79–87. https://doi.org/10.1016/j.rser.2015.03.038.
bios.2010.07.097.
[11] Milián YE, Gutiérrez A, Grágeda M, Ushak S. A review on encapsulation
[35] Du K, Calautit J, Eames P, Wu Y. A state-of-the-art review of the application of
techniques for inorganic phase change materials and the influence on their
phase change materials (PCM) in Mobilized-Thermal Energy Storage (M-TES) for
thermophysical properties. Renew. Sustain. Energy Rev. 2017;73(June 2016):
recovering low-temperature industrial waste heat (IWH) for distributed heat
983–99. https://doi.org/10.1016/j.rser.2017.01.159.
supply. Renew. Energy 2021;168:1040–57. https://doi.org/10.1016/j.
[12] Singh P, Sharma RK, Ansu AK, Goyal R, Sarı A, Tyagi VV. A comprehensive
renene.2020.12.057.
review on development of eutectic organic phase change materials and their
[36] White SD, Yarrall MG, Cleland DJ, Hedley RA. Modelling the performance of a
composites for low and medium range thermal energy storage applications. Sol.
transcritical CO2 heat pump for high temperature heating. Int. J. Refrig. 2002;25
Energy Mater. Sol. Cells 2021;223(December 2020):110955. https://doi.org/
(4):479–86. https://doi.org/10.1016/S0140-7007(01)00021-4.
10.1016/j.solmat.2020.110955.
[37] Zhang X, Wang F, Fan X, Duan H, Zhu F. An investigation of a heat pump system
[13] Mourad A, Aissa A, Said Z, Younis O, Iqbal M, Alazzam A. Recent advances on the
using CO2/propane mixture as a working fluid. Int. J. Green Energy 2017;14(1):
applications of phase change materials for solar collectors, practical limitations,
105–11. https://doi.org/10.1080/15435075.2016.1253577.
and challenges: a critical review. J. Energy Storage 2022;49(January):104186.
[38] Fanney AH, Terlizzi CP. Testing of refrigerant-charged solar domestic hot water
https://doi.org/10.1016/j.est.2022.104186.
systems. Sol. Energy 1985;35(4):353–66. https://doi.org/10.1016/0038-092X
[14] Naveenkumar R, et al. Review on phase change materials for solar energy storage
(85)90143-4.
applications, 29. Berlin Heidelberg: Springer; 2022.
[39] Abhat A. Low temperature latent heat thermal energy storage: Heat storage
[15] Tyagi PK, Kumar R, Said Z. Recent advances on the role of nanomaterials for
materials. Sol. Energy 1983;30(4):313–32. https://doi.org/10.1016/0038-092X
improving the performance of photovoltaic thermal systems: Trends, challenges
(83)90186-X.
and prospective. Nano Energy 2022;93(August 2021):106834. https://doi.org/
[40] Fallahi A, Guldentops G, Tao M, Granados-Focil S, Van Dessel S. Review on solid-
10.1016/j.nanoen.2021.106834.
solid phase change materials for thermal energy storage: molecular structure and
[16] Tyagi PK, Kumar R, Said Z. Recent advances on the role of nanomaterials for
thermal properties. Appl. Therm. Eng. 2017;127:1427–41. https://doi.org/
improving the performance of photovoltaic thermal systems: Trends, challenges
10.1016/j.applthermaleng.2017.08.161.
and prospective. Nano Energy 2022;93(December 2021):106834. https://doi.
[41] Guldentops G, Van Dessel S. Building envelope systems with transparent solid-
org/10.1016/j.nanoen.2021.106834.
solid phase changing material. In: AEI 2017 Resil. Integr. Build. - Proc. Archit. Eng.
[17] Qiu L, Ouyang Y, Feng Y, Zhang X. Review on micro/nano phase change materials
Natl. Conf. 2017; 2017. p. 247–65. https://doi.org/10.1061/
for solar thermal applications. Renew. Energy 2019;140:513–38. https://doi.org/
9780784480502.021.
10.1016/j.renene.2019.03.088.
[42] Su W, Darkwa J, Kokogiannakis G. Review of solid-liquid phase change materials
[18] Ghasemi K, Tasnim S, Mahmud S. PCM, nano/microencapsulation and slurries: a
and their encapsulation technologies. Renew. Sustain. Energy Rev. 2015;48:
review of fundamentals, categories, fabrication, numerical models and
373–91. https://doi.org/10.1016/j.rser.2015.04.044.
applications. Sustain. Energy Technol. Assessments 2022;52(PB):102084. https://
doi.org/10.1016/j.seta.2022.102084.

76
S.A. Albdour et al.
[43] Jones BJ, Sun D, Krishnan S, Garimella SV. Experimental and numerical study of
melting in a cylinder. Int. J. Heat Mass Transf. 2006;49(15–16):2724–38. https://
doi.org/10.1016/j.ijheatmasstransfer.2006.01.006.
[44] H. M. Bele ́n Zalba, Jose ́ M, Mari n,́ Luisa F. Cabeza, Review on thermal energy
storage with phase change: materials, heat transfer analysis and applications, vol. 704.
2003.
[45] Pandey AK, Hossain MS, Tyagi VV, Abd Rahim N, Selvaraj JAL, Sari A. Novel
approaches and recent developments on potential applications of phase change
materials in solar energy. Renew. Sustain. Energy Rev. 2018;82(July 2017):
281–323. https://doi.org/10.1016/j.rser.2017.09.043.
[46] Kenisarin MM. High-temperature phase change materials for thermal energy
storage. Renew. Sustain. Energy Rev. 2010;14(3):955–70. https://doi.org/
10.1016/j.rser.2009.11.011.
[47] Pereira da Cunha J, Eames P. Thermal energy storage for low and medium
temperature applications using phase change materials - A review. Appl. Energy
2016;177:227–38. https://doi.org/10.1016/j.apenergy.2016.05.097.
[48] Dimaano MNR, Watanabe T. Performance investigation of the capric and lauric
acid mixture as latent heat energy storage for a cooling system. Sol. Energy 2002;
72(3):205–15. https://doi.org/10.1016/S0038-092X(01)00101-3.
[49] Sari A, Kaygusuz K. Thermal performance of a eutectic mixture of lauric and
stearic acids as PCM encapsulated in the annulus of two concentric pipes. Sol.
Energy 2002;72(6):493–504. https://doi.org/10.1016/S0038-092X(02)00026-9.
[50] Chinnasamy V, Appukuttan S. Preparation and thermal properties of lauric acid/
myristyl alcohol as a novel binary eutectic phase change material for indoor
thermal comfort. Energy Storage 2019;1(5):1–9. https://doi.org/10.1002/
est2.80.
[51] Tyagi VV, Buddhi D. PCM thermal storage in buildings: a state of art. Renew.
Sustain. Energy Rev. 2007;11(6):1146–66. https://doi.org/10.1016/j.
rser.2005.10.002.
[52] Baetens R, Jelle BP, Gustavsen A. Phase change materials for building
applications: a state-of-the-art review. Energy Build 2010;42(9):1361–8. https://
doi.org/10.1016/j.enbuild.2010.03.026.
[53] Huang WM, et al. Thermo/chemo-responsive shape memory effect in polymers: a
sketch of working mechanisms, fundamentals and optimization. J. Polym. Res.
2012;19(9). https://doi.org/10.1007/s10965-012-9952-z.
[54] Cabeza L, Mehling H. Heat and cold storage with PCM. An up to date introduction
into basics and applications - Publisher 2008. ISBN:978-3-540-68557-9.
[55] Ouchi K, Gamache P, Acworth I, Watanabe S. Measurement of isoflavones using
liquid chromatography with multi-channel coulometric electrochemical
detection. BioFactors 2004;22(1–4):353–6. https://doi.org/10.1002/
biof.5520220169.
[56] Zayed ME, et al. Recent progress in phase change materials storage containers:
geometries, design considerations and heat transfer improvement methods.
J. Energy Storage 2020;30(January):101341. https://doi.org/10.1016/j.
est.2020.101341.
[57] Dutil Y, Rousse DR, Ben Salah N, Lassue S, Zalewski L. A review on phase-change
materials: mathematical modeling and simulations. Renew. Sustain. Energy Rev.
2011;15(1):112–30. https://doi.org/10.1016/j.rser.2010.06.011.
[58] Olivares RI, Edwards W. LiNO3-NaNO3-KNO3 salt for thermal energy storage:
Thermal stability evaluation in different atmospheres. Thermochim. Acta 2013;
560:34–42. https://doi.org/10.1016/j.tca.2013.02.029.
[59] Jankowski NR, McCluskey FP. A review of phase change materials for vehicle
component thermal buffering. Appl. Energy 2014;113:1525–61. https://doi.org/
10.1016/j.apenergy.2013.08.026.
[60] Sharma A, Sharma SD, Buddhi D. Accelerated thermal cycle test of acetamide,
stearic acid and paraffin wax for solar thermal latent heat storage applications.
Energy Convers. Manag. 2002;43(14):1923–30. https://doi.org/10.1016/S0196-
8904(01)00131-5.
[61] Sharma A, Tyagi VV, Chen CR, Buddhi D. Review on thermal energy storage with
phase change materials and applications. Renew. Sustain. Energy Rev. 2009;13
(2):318–45. https://doi.org/10.1016/j.rser.2007.10.005.
[62] Veerakumar C, Sreekumar A. Phase change material based cold thermal energy
storage: materials, techniques and applications - a review. Int. J. Refrig. 2016;67
(June):271–89. https://doi.org/10.1016/j.ijrefrig.2015.12.005.
[63] Günther E, Schmid T, Mehling H, Hiebler S, Huang L. Subcooling in hexadecane
emulsions. Int. J. Refrig. 2010;33(8):1605–11. https://doi.org/10.1016/j.
ijrefrig.2010.07.022.
[64] Adachi T, Daudah D, Tanaka G. Effects of supercooling degree and specimen size
on supercooling duration of erythritol. ISIJ Int 2014;54(12):2790–5. https://doi.
org/10.2355/isijinternational.54.2790.
[65] Zahir MH, Mohamed SA, Saidur R, Al-Sulaiman FA. Supercooling of phase-change
materials and the techniques used to mitigate the phenomenon. Appl. Energy
2019;240(February):793–817. https://doi.org/10.1016/j.apenergy.2019.02.045.
[66] Dutkowski K, Kruzel M, Zajączkowski B, Białko B. The experimental investigation
of mPCM slurries density at phase change temperature. Int. J. Heat Mass Transf.
2020;159. https://doi.org/10.1016/j.ijheatmasstransfer.2020.120083.
[67] Nada SA, El-Nagar DH, Hussein HMS. Improving the thermal regulation and
efficiency enhancement of PCM-Integrated PV modules using nano particles.
Energy Convers. Manag. 2018;166(May):735–43. https://doi.org/10.1016/j.
enconman.2018.04.035.
[68] Ansyah PR, Waluyo J, Suhanan MNajib, Anggara F. Thermal behavior of melting
paraffin wax process in cylindrical capsule by experimental study. AIP Conf. Proc.
2018;2001(August). https://doi.org/10.1063/1.5049968.
[69] Tan P, Lindberg P, Eichler K, Löveryd P, Johansson P, Kalagasidis AS. Effect of
phase separation and supercooling on the storage capacity in a commercial latent
heat thermal energy storage: experimental cycling of a salt hydrate PCM.
77
Progress in Energy and Combustion Science 93 (2022) 101037
J. Energy Storage 2020;29(April):101266. https://doi.org/10.1016/j.
est.2020.101266.
[70] Huo X, et al. Chitosan composite microencapsulated comb-like polymeric phase
change material via coacervation microencapsulation. Carbohydr. Polym. 2018;
200(August):602–10. https://doi.org/10.1016/j.carbpol.2018.08.003.
[71] Sheng N, Nomura T, Zhu C, Habazaki H, Akiyama T. Cotton-derived carbon
sponge as support for form-stabilized composite phase change materials with
enhanced thermal conductivity. Sol. Energy Mater. Sol. Cells 2019;192(October
2018):8–15. https://doi.org/10.1016/j.solmat.2018.12.018.
[72] Zhao Q, et al. Graphene oxide Pickering phase change material emulsions with
high thermal conductivity and photo-thermal performance for thermal energy
management. Colloids Surfaces A Physicochem. Eng. Asp. 2019;575(January):
42–9. https://doi.org/10.1016/j.colsurfa.2019.05.007.
[73] Hassabo AG, Mohamed AL. Enhancement the thermo-regulating property of
cellulosic fabric using encapsulated paraffins in modified pectin. Carbohydr.
Polym. 2017;165:421–8. https://doi.org/10.1016/j.carbpol.2017.02.074.
[74] Yazdani MR, Etula J, Zimmerman JB, Seppälä A. Ionic cross-linked polyvinyl
alcohol tunes vitrification and cold-crystallization of sugar alcohol for long-term
thermal energy storage. Green Chem 2020;22(16):5447–62. https://doi.org/
10.1039/d0gc01427c.
[75] Adesina A. Use of phase change materials in concrete: current challenges. Renew.
Energy Environ. Sustain. 2019;4(9). https://doi.org/10.1051/rees/2019006.
[76] Mahdi JM, Lohrasbi S, Nsofor EC. Hybrid heat transfer enhancement for latent-
heat thermal energy storage systems: a review. Int. J. Heat Mass Transf. 2019;
137:630–49. https://doi.org/10.1016/j.ijheatmasstransfer.2019.03.111.
[77] Xu M, Akhtar S, Zueter AF, Alzoubi MA, Sushama L, Sasmito AP. Asymptotic
analysis of a two-phase Stefan problem in annulus: application to outward
solidification in phase change materials. Appl. Math. Comput. 2021;408:126343.
https://doi.org/10.1016/j.amc.2021.126343.
[78] McLaggan MS, Hadden RM, Gillie M. Flammability assessment of phase change
material wall lining and insulation materials with different weight fractions.
Energy Build 2017;153:439–47. https://doi.org/10.1016/j.enbuild.2017.08.012.
[79] da Cunha SRL, de Aguiar JLB. Phase change materials and energy efficiency of
buildings: a review of knowledge. J. Energy Storage November 2019;27:2020.
https://doi.org/10.1016/j.est.2019.101083.
[80] Agyenim F, Hewitt N, Eames P, Smyth M. A review of materials, heat transfer and
phase change problem formulation for latent heat thermal energy storage systems
(LHTESS). Renew. Sustain. Energy Rev. 2010;14(2):615–28. https://doi.org/
10.1016/j.rser.2009.10.015.
[81] Esen M, Durmuş A, Durmuş A. Geometric design of solar-aided latent heat store
depending on various parameters and phase change materials. Sol. Energy 1998;
62(1):19–28. https://doi.org/10.1016/S0038-092X(97)00104-7.
[82] Agyenim F, Eames P, Smyth M. Heat transfer enhancement in medium
temperature thermal energy storage system using a multitube heat transfer array.
Renew. Energy 2010;35(1):198–207. https://doi.org/10.1016/j.
renene.2009.03.010.
[83] Seddegh S, Wang X, Joybari MM, Haghighat F. Investigation of the effect of
geometric and operating parameters on thermal behavior of vertical shell-and-
tube latent heat energy storage systems. Energy 2017;137:69–82. https://doi.
org/10.1016/j.energy.2017.07.014.
[84] Zhao J, Zhai J, Lu Y, Liu N. Theory and experiment of contact melting of phase
change materials in a rectangular cavity at different tilt angles. Int. J. Heat Mass
Transf. 2018;120:241–9. https://doi.org/10.1016/j.
ijheatmasstransfer.2017.12.006.
[85] Nazzi Ehms JH, De Césaro Oliveski R, Oliveira Rocha LA, Biserni C. Theoretical
and numerical analysis on phase change materials (PCM): a case study of the
solidification process of erythritol in spheres. Int. J. Heat Mass Transf. 2018;119:
523–32. https://doi.org/10.1016/j.ijheatmasstransfer.2017.11.124.
[86] Dhaidan NS, Khodadadi JM. Melting and convection of phase change materials in
different shape containers: a review. Renew. Sustain. Energy Rev. 2015;43:
449–77. https://doi.org/10.1016/j.rser.2014.11.017.
[87] Hajighafoori Boukani N, Dadvand A, Chamkha AJ. Melting of a Nano-enhanced
Phase Change Material (NePCM) in partially-filled horizontal elliptical capsules
with different aspect ratios. Int. J. Mech. Sci. 2018;149(June):164–77. https://
doi.org/10.1016/j.ijmecsci.2018.09.056.
[88] Tan FL. Constrained and unconstrained melting inside a sphere. Int. Commun.
Heat Mass Transf. 2008;35(4):466–75. https://doi.org/10.1016/j.
icheatmasstransfer.2007.09.008.
[89] Sattari H, Mohebbi A, Afsahi MM, Azimi Yancheshme A. CFD simulation of
melting process of phase change materials (PCMs) in a spherical capsule. Int. J.
Refrig. 2017;73:209–18. https://doi.org/10.1016/j.ijrefrig.2016.09.007.
[90] Sparrow EM, Geiger GT. Melting in a horizontal tube with the solid either
constrained or free to fall under gravity. Int. J. Heat Mass Transf. 1986;29(7):
1007–19. https://doi.org/10.1016/0017-9310(86)90200-0.
[91] Zhou J, Chen Z, Liu D, Li J. Experimental study on melting in a rectangular
enclosure heated below with discrete heat sources. J. Therm. Sci. 2001;10(3):
254–9. https://doi.org/10.1007/s11630-001-0028-3.
[92] Wang Y, Amiri A, Vafai K. An experimental investigation of the melting process in
a rectangular enclosure. Int. J. Heat Mass Transf. 1999;42(19):3659–72. https://
doi.org/10.1016/S0017-9310(99)00024-1.
[93] Fukai J, Hamada Y, Morozumi Y, Miyatake O. Effect of carbon-fiber brushes on
conductive heat transfer in phase change materials. Int. J. Heat Mass Transf.
2002;45(24):4781–92. https://doi.org/10.1016/S0017-9310(02)00179-5.
[94] El-Dessouky H, Al-Juwayhel F. Effectiveness of a thermal energy storage system
using phase-change materials. Energy Convers. Manag. 1997;38(6):601–17.
https://doi.org/10.1016/S0196-8904(96)00072-6.
S.A. Albdour et al.
[95] Hamada Y, Ohtsu W, Fukai J. Thermal response in thermal energy storage
material around heat transfer tubes: Effect of additives on heat transfer rates. Sol.
Energy 2003;75(4):317–28. https://doi.org/10.1016/j.solener.2003.07.028.
[96] Hirata T, Nishida K. An analysis of heat transfer using equivalent thermal
conductivity of liquid phase during melting inside an isothermally heated
horizontal cylinder. Int. J. Heat Mass Transf. 1989;32(9):1663–70. https://doi.
org/10.1016/0017-9310(89)90049-5.
[97] Rathod Manish K, Jyotirmay B. Development of Correlation for Melting Time of
Phase Change Material in Latent Heat Storage Unit. Energy Procedia 2015;75:
2125–30. https://doi.org/10.1016/j.egypro.2015.07.339.
[98] Solomon AD. Melt time and heat flux for a simple PCM body. Sol. Energy 1979;22
(3):251–7. https://doi.org/10.1016/0038-092X(79)90140-3.
[99] Liu M, Saman W, Bruno F. Review on storage materials and thermal performance
enhancement techniques for high temperature phase change thermal storage
systems. Renew. Sustain. Energy Rev. 2012;16(4):2118–32. https://doi.org/
10.1016/j.rser.2012.01.020.
[100] Kalapala L, Devanuri JK. Influence of operational and design parameters on the
performance of a PCM based heat exchanger for thermal energy storage – A
review. J. Energy Storage 2018;20(July):497–519. https://doi.org/10.1016/j.
est.2018.10.024.
[101] Agyenim F, Eames P, Smyth M. A comparison of heat transfer enhancement in a
medium temperature thermal energy storage heat exchanger using fins. Sol.
Energy 2009;83(9):1509–20. https://doi.org/10.1016/j.solener.2009.04.007.
[102] Yang X, Lu Z, Bai Q, Zhang Q, Jin L, Yan J. Thermal performance of a shell-and-
tube latent heat thermal energy storage unit: role of annular fins. Appl. Energy
2017;202:558–70. https://doi.org/10.1016/j.apenergy.2017.05.007.
[103] Wang J, Chen G, Jiang H. Theoretical study on a novel phase change process. Int.
J. Energy Res. 1999;23(4):287–94. https://doi.org/10.1002/(SICI)1099-114X
(19990325)23:4<287::AID-ER476>3.0.CO;2-K.
[104] Li YQ, He YL, Song HJ, Xu C, Wang WW. Numerical analysis and parameters
optimization of shell-and-tube heat storage unit using three phase change
materials. Renew. Energy 2013;59:92–9. https://doi.org/10.1016/j.
renene.2013.03.022.
[105] Li YQ, He YL, Wang ZF, Xu C, Wang W. Exergy analysis of two phase change
materials storage system for solar thermal power with finite-time
thermodynamics. Renew. Energy 2012;39(1):447–54. https://doi.org/10.1016/j.
renene.2011.08.026.
[106] Michels H, Pitz-Paal R. Cascaded latent heat storage for parabolic trough solar
power plants. Sol. Energy 2007;81(6):829–37. https://doi.org/10.1016/j.
solener.2006.09.008.
[107] Shao J, Darkwa J, Kokogiannakis G. Review of phase change emulsions (PCMEs)
and their applications in HVAC systems. Energy Build 2015;94:200–17. https://
doi.org/10.1016/j.enbuild.2015.03.003.
[108] T. Coradin, Nanomaterials: a Danger or a Promise? A Chemical and Biological
Perspective. 2012.
[109] Huang L, Petermann M, Doetsch C. Evaluation of paraffin/water emulsion as a
phase change slurry for cooling applications. Energy 2009;34(9):1145–55.
https://doi.org/10.1016/j.energy.2009.03.016.
[110] “Doug H. Everett basic principles of colloid science RSC paperbacks.pdf.” .
[111] Applied Surfactants. T. T. F. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA;
2005. p. 2005. Print.
[112] Pathak M. Nanoemulsions and Their Stability for Enhancing Functional Properties
of Food Ingredients. Elsevier Inc.; 2017.
[113] Jaiswal M, Dudhe R, Sharma PK. Nanoemulsion: an advanced mode of drug
delivery system. 3 Biotech 2015;5(2):123–7. https://doi.org/10.1007/s13205-
014-0214-0.
[114] Kumar A, Li S, Cheng CM, Lee D. Recent developments in phase inversion
emulsification. Ind. Eng. Chem. Res. 2015;54(34):8375–96. https://doi.org/
10.1021/acs.iecr.5b01122.
[115] Yamashita Y, Miyahara R, Sakamoto K. Emulsion and emulsification technology.
Elsevier Inc.; 2017.
[116] Xiong T, Zheng L, Shah KW. Nano-enhanced phase change materials (NePCMs): a
review of numerical simulations. Appl. Therm. Eng. 2020;178(February):115492.
https://doi.org/10.1016/j.applthermaleng.2020.115492.
[117] Zeng JL, et al. Effects of MWNTs on phase change enthalpy and thermal
conductivity of a solid-liquid organic PCM. J. Therm. Anal. Calorim. 2009;95(2):
507–12. https://doi.org/10.1007/s10973-008-9275-9.
[118] Reji Kumar R, Samykano M, Pandey AK, Kadirgama K, Tyagi VV. Phase change
materials and nano-enhanced phase change materials for thermal energy storage
in photovoltaic thermal systems: a futuristic approach and its technical
challenges. Renew. Sustain. Energy Rev. 2020;133(April):110341. https://doi.
org/10.1016/j.rser.2020.110341.
[119] Jegadheeswaran S, Sundaramahalingam A, Pohekar SD. High-conductivity
nanomaterials for enhancing thermal performance of latent heat thermal energy
storage systems. J. Therm. Anal. Calorim. 2019;138(2):1137–66. https://doi.org/
10.1007/s10973-019-08297-3.
[120] Capek I. Nanocomposite Structures and Dispersions Science and Nanotechnology
- Fundamental Principles and Colloidal Particles 2006;23(S1).
[121] Kim P, Shi L, Majumdar A, McEuen PL. Thermal transport measurements of
individual multiwalled nanotubes. Phys. Rev. Lett. 2001;87(21). https://doi.org/
10.1103/PhysRevLett.87.215502. 215502-1-215502–4.
[122] Cui Y, Liu C, Hu S, Yu X. The experimental exploration of carbon nanofiber and
carbon nanotube additives on thermal behavior of phase change materials. Sol.
Energy Mater. Sol. Cells 2011;95(4):1208–12. https://doi.org/10.1016/j.
solmat.2011.01.021.
78
Progress in Energy and Combustion Science 93 (2022) 101037
[123] Zhang M, Wang C, Luo A, Liu Z, Zhang X. Molecular dynamics simulation on
thermophysics of paraffin/EVA/graphene nanocomposites as phase change
materials. Appl. Therm. Eng. 2020;166(November 2019):114639. https://doi.
org/10.1016/j.applthermaleng.2019.114639.
[124] Leong KY, Abdul Rahman MR, Gurunathan BA. Nano-enhanced phase change
materials: a review of thermo-physical properties, applications and challenges.
J. Energy Storage 2019;21(October 2018):18–31. https://doi.org/10.1016/j.
est.2018.11.008.
[125] Mingzheng Z, Guodong X, Jian L, Lei C, Lijun Z. Analysis of factors influencing
thermal conductivity and viscosity in different kinds of surfactant solutions. Exp.
Therm. Fluid Sci. 2012;36:22–9. https://doi.org/10.1016/j.
expthermflusci.2011.07.014.
[126] Asadi A, et al. Effect of sonication characteristics on stability, thermophysical
properties, and heat transfer of nanofluids: a comprehensive review. Ultrason.
Sonochem. 2019;58(February). https://doi.org/10.1016/j.
ultsonch.2019.104701.
[127] Sauter C, Schuchmann HP. High pressure for dispersing and deagglomerating
nanoparticles in aqueous solutions. Chem. Eng. Technol. 2007;30(10):1401–5.
https://doi.org/10.1002/ceat.200700115.
[128] Silambarasan M, Manikandan S, Rajan KS. Viscosity and thermal conductivity of
dispersions of sub-micron TiO 2 particles in water prepared by stirred bead
milling and ultrasonication. Int. J. Heat Mass Transf. 2012;55(25–26):
7991–8002. https://doi.org/10.1016/j.ijheatmasstransfer.2012.08.030.
[129] Piquot J, Nithiyanantham U, Grosu Y, Faik A. Spray-graphitization as a protection
method against corrosion by molten nitrate salts and molten salts based
nanofluids for thermal energy storage applications. Sol. Energy Mater. Sol. Cells
2019;200(January):110024. https://doi.org/10.1016/j.solmat.2019.110024.
[130] Timofeeva EV, Moravek MR, Singh D. Improving the heat transfer efficiency of
synthetic oil with silica nanoparticles. J. Colloid Interface Sci. 2011;364(1):71–9.
https://doi.org/10.1016/j.jcis.2011.08.004.
[131] Sharaf OZ, Taylor RA, Abu-Nada E. On the colloidal and chemical stability of
solar nanofluids: From nanoscale interactions to recent advances. Phys. Rep.
2020;867:1–84. https://doi.org/10.1016/j.physrep.2020.04.005.
[132] Dsilva Winfred Rufuss D, Suganthi L, Iniyan S, Davies PA. Effects of nanoparticle-
enhanced phase change material (NPCM) on solar still productivity. J. Clean.
Prod. 2018;192:9–29. https://doi.org/10.1016/j.jclepro.2018.04.201.
[133] Li JF, Lu W, Zeng YB, Luo ZP. Simultaneous enhancement of latent heat and
thermal conductivity of docosane-based phase change material in the presence of
spongy graphene. Sol. Energy Mater. Sol. Cells 2014;128:48–51. https://doi.org/
10.1016/j.solmat.2014.05.018.
[134] Zeng JL, et al. Effects of copper nanowires on the properties of an organic phase
change material. Sol. Energy Mater. Sol. Cells 2012;105:174–8. https://doi.org/
10.1016/j.solmat.2012.06.013.
[135] Suresh Kumar KR, Parameshwaran R, Kalaiselvam S. Preparation and
characterization of hybrid nanocomposite embedded organic methyl ester as
phase change material. Sol. Energy Mater. Sol. Cells 2017;171(January):148–60.
https://doi.org/10.1016/j.solmat.2017.06.031.
[136] George M, Pandey AK, Abd Rahim N, Tyagi VV, Shahabuddin S, Saidur R. A novel
polyaniline (PANI)/paraffin wax nano composite phase change material: Superior
transition heat storage capacity, thermal conductivity and thermal reliability. Sol.
Energy 2020;204(April):448–58. https://doi.org/10.1016/j.solener.2020.04.087.
[137] Şahan N, Fois M, Paksoy H. Improving thermal conductivity phase change
materials - A study of paraffin nanomagnetite composites. Sol. Energy Mater. Sol.
Cells 2015;137:61–7. https://doi.org/10.1016/j.solmat.2015.01.027.
[138] Chandrasekaran P, Cheralathan M, Kumaresan V, Velraj R. 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 2014;72:636–42. https://doi.org/10.1016/j.
energy.2014.05.089.
[139] V. K P Suresh S, Praveen B, Venugopal A, Nair SC. Pentaerythritol with alumina
nano additives for thermal energy storage applications. J. Energy Storage 2017;
13:359–77. https://doi.org/10.1016/j.est.2017.08.002.
[140] Parameshwaran R, Jayavel R, Kalaiselvam S. Study on thermal properties of
organic ester phase-change material embedded with silver nanoparticles.
J. Therm. Anal. Calorim. 2013;114(2):845–58. https://doi.org/10.1007/s10973-
013-3064-9.
[141] Elgafy A, Lafdi K. Effect of carbon nanofiber additives on thermal behavior of
phase change materials. Carbon N. Y. 2005;43(15):3067–74. https://doi.org/
10.1016/j.carbon.2005.06.042.
[142] Fang G, Tang F, Cao L. Preparation, thermal properties and applications of shape-
stabilized thermal energy storage materials. Renew. Sustain. Energy Rev. 2014;
40:237–59. https://doi.org/10.1016/j.rser.2014.07.179.
[143] Feng D, et al. Review on nanoporous composite phase change materials:
Fabrication, characterization, enhancement and molecular simulation. Renew.
Sustain. Energy Rev. 2019;109(April):578–605. https://doi.org/10.1016/j.
rser.2019.04.041.
[144] Zhang S, et al. A review of phase change heat transfer in shape-stabilized phase
change materials (ss-PCMs) based on porous supports for thermal energy storage.
Renew. Sustain. Energy Rev. 2021;135(January 2020):110127. https://doi.org/
10.1016/j.rser.2020.110127.
[145] Huang X, et al. Shape-stabilized phase change materials based on porous supports
for thermal energy storage applications. Chem. Eng. J. 2019;356(June 2018):
641–61. https://doi.org/10.1016/j.cej.2018.09.013.
[146] Li WQ, Qu ZG, Zhang BL, Zhao K, Tao WQ. Thermal behavior of porous stainless-
steel fiber felt saturated with phase change material. Energy 2013;55:846–52.
https://doi.org/10.1016/j.energy.2013.02.064.
S.A. Albdour et al.
[147] Xiao X, Zhang P, Li M. Effective thermal conductivity of open-cell metal foams
impregnated with pure paraffin for latent heat storage. Int. J. Therm. Sci. 2014;81
(1):94–105. https://doi.org/10.1016/j.ijthermalsci.2014.03.006.
[148] Fleming E, Wen S, Shi L, Da Silva AK. Experimental and theoretical analysis of an
aluminum foam enhanced phase change thermal storage unit. Int. J. Heat Mass
Transf. 2015;82:273–81. https://doi.org/10.1016/j.
ijheatmasstransfer.2014.11.022.
[149] Diani A, Campanale M. Transient melting of paraffin waxes embedded in
aluminum foams: Experimental results and modeling. Int. J. Therm. Sci. 2019;144
(June):119–28. https://doi.org/10.1016/j.ijthermalsci.2019.06.004.
[150] Yang X, Feng S, Zhang Q, Chai Y, Jin L, Lu TJ. The role of porous metal foam on
the unidirectional solidification of saturating fluid for cold storage. Appl. Energy
2017;194:508–21. https://doi.org/10.1016/j.apenergy.2016.09.050.
[151] Xiao X, Zhang P, Li M. Preparation and thermal characterization of paraffin/metal
foam composite phase change material. Appl. Energy 2013;112:1357–66. https://
doi.org/10.1016/j.apenergy.2013.04.050.
[152] Arshad A, Jabbal M, Yan Y, Darkwa J. The micro-/nano-PCMs for thermal energy
storage systems: a state of art review. Int. J. Energy Res. 2019;43(11):5572–620.
https://doi.org/10.1002/er.4550.
[153] S. K. Ghosh, Functional Coatings: By Polymer Microencapsulation. 2006.
[154] Cárdenas-Ramírez C, Jaramillo F, Gómez M. Systematic review of encapsulation
and shape-stabilization of phase change materials. J. Energy Storage 2020;30(52):
101495. https://doi.org/10.1016/j.est.2020.101495.
[155] Lee J, Jo B. Surfactant-free microencapsulation of sodium nitrate for high
temperature thermal energy storage. Mater. Lett. 2020;268:127576. https://doi.
org/10.1016/j.matlet.2020.127576.
[156] Jamekhorshid A, Sadrameli SM, Farid M. A review of microencapsulation
methods of phase change materials (PCMs) as a thermal energy storage (TES)
medium. Renew. Sustain. Energy Rev. 2014;31:531–42. https://doi.org/10.1016/
j.rser.2013.12.033.
[157] Jurkowska M, Szczygieł I. Review on properties of microencapsulated phase
change materials slurries (mPCMS. Appl. Therm. Eng. 2016;98:365–73. https://
doi.org/10.1016/j.applthermaleng.2015.12.051.
[158] Hawlader MNA, Uddin MS, Khin MM. Microencapsulated PCM thermal-energy
storage system. Appl. Energy 2003;74(1–2):195–202. https://doi.org/10.1016/
S0306-2619(02)00146-0.
[159] Wei J, Li Z, Liu L, Liu X. Preparation and characterization of novel polyamide
paraffin MEPCM by interfacial polymerization technique. J. Appl. Polym. Sci.
2013;127(6):4588–93. https://doi.org/10.1002/app.37681.
[160] Jin Z, Wang Y, Liu J, Yang Z. Synthesis and properties of paraffin capsules as
phase change materials. Polymer (Guildf) 2008;49(12):2903–10. https://doi.org/
10.1016/j.polymer.2008.04.030.
[161] Zhang H, Wang X, Wu D. Silica encapsulation of n-octadecane via sol-gel process:
a novel microencapsulated phase-change material with enhanced thermal
conductivity and performance. J. Colloid Interface Sci. 2010;343(1):246–55.
https://doi.org/10.1016/j.jcis.2009.11.036.
[162] Fang G, Chen Z, Li H. Synthesis and properties of microencapsulated paraffin
composites with SiO2 shell as thermal energy storage materials. Chem. Eng. J.
2010;163(1–2):154–9. https://doi.org/10.1016/j.cej.2010.07.054.
[163] Zhang H, Wang X. Synthesis and properties of microencapsulated n-octadecane
with polyurea shells containing different soft segments for heat energy storage
and thermal regulation. Sol. Energy Mater. Sol. Cells 2009;93(8):1366–76.
https://doi.org/10.1016/j.solmat.2009.02.021.
[164] Luo J, Zou D, Wang Y, Wang S, Huang L. Battery thermal management systems
(BTMs) based on phase change material (PCM): a comprehensive review. Chem.
Eng. J. 2022;430(P1):132741. https://doi.org/10.1016/j.cej.2021.132741.
[165] Kumar S, Das MK, Rath P. Application of TCE-PCM based heat sinks for cooling of
electronic components : a review, 59. Elsevier; 2016.
[166] Pakrouh R, Hosseini MJ, Ranjbar AA. A parametric investigation of a PCM-based
pin fin heat sink. Mech. Sci. 2015;6(1):65–73. https://doi.org/10.5194/ms-6-65-
2015.
[167] Nayak KC, Saha SK, Srinivasan K, Dutta P. A numerical model for heat sinks with
phase change materials and thermal conductivity enhancers. Int. J. Heat Mass
Transf. 2006;49(11):1833–44. https://doi.org/10.1016/j.
ijheatmasstransfer.2005.10.039.
[168] Tang Z, Qi C, Tian Z, Chen L. Thermal management of electronic components
based on new wave bio-inspired structures and nanofluids. Int. Commun. Heat
Mass Transf. 2022;131:105840. https://doi.org/10.1016/j.
icheatmasstransfer.2021.105840.
[169] Weinstein RD, Kopec TC, Fleischer AS, D’Addio E, Bessel CA. The Experimental
Exploration of Embedding Phase Change Materials With Graphite Nanofibers for
the Thermal Management of Electronics. J. Heat Transfer Mar. 2008;130(4).
https://doi.org/10.1115/1.2818764.
[170] Fan L-W, et al. Transient performance of a PCM-based heat sink with high aspect-
ratio carbon nanofillers. Appl. Therm. Eng. 2015;75:532–40. https://doi.org/
10.1016/j.applthermaleng.2014.10.050.
[171] Kumar PManoj, et al. Experimental analysis of a heat sink for electronic chipset
cooling using a nano improved PCM (NIPCM),”. Mater. Today Proc 2022;56:
1527–31. https://doi.org/10.1016/j.matpr.2022.01.178.
[172] R. J. Warzoha and R. D. Weinstein, “Quantification of the Impact of Embedded
Graphite Nanofibers on the Transient Thermal Response of Paraffin Phase Change
Material Exposed to High Heat Fluxes,” vol. 134, no. JULY, pp. 1–10, 2012, doi:
10.1115/1.4006008.
[173] Nazari M, Karami M, Ashouri M. Comparing the thermal performance of water,
Ethylene Glycol, Alumina and CNT nanofluids in CPU cooling: Experimental
79
Progress in Energy and Combustion Science 93 (2022) 101037
study. Exp. Therm. Fluid Sci. 2014;57(September):371–7. https://doi.org/
10.1016/j.expthermflusci.2014.06.003.
[174] Cao Y, et al. Designing a system for battery thermal management: Cooling LIBs by
nano-encapsulated phase change material,” Case Stud. Therm. Eng. 2022;33:
101943. https://doi.org/10.1016/j.csite.2022.101943.
[175] Choi J, Jeon J, Kim Y. Performance characteristics of a MPCM slurry cooled unit
designed for telecommunication equipment. J. Mech. Sci. Technol. 2008;22(3):
575–82. https://doi.org/10.1007/s12206-007-1212-5.
[176] Sharma CS, et al. Energy efficient hotspot-targeted embedded liquid cooling of
electronics. Appl. Energy 2015;138:414–22. https://doi.org/10.1016/j.
apenergy.2014.10.068.
[177] Ye J, Mo S, Jia L, Chen Y. Experimental performance of a LED thermal
management system with suspended microencapsulated phase change material.
Appl. Therm. Eng. 2022;207:118155. https://doi.org/10.1016/j.
applthermaleng.2022.118155.
[178] Yousef MS, Sharaf M, Huzayyin ASS. Energy, exergy, economic, and
enviroeconomic assessment of a photovoltaic module incorporated with a
paraffin-metal foam composite: an experimental study. Energy 2022;238:121807.
https://doi.org/10.1016/j.energy.2021.121807.
[179] Aramesh M, Shabani B. Metal foams application to enhance the thermal
performance of phase change materials: a review of experimental studies to
understand the mechanisms. J. Energy Storage 2022;50:104650. https://doi.org/
10.1016/j.est.2022.104650.
[180] NematpourKeshteli A, Iasiello M, Langella G, Bianco N. Enhancing PCMs thermal
conductivity: a comparison among porous metal foams, nanoparticles and finned
surfaces in triplex tube heat exchangers. Appl. Therm. Eng. 2022;212:118623.
https://doi.org/10.1016/j.applthermaleng.2022.118623.
[181] Al-Jethelah M, Ebadi S, Venkateshwar K, Tasnim SH, Mahmud S, Dutta A.
Charging nanoparticle enhanced bio-based PCM in open cell metallic foams: an
experimental investigation. Appl. Therm. Eng. 2019;148:1029–42. https://doi.
org/10.1016/j.applthermaleng.2018.11.121.
[182] Hu X, Zhu F, Gong X. Experimental and numerical study on the thermal behavior
of phase change material infiltrated in low porosity metal foam. J. Energy Storage
2019;26(October):101005. https://doi.org/10.1016/j.est.2019.101005.
[183] Li WQ, Qu ZG, He YL, Tao YB. Experimental study of a passive thermal
management system for high-powered lithium ion batteries using porous metal
foam saturated with phase change materials. J. Power Sources 2014;255:9–15.
https://doi.org/10.1016/j.jpowsour.2014.01.006.
[184] K. Lafdi, O. Mesalhy, and S. Shaikh, “Experimental study on the influence of foam
porosity and pore size on the melting of phase change materials,” vol. 083549,
2007, doi: 10.1063/1.2802183.
[185] Liu Y, Duan J, He X, Wang Y. Experimental investigation on the heat transfer
enhancement in a novel latent heat thermal storage equipment. Appl. Therm. Eng.
2018;142:361–70. https://doi.org/10.1016/j.applthermaleng.2018.07.009.
[186] Li WQ, et al. Microencapsulated phase change material (MEPCM) saturated in
metal foam as an efficient hybrid PCM for passive thermal management: a
numerical and experimental study. Appl. Therm. Eng. 2019;146:413–21. https://
doi.org/10.1016/j.applthermaleng.2018.10.006.
[187] A. Clerici, “World Energy Resources 2013 Survey,” 2013.
[188] Tian Y, Zhao CY. A review of solar collectors and thermal energy storage in solar
thermal applications. Appl. Energy 2013;104:538–53. https://doi.org/10.1016/j.
apenergy.2012.11.051.
[189] Pal RK, Kumar KR. Investigations of Thermo-Hydrodynamics, Structural Stability,
and Thermal Energy Storage for Direct Steam Generation in Parabolic Trough
Solar Collector: a Comprehensive Review. J. Clean. Prod. 2021;311(May):
127550. https://doi.org/10.1016/j.jclepro.2021.127550.
[190] Bhalla V, Tyagi H. Parameters influencing the performance of nanoparticles-laden
fluid-based solar thermal collectors: a review on optical properties. Renew.
Sustain. Energy Rev. 2018;84(March):12–42. https://doi.org/10.1016/j.
rser.2017.12.007.
[191] Serale G, Goia F, Perino M. Numerical model and simulation of a solar thermal
collector with slurry Phase Change Material (PCM) as the heat transfer fluid. Sol.
Energy 2016;134:429–44. https://doi.org/10.1016/j.solener.2016.04.030.
[192] Deceased JAD, Beckman WA. Solar engineering of thermal processes 1982;3(3).
[193] Evangelisti L, De Lieto Vollaro R, Asdrubali F. Latest advances on solar thermal
collectors: a comprehensive review. Renew. Sustain. Energy Rev. 2019;114
(August):109318. https://doi.org/10.1016/j.rser.2019.109318.
[194] Tyagi VV, Kaushik SC, Tyagi SK. Advancement in solar photovoltaic/thermal
(PV/T) hybrid collector technology. Renew. Sustain. Energy Rev. 2012;16(3):
1383–98. https://doi.org/10.1016/j.rser.2011.12.013.
[195] Akbarzadeh S, Valipour MS. Heat transfer enhancement in parabolic trough
collectors: a comprehensive review. Renew. Sustain. Energy Rev. 2018;92
(February):198–218. https://doi.org/10.1016/j.rser.2018.04.093.
[196] Fan F, Qi C, Tang J, Liu Q, Wang X, Yan Y. A novel thermal efficiency analysis on
the thermo-hydraulic performance of nanofluids in an improved heat exchange
system under adjustable magnetic field. Appl. Therm. Eng. 2020;179(December
2019):115688. https://doi.org/10.1016/j.applthermaleng.2020.115688.
[197] Vengadesan E, Senthil R. A review on recent developments in thermal
performance enhancement methods of flat plate solar air collector. Renew.
Sustain. Energy Rev. 2020;134(August):110315. https://doi.org/10.1016/j.
rser.2020.110315.
[198] Xu B, Li P, Chan C. Application of phase change materials for thermal energy
storage in concentrated solar thermal power plants: a review to recent
developments. Appl. Energy 2015;160:286–307. https://doi.org/10.1016/j.
apenergy.2015.09.016.
S.A. Albdour et al.
[199] M. A. Al-hanaei, Sara, Sara Al-Shomali and Mechanic, “PERFORMANCE MODEL
OF SHAMS I SOLAR POWER PLANT Sara,” no. July 2014, pp. 1–8, 2020.
[200] Abutayeh M, Jeong K. Retrofitting solar power plants with thermal energy
storage. Int. J. Renew. Energy Technol. 2020;11(2):165. https://doi.org/
10.1504/ijret.2020.108308.
[201] He YL, et al. Perspective of concentrating solar power. Energy 2020;198:117373.
https://doi.org/10.1016/j.energy.2020.117373.
[202] Mehos M, Jorgenson J, Denholm P, Turchi C. An Assessment of the Net Value of
CSP Systems Integrated with Thermal Energy Storage. Energy Procedia 2015;69:
2060–71. https://doi.org/10.1016/j.egypro.2015.03.219.
[203] Nisha S, Pal RK, Kumar KR. Direct steam generation in parabolic trough solar
collector: analytical modelling for prediction of flow pattern. AIP Conf. Proc.
2019;2091(April). https://doi.org/10.1063/1.5096497.
[204] Sandá A, Moya SL, Valenzuela L. Modelling and simulation tools for direct steam
generation in parabolic-trough solar collectors: a review. Renew. Sustain. Energy
Rev. 2019;113(June):109226. https://doi.org/10.1016/j.rser.2019.06.033.
[205] Addad Y, Abutayeh M, Abu-Nada E. Effects of Nanofluids on the Performance of a
PCM-Based Thermal Energy Storage System. J. Energy Eng. 2017;143(4):
04017006. https://doi.org/10.1061/(asce)ey.1943-7897.0000433.
[206] Wong KV, De Leon O. Applications of nanofluids: Current and future. Adv. Mech.
Eng. 2010;2010(January 2010). https://doi.org/10.1155/2010/519659.
[207] Said Z, Hachicha AA, Aberoumand S, Yousef BAA, Sayed ET, Bellos E. Recent
advances on nanofluids for low to medium temperature solar collectors: energy,
exergy, economic analysis and environmental impact. Prog. Energy Combust. Sci.
2021;84. https://doi.org/10.1016/j.pecs.2020.100898.
[208] Baïri A. Natural convection between concentric and inclined hemispherical
cavities filled with Cu-water nanofluid. J. Mol. Liq. 2018;249:1263–70. https://
doi.org/10.1016/j.molliq.2017.11.079.
[209] Vijayakumaar SC, Shankar RLakshmi, Babu K. Effect of CNT-H2O nanofluid on
the performance of solar flat plate collector-an experimental investigation. In:
Proc. Int. Conf. "Advanced Nanomater. Emerg. Eng. Technol. ICANMEET 2013;
2013. p. 197–9. https://doi.org/10.1109/ICANMEET.2013.6609275.
[210] Anin Vincely D, Natarajan E. Experimental investigation of the solar FPC
performance using graphene oxide nanofluid under forced circulation. Energy
Convers. Manag. 2016;117:1–11. https://doi.org/10.1016/j.
enconman.2016.03.015.
[211] Iranmanesh S, Ong HC, Ang BC, Sadeghinezhad E, Esmaeilzadeh A, Mehrali M.
Thermal performance enhancement of an evacuated tube solar collector using
graphene nanoplatelets nanofluid. J. Clean. Prod. 2017;162:121–9. https://doi.
org/10.1016/j.jclepro.2017.05.175.
[212] Fayaz H, Nasrin R, Rahim NA, Hasanuzzaman M. Energy and exergy analysis of
the PVT system: Effect of nanofluid flow rate. Sol. Energy 2018;169(May):
217–30. https://doi.org/10.1016/j.solener.2018.05.004.
[213] Keblinski P, Prasher R, Eapen J. Thermal conductance of nanofluids: Is the
controversy over? J. Nanoparticle Res. 2008;10(7):1089–97. https://doi.org/
10.1007/s11051-007-9352-1.
[214] Gao JW, Zheng RT, Ohtani H, Zhu DS, Chen G. Experimental investigation of heat
conduction mechanisms in nanofluids. Clue on clustering. Nano Lett 2009;9(12):
4128–32. https://doi.org/10.1021/nl902358m.
[215] Alawi OA, et al. Nanofluids for flat plate solar collectors: Fundamentals and
applications. J. Clean. Prod. 2021;291. https://doi.org/10.1016/j.
jclepro.2020.125725.
[216] Abutayeh M, Addad Y, Abu-Nada E, Alazzam A. Doping solar field heat transfer
fluid with nanoparticles. J. Sol. Energy Eng. Trans. ASME 2019;141(1). https://
doi.org/10.1115/1.4041157.
[217] Rathod APS, Mittal P, Kumar B. Analysis of factors affecting the solar radiation
received by any region. In: 2016 Int. Conf. Emerg. Trends Commun. Technol.
ETCT 2016; 2017. p. 1–4. https://doi.org/10.1109/ETCT.2016.7882980.
[218] Abutayeh M, Alazzam A. Adapting Steady-State Solar Power Models to Include
Transients. J. Sol. Energy Eng. Trans. ASME 2017;139(2):1–7. https://doi.org/
10.1115/1.4034928.
[219] Kumar PManoj, et al. Investigating a single slope solar still with a nano-phase
change material. Mater. Today Proc. 2021;45(xxxx):7922–5. https://doi.org/
10.1016/j.matpr.2020.12.804.
[220] Kabeel AE, Sathyamurthy R, Manokar AM, Sharshir SW, Essa FA, Elshiekh AH.
Experimental study on tubular solar still using Graphene Oxide Nano particles in
Phase Change Material (NPCM’s) for fresh water production. J. Energy Storage
2020;28(December 2019):101204. https://doi.org/10.1016/j.est.2020.101204.
[221] Skoplaki E, Palyvos JA. On the temperature dependence of photovoltaic module
electrical performance: a review of efficiency/power correlations. Sol. Energy
2009;83(5):614–24. https://doi.org/10.1016/j.solener.2008.10.008.
[222] Zhang X, Zhao X, Smith S, Xu J, Yu X. Review of R&D progress and practical
application of the solar photovoltaic/thermal (PV/T) technologies. Renew.
Sustain. Energy Rev. 2012;16(1):599–617. https://doi.org/10.1016/j.
rser.2011.08.026.
[223] Ho CJ, Chou WL, Lai CM. Thermal and electrical performance of a water-surface
floating PV integrated with a water-saturated MEPCM layer. Energy Convers.
Manag. 2015;89:862–72. https://doi.org/10.1016/j.enconman.2014.10.039.
[224] Maatallah T, Zachariah R, Al-Amri FG. Exergo-economic analysis of a serpentine
flow type water based photovoltaic thermal system with phase change material
(PVT-PCM/water. Sol. Energy 2019;193(September):195–204. https://doi.org/
10.1016/j.solener.2019.09.063.
[225] Qiu Z, Ma X, Zhao X, Li P, Ali S. Experimental investigation of the energy
performance of a novel Micro-encapsulated Phase Change Material (MPCM)
slurry based PV/T system. Appl. Energy 2016;165:260–71. https://doi.org/
10.1016/j.apenergy.2015.11.053.
80
Progress in Energy and Combustion Science 93 (2022) 101037
[226] Hossain MS, Pandey AK, Selvaraj J, Rahim NA, Islam MM, Tyagi VV. Two side
serpentine flow based photovoltaic-thermal-phase change materials (PVT-PCM)
system: Energy, exergy and economic analysis. Renew. Energy 2019;136:
1320–36. https://doi.org/10.1016/j.renene.2018.10.097.
[227] Javadi FS, Metselaar HSC, Ganesan P. Performance improvement of solar thermal
systems integrated with phase change materials (PCM), a review. Sol. Energy
2020;206(May):330–52. https://doi.org/10.1016/j.solener.2020.05.106.
[228] Crespo A, Barreneche C, Ibarra M, Platzer W. Latent thermal energy storage for
solar process heat applications at medium-high temperatures – A review. Sol.
Energy 2019;192(July 2018):3–34. https://doi.org/10.1016/j.
solener.2018.06.101.
[229] Laing DLD, Bauer T, Steinmann W-D. Advanced high temperature latent heat
storage system –design and test results. In: The 11th International Conference on
Thermal Energy Storage; 2009. p. 1–8.
[230] Galione PA, Pérez-Segarra CD, Rodríguez I, Oliva A, Rigola J. Multi-layered solid-
PCM thermocline thermal storage concept for CSP plants. Numerical analysis and
perspectives. Appl. Energy 2015;142:337–51. https://doi.org/10.1016/j.
apenergy.2014.12.084.
[231] Prieto C, Cabeza LF. Thermal energy storage (TES) with phase change materials
(PCM) in solar power plants (CSP). Concept and plant performance. Appl. Energy
2019;254(July):113646. https://doi.org/10.1016/j.apenergy.2019.113646.
[232] Agency IE. Modernising building energy codes. ASHRAE J 2013;55(August).
[233] M. van der Hoeven, Transition to Sustainable Buildings. 2013.
[234] Tyagi VV, et al. Phase change material based advance solar thermal energy
storage systems for building heating and cooling applications : a prospective
research approach. Sustain. Energy Technol. Assessments 2021;47(March):
101318. https://doi.org/10.1016/j.seta.2021.101318.
[235] Memon SA. Phase change materials integrated in building walls: a state of the art
review. Renew. Sustain. Energy Rev. 2014;31:870–906. https://doi.org/10.1016/
j.rser.2013.12.042.
[236] Wang Q, Wu R, Wu Y, Zhao CY. Parametric analysis of using PCM walls for
heating loads reduction. Energy Build 2018;172:328–36. https://doi.org/
10.1016/j.enbuild.2018.05.012.
[237] Zhang Y, et al. Thermal Performance of New Hybrid Solar Energy-phase Change
Storage-floor Radiant Heating System. Procedia Eng 2016;146:89–99. https://
doi.org/10.1016/j.proeng.2016.06.357.
[238] Barzin R, Chen JJJ, Young BR, Farid MM. Application of PCM underfloor heating
in combination with PCM wallboards for space heating using price based control
system. Appl. Energy 2015;148:39–48. https://doi.org/10.1016/j.
apenergy.2015.03.027.
[239] Griffiths PW, Eames PC. Performance of chilled ceiling panels using phase change
material slurries as the heat transport medium. Appl. Therm. Eng. 2007;27(10):
1756–60. https://doi.org/10.1016/j.applthermaleng.2006.07.009.
[240] Liu C, Wu Y, Zhu Y, Li D, Ma L. Experimental investigation of optical and thermal
performance of a PCM-glazed unit for building applications. Energy Build 2018;
158:794–800. https://doi.org/10.1016/j.enbuild.2017.10.069.
[241] De Falco M, Capocelli M, Giannattasio A. Performance analysis of an innovative
PCM-based device for cold storage in the civil air conditioning. Energy Build
2016;122:1–10. https://doi.org/10.1016/j.enbuild.2016.04.016.
[242] Kamali S. Review of free cooling system using phase change material for building.
Energy Build 2014;80:131–6. https://doi.org/10.1016/j.enbuild.2014.05.021.
[243] De Gracia A, Cabeza LF. Phase change materials and thermal energy storage for
buildings. Energy Build 2015;103:414–9. https://doi.org/10.1016/j.
enbuild.2015.06.007.
[244] De Gracia A, Navarro L, Castell A, Ruiz-Pardo Á, Álvarez S, Cabeza LF. Thermal
analysis of a ventilated facade with PCM for cooling applications. Energy Build
2013;65:508–15. https://doi.org/10.1016/j.enbuild.2013.06.032.
[245] Kheradmand M, Azenha M, de Aguiar JLB, Castro-Gomes J. Experimental and
numerical studies of hybrid PCM embedded in plastering mortar for enhanced
thermal behaviour of buildings. Energy 2016;94:250–61. https://doi.org/
10.1016/j.energy.2015.10.131.
[246] Huang HJ, Chen XD, Yuan WK. Microencapsulation based on emulsification for
producing pharmaceutical products: a literature review. Dev. Chem. Eng. Miner.
Process. 2006;14(3–4):515–44. https://doi.org/10.1002/apj.5500140318.
[247] Y Yeo PK, Baek N. Microencapsulation Methods for Delivery of Protein Drugs.
Biochem. Bioprocess Eng. 2001;6:213–30.
[248] Wurster DE. Air-suspension technique of coating drug particles. A preliminary
report. J. Am. Pharm. Assoc. 1959;48(8):451–4. https://doi.org/10.1002/
jps.3030480808 [Online]. Available:.
[249] Werner SRL, Jones JR, Paterson AHJ, Archer RH, Pearce DL. Air-suspension
particle coating in the food industry: Part I - state of the art. Powder Technol
2007;171(1):25–33. https://doi.org/10.1016/j.powtec.2006.08.014.
[250] Billon A, Bataille B, Cassanas G, Jacob M. Development of spray-dried
acetaminophen microparticles using experimental designs. Int. J. Pharm. 2000;
203(1–2):159–68. https://doi.org/10.1016/S0378-5173(00)00448-8.
[251] Ré MI. Microencapulsation of spray drying. Dry. Technol. 1998;16(6):1195–236.
https://doi.org/10.1080/07373939808917460.
[252] Li M, Rouaud O, Poncelet D. Microencapsulation by solvent evaporation: State of
the art for process engineering approaches. Int. J. Pharm. 2008;363(1–2):26–39.
https://doi.org/10.1016/j.ijpharm.2008.07.018.
[253] International Energy Agency. Renewables in Global Energy Supply. Renew.
Energy 2007;(January):30 [Online]. Available: http://www.iea.org/papers
/2006/renewable_factsheet.pdf.
[254] Alva G, Lin Y, Liu L, Fang G. Synthesis, characterization and applications of
microencapsulated phase change materials in thermal energy storage: a review.
Energy Build 2017;144:276–94. https://doi.org/10.1016/j.enbuild.2017.03.063.
S.A. Albdour et al.
[255] Lu S, et al. Preparation and characterization of cross-linked polyurethane shell
microencapsulated phase change materials by interfacial polymerization. Mater.
Lett. 2018;211:36–9. https://doi.org/10.1016/j.matlet.2017.09.074.
[256] and Siddhan AKAP, Jassal M. Core content and stability of n-octadecane
containing polyurea microencapsules produced by interfacial polymerization.
J. Appl. Polym. Sci. 2007;106(5):786–92. https://doi.org/10.1002/app.
[257] Kim J, Cho G. Thermal Storage/Release, Durability, and Temperature Sensing
Properties of Thermostatic Fabrics Treated with Octadecane-Containing
Microcapsules. Text. Res. J. 2002;72(12):1093–8. https://doi.org/10.1177/
004051750207201209.
[258] Cho JS, Kwon A, Cho CG. Microencapsulation of octadecane as a phase-change
material by interfacial polymerization in an emulsion system. Colloid Polym. Sci.
2002;280(3):260–6. https://doi.org/10.1007/s00396-001-0603-x.
[259] Su JF, Wang LX, Ren L, Huang Z, Meng XW. Preparation and characterization of
polyurethane microcapsules containing n-octadecane with styrene-maleic
anhydride as a surfactant by interfacial polycondensation. J. Appl. Polym. Sci.
2006;102(5):4996–5006. https://doi.org/10.1002/app.25001.
[260] Lan X-Z ZT, Tan Z-C, Zou G-L, Sun L-X. Microencapsulation of n-eicosane as
energy storage material. Chin J Chem 2004;22(20373072):411–4.
[261] Lone S, Lee HM, Kim GM, Koh WG, Cheong IW. Facile and highly efficient
microencapsulation of a phase change material using tubular microfluidics.
Colloids Surfaces A Physicochem. Eng. Asp. 2013;422:61–7. https://doi.org/
10.1016/j.colsurfa.2013.01.035.
[262] Shi J, Wu X, Sun R, Ban B, Li J, Chen J. Nano-encapsulated phase change
materials prepared by one-step interfacial polymerization for thermal energy
storage. Mater. Chem. Phys. 2019;231(April):244–51. https://doi.org/10.1016/j.
matchemphys.2019.04.032.
[263] Nikpourian H, Bahramian AR, Abdollahi M. On the thermal performance of a
novel PCM nanocapsule: The effect of core/shell. Renew. Energy 2020;151(xxxx):
322–31. https://doi.org/10.1016/j.renene.2019.11.027.
[264] Borreguero AM, Valverde JL, Rodríguez JF, Barber AH, Cubillo JJ, Carmona M.
Synthesis and characterization of microcapsules containing Rubitherm®RT27
obtained by spray drying. Chem. Eng. J. 2011;166(1):384–90. https://doi.org/
10.1016/j.cej.2010.10.055.
[265] Zuo DZCJD, Zhan J, Luo CY, Dong BQ, Xing FX. Characteristics and release
property of polylactic acid/sodium monofluorophosphate microcapsules prepared
by spray drying. Adv. Powder. Technol 2017;28(8):2805–11. https://doi.org/
10.3390/PR8080889.
[266] Baek KH, Lee JY, Kim JH. Core/shell structured PCM nanocapsules obtained by
resin fortified emulsion process. J. Dispers. Sci. Technol. 2007;28(7):1059–65.
https://doi.org/10.1080/01932690701524281.
[267] Fang Y, Yu H, Wan W, Gao X, Zhang Z. Preparation and thermal performance of
polystyrene/n-tetradecane composite nanoencapsulated cold energy storage
phase change materials. Energy Convers. Manag. 2013;76:430–6. https://doi.
org/10.1016/j.enconman.2013.07.060.
[268] Fang Y, Kuang S, Gao X, Zhang Z. Preparation and characterization of novel
nanoencapsulated phase change materials. Energy Convers. Manag. 2008;49(12):
3704–7. https://doi.org/10.1016/j.enconman.2008.06.027.
[269] Fuensanta M, Paiphansiri U, Romero-Sánchez MD, Guillem C, López-Buendía ÁM,
Landfester K. Thermal properties of a novel nanoencapsulated phase change
material for thermal energy storage. Thermochim. Acta 2013;565:95–101.
https://doi.org/10.1016/j.tca.2013.04.028.
[270] Wang Y, Zhang Y, Xia T, Zhao W, Yang W. Effects of fabricated technology on
particle size distribution and thermal properties of stearic-eicosanoic acid/
polymethylmethacrylate nanocapsules. Sol. Energy Mater. Sol. Cells 2014;120
(PART B):481–90. https://doi.org/10.1016/j.solmat.2013.09.028.
[271] Graham M, Shchukina E, De Castro PF, Shchukin D. Nanocapsules containing salt
hydrate phase change materials for thermal energy storage. J. Mater. Chem. A
2016;4(43):16906–12. https://doi.org/10.1039/c6ta06189c.
[272] Alkan C, Sari A, Karaipekli A, Uzun O. Preparation, characterization, and thermal
properties of microencapsulated phase change material for thermal energy
storage. Sol. Energy Mater. Sol. Cells 2009;93(1):143–7. https://doi.org/
10.1016/j.solmat.2008.09.009.
[273] Hu X, Huang Z, Zhang Y. Preparation of CMC-modified melamine resin spherical
nano-phase change energy storage materials. Carbohydr. Polym. 2014;101(1):
83–8. https://doi.org/10.1016/j.carbpol.2013.08.091.
[274] Hu X, Huang Z, Yu X, Li B. Preparation and Thermal Energy Storage of
Carboxymethyl Cellulose-Modified Nanocapsules. Bioenergy Res 2013;6(4):
1135–41. https://doi.org/10.1007/s12155-013-9299-2.
[275] Niu X, Xu Q, Zhang Y, Zhang Y, Yan Y, Liu T. Fabrication and properties of micro-
nanoencapsulated phase change materials for internally-cooled liquid desiccant
dehumidification. Nanomaterials 2017;7(5). https://doi.org/10.3390/
nano7050096.
[276] Karthikeyan M, Ramachandran T, Sundaram OLS. Nanoencapsulated phase
change materials based on polyethylene glycol for creating thermoregulating
cotton. J. Ind. Text. 2014;44(1):130–46. https://doi.org/10.1177/
1528083713480378.
[277] HG Yuan RW, Kalfas G. Suspension polymerization. J Macromol Sci C 1991;31
(2–3):215–99.
[278] Scale-up in suspension polymerization. J Appl Polym Sci 1976;20:2299–303.
[279] Arshady R. Suspension, emulsion, and dispersion polymerization: a
methodological survey. Colloid Polym. Sci. 1992;270(8):717–32. https://doi.org/
10.1007/BF00776142.
[280] Alay S, Göde F, Alkan C. Preparation and characterization of poly
(methylmethacrylate-coglycidyl methacrylate)/n-hexadecane nanocapsules as a
81
Progress in Energy and Combustion Science 93 (2022) 101037
fiber additive for thermal energy storage. Fibers Polym 2010;11(8):1089–93.
https://doi.org/10.1007/s12221-010-1089-2.
[281] Deveci SS, Basal G. Preparation of PCM microcapsules by complex coacervation of
silk fibroin and chitosan. Colloid Polym. Sci. 2009;287(12):1455–67. https://doi.
org/10.1007/s00396-009-2115-z.
[282] Özonur Y, Mazman M, Paksoy HÖ, Evliya H. Microencapsulation of coco fatty
acid mixture for thermal energy storage with phase change material. Int. J.
Energy Res. 2006;30(10):741–9. https://doi.org/10.1002/er.1177.
[283] Bayés-García L, Ventolà L, Cordobilla R, Benages R, Calvet T, Cuevas-Diarte MA.
Phase Change Materials (PCM) microcapsules with different shell compositions:
Preparation, characterization and thermal stability. Sol. Energy Mater. Sol. Cells
2010;94(7):1235–40. https://doi.org/10.1016/j.solmat.2010.03.014.
[284] Li W, Zhang XX, Wang XC, Niu JJ. Preparation and characterization of
microencapsulated phase change material with low remnant formaldehyde
content. Mater. Chem. Phys. 2007;106(2–3):437–42. https://doi.org/10.1016/j.
matchemphys.2007.06.030.
[285] G. D. Ram MK, Jotshi ChK, Stefanakos EK, “Method of encapsulating a phase
change material with a metal oxide,” 2014.
[286] Wang LY, Tsai PS, Yang YM. Preparation of silica microspheres encapsulating
phase-change material by sol-gel method in O/W emulsion. J. Microencapsul.
2006;23(1):3–14. https://doi.org/10.1080/02652040500286045.
[287] Chen Z, Cao L, Shan F, Fang G. Preparation and characteristics of
microencapsulated stearic acid as composite thermal energy storage material in
buildings. Energy Build 2013;62:469–74. https://doi.org/10.1016/j.
enbuild.2013.03.025.
[288] Li M, Wu Z, Tan J. Properties of form-stable paraffin/silicon dioxide/expanded
graphite phase change composites prepared by sol-gel method. Appl. Energy
2012;92:456–61. https://doi.org/10.1016/j.apenergy.2011.11.018.
[289] Cao L, Tang F, Fang G. Synthesis and characterization of microencapsulated
paraffin with titanium dioxide shell as shape-stabilized thermal energy storage
materials in buildings. Energy Build 2014;72:31–7. https://doi.org/10.1016/j.
enbuild.2013.12.028.
[290] Chai L, Wang X, Wu D. Development of bifunctional microencapsulated phase
change materials with crystalline titanium dioxide shell for latent-heat storage
and photocatalytic effectiveness. Appl. Energy 2015;138:661–74. https://doi.
org/10.1016/j.apenergy.2014.11.006.
[291] S. Tahan Latibari, M. M. Mehrali, M. M. Mehrali, T. M. Indra Mahlia, and H. S.
Cornelis Metselaar, “Synthesis, characterization and thermal properties of
nanoencapsulated phase change materials via sol-gel method,” Energy, vol. 61, pp.
664–672, 2013, doi: 10.1016/j.energy.2013.09.012.
[292] Latibari STahan, et al. Facile synthesis and thermal performances of stearic acid/
titania core/shell nanocapsules by sol-gel method. Energy 2015;85:635–44.
https://doi.org/10.1016/j.energy.2015.04.008.
[293] Yuan H, Bai H, Wang Y. Preparation and characterization of stearic acid/SiO2
nano-encapsulated phase change materials via Sol-gel Method,” Energy Technol.
2016 Carbon Dioxide Manag. Other Technol. 2016:99–106. https://doi.org/
10.1007/978-3-319-48182-1_12.
[294] Lee J, Jo B. Nanoencapsulation of binary nitrate molten salts for thermal energy
storage: Synthesis, thermal performance, and thermal reliability. Sol. Energy
Mater. Sol. Cells 2021;230(July):111284. https://doi.org/10.1016/j.
solmat.2021.111284.
[295] C. Shaw and D. Ph, Essential Chemistry for Formulators of Semisolid and Liquid
Dosages. 2016.
[296] Zhu S, Zou D, Bao J, Ma Q, Wang Y, Hu Y. Synthesis and characterization of a
novel high durability alloy microcapsule for thermal energy storage. Sol. Energy
Mater. Sol. Cells 2021;230(July):111262. https://doi.org/10.1016/j.
solmat.2021.111262.
[297] Lan W, Shang B, Wu R, Yu X, Hu R, Luo X. Thermally-enhanced nanoencapsulated
phase change materials for latent functionally thermal fluid. Int. J. Therm. Sci.
2021;159(September 2020):106619. https://doi.org/10.1016/j.
ijthermalsci.2020.106619.
[298] SN M. Visualization of polymers at surfaces and interfaces with atomic force
microscopy. Handbook of Surfaces and Interfaces of Materials, 2. Academic Press;
2001.
[299] Huang YT, et al. Carbon nanotube-enhanced double-walled phase-change
microcapsules for thermal energy storage. J. Mater. Chem. A 2017;5(16):
7482–93. https://doi.org/10.1039/c6ta09712j.
[300] Kaliva M, Vamvakaki M. Materials Characterization. Elsevier Inc.; 2010. vol.
1242.
[301] Lin Y, Zhu C, Alva G, Fang G. Microencapsulation and thermal properties of
myristic acid with ethyl cellulose shell for thermal energy storage. Appl. Energy
2018;231(September):494–501. https://doi.org/10.1016/j.
apenergy.2018.09.154.
[302] Wang H, Ma W, Zhang J, Yang Z, Zong D. Novel synthesis of silica coated palmitic
acid nanocapsules for thermal energy storage. J. Energy Storage 2020;30(March):
101402. https://doi.org/10.1016/j.est.2020.101402.
[303] Yesilkir-Baydar S, Oztel ON, Cakir-Koc R, Candayan A. Evaluation techniques.
Elsevier Ltd; 2017.
[304] Mahoney J, Monroe C, Swartley AM, Ucak-Astarlioglu MG, Zoto CA. Surface
analysis using X-ray photoelectron spectroscopy. Spectrosc. Lett. 2020;53(10):
726–36. https://doi.org/10.1080/00387010.2020.1824197.
[305] J. Bergström, Mechanics of Solid Polymers: Theory and Computational Modeling.
2015.
[306] Li Y, Yu S, Chen P, Rojas R, Hajian A, Berglund L. Cellulose nanofibers enable
paraffin encapsulation and the formation of stable thermal regulation
S.A. Albdour et al.
nanocomposites. Nano Energy 2017;34(December 2016):541–8. https://doi.org/
10.1016/j.nanoen.2017.03.010.
[307] He F, Wang X, Wu D. New approach for sol-gel synthesis of microencapsulated n-
octadecane phase change material with silica wall using sodium silicate
precursor. Energy 2014;67:223–33. https://doi.org/10.1016/j.
energy.2013.11.088.
[308] S. Wen, J. Liu, and J. Deng, Fluid inclusion effect in flotation of sulfide minerals.
2019.
[309] Zhang K, Wang J, Xu L, Xie H, Guo Z. Preparation and thermal characterization of
n-octadecane/pentafluorostyrene nanocapsules for phase-change energy storage.
J. Energy Storage December 2020;35:2021. https://doi.org/10.1016/j.
est.2021.102327.
[310] A. Synetos DT. Invasive Imaging Techniques Coronary Artery Disease: From
Biology to Clinical Practice 2017;9(2):359.
[311] Yuan K, Wang H, Liu J, Fang X, Zhang Z. Novel slurry containing graphene oxide-
grafted microencapsulated phase change material with enhanced thermo-physical
properties and photo-thermal performance. Sol. Energy Mater. Sol. Cells 2015;
143:29–37. https://doi.org/10.1016/j.solmat.2015.06.034.
[312] Huang H, Shi T, He R, Wang J, Chu PK, Yu XF. Phase-Changing Microcapsules
Incorporated with Black Phosphorus for Efficient Solar Energy Storage. Adv. Sci.
2020;7(23):1–7. https://doi.org/10.1002/advs.202000602.
[313] Koshy O, Subramanian L, Thomas S. Differential Scanning Calorimetry in
Nanoscience and Nanotechnology. Elsevier Inc.; 2017. vol. 3.
[314] Methaapanon R, Kornbongkotmas S, Ataboonwongse C, Soottitantawat A.
Microencapsulation of n-octadecane and methyl palmitate phase change
materials in silica by spray drying process. Powder Technol 2020;361:910–6.
https://doi.org/10.1016/j.powtec.2019.10.114.
[315] Ma Y, Chu X, Tang G, Yao Y. The effect of different soft segments on the formation
and properties of binary core microencapsulated phase change materials with
polyurea/polyurethane double shell. J. Colloid Interface Sci. 2013;392(1):
407–14. https://doi.org/10.1016/j.jcis.2012.10.052.
[316] Su J, Ren L, Wang L. Preparation and mechanical properties of thermal energy
storage microcapsules. Colloid Polym. Sci. 2005;284(2):224–8. https://doi.org/
10.1007/s00396-005-1368-4.
[317] Su JF, Wang SB, Zhang YY, Huang Z. Physicochemical properties and mechanical
characters of methanol-modified melamine-formaldehyde (MMF) shell
microPCMs containing paraffin. Colloid Polym. Sci. 2011;289(2):111–9. https://
doi.org/10.1007/s00396-010-2328-1.
[318] Giro-Paloma J, Konuklu Y, Fernández AI. Preparation and exhaustive
characterization of paraffin or palmitic acid microcapsules as novel phase change
material. Sol. Energy 2015;112:300–9. https://doi.org/10.1016/j.
solener.2014.12.008.
[319] Giro-Paloma J, Alkan C, Chimenos JM, Fernández AI. Comparison of
Microencapsulated Phase Change Materials prepared at laboratory containing the
same core and different shell material. Appl. Sci. 2017;7(7). https://doi.org/
10.3390/app7070723.
[320] Hu J, Chen HQ, Zhang Z. Mechanical properties of melamine formaldehyde
microcapsules for self-healing materials. Mater. Chem. Phys. 2009;118(1):63–70.
https://doi.org/10.1016/j.matchemphys.2009.07.004.
[321] Yin D, Ma L, Liu J, Zhang Q. Pickering emulsion: a novel template for
microencapsulated phase change materials with polymer-silica hybrid shell.
Energy 2014;64:575–81. https://doi.org/10.1016/j.energy.2013.10.004.
[322] Qiu X, Lu L, Wang J, Tang G, Song G. Fabrication, thermal properties and thermal
stabilities of microencapsulated n-alkane with poly(lauryl methacrylate) as shell.
Thermochim. Acta 2015;620:10–7. https://doi.org/10.1016/j.tca.2015.10.001.
[323] Song XQ, Li YX, Wang JW. Preparation and characterization of Hexadecane
microcapsule phase change materials by in-situ polymerization. Adv. Mater. Res.
2013;815:367–70. https://doi.org/10.4028/www.scientific.net/AMR.815.367.
[324] Su JF, Wang LX, Ren L. Synthesis of polyurethane microPCMs containing n-
octadecane by interfacial polycondensation: Influence of styrene-maleic
anhydride as a surfactant. Colloids Surfaces A Physicochem. Eng. Asp. 2007;299
(1–3):268–75. https://doi.org/10.1016/j.colsurfa.2006.11.051.
[325] Konuklu Y, Unal M, Paksoy HO. Microencapsulation of caprylic acid with
different wall materials as phase change material for thermal energy storage. Sol.
Energy Mater. Sol. Cells 2014;120:536–42. https://doi.org/10.1016/j.
solmat.2013.09.035. PART B.
[326] Zhang XX, Fan YF, Tao XM, Yick KL. Fabrication and properties of microcapsules
and nanocapsules containing n-octadecane. Mater. Chem. Phys. 2004;88(2–3):
300–7. https://doi.org/10.1016/j.matchemphys.2004.06.043.
[327] Fang G, Li H, Yang F, Liu X, Wu S. Preparation and characterization of nano-
encapsulated n-tetradecane as phase change material for thermal energy storage.
Chem. Eng. J. 2009;153(1–3):217–21. https://doi.org/10.1016/j.
cej.2009.06.019.
[328] Dechao Hu WM, Wang Zhiqiang. Fabrication and characterization of a novel
polyurethane microencapsulated phase change materials for thermal energy
storage. Prog. Org. Coatings 2021;151(1):1–5 [Online]. Available: www.pnas.org
/cgi/content/short/1415439112.
[329] Wu X, Fan M, Cui S, Tan G, Shen X. Novel Na2SO4@SiO2 phase change material
with core-shell structures for high temperature thermal storage. Sol. Energy
Mater. Sol. Cells 2018;178(February):280–8. https://doi.org/10.1016/j.
solmat.2018.01.030.
[330] Li J, Lu W, Luo Z, Zeng Y. Thermal stability of sodium nitrate microcapsules for
high-temperature thermal energy storage. Sol. Energy Mater. Sol. Cells 2017;171
(October 2016):106–17. https://doi.org/10.1016/j.solmat.2017.06.028.
[331] Ji W, Cheng X, Chen H, Li L, Li Y, Liu Z. Efficient synthesis of regular spherical
GO/SiO2@Solar Salt microcapsules to enhance heat-storage capacity and cycle
82
Progress in Energy and Combustion Science 93 (2022) 101037
stability. Energy Convers. Manag. 2021;245(June):114637. https://doi.org/
10.1016/j.enconman.2021.114637.
[332] Qiu Z, et al. Physical instability suppression of microencapsulated phase change
material(Mpcm) suspensions. J. Therm. Sci. Technol. 2018;13(2):1–13. https://
doi.org/10.1299/jtst.2018jtst0033.
[333] Wang L, et al. Stability and thermophysical properties of binary propanol-water
mixtures-based microencapsulated phase change material suspensions. J. Heat
Transfer 2015;137(9):1–5. https://doi.org/10.1115/1.4030235.
[334] Wang Z, Qu J, Zhang R, Han X, Wu J. Photo-thermal performance evaluation on
MWCNTs-dispersed microencapsulated PCM slurries for direct absorption solar
collectors. J. Energy Storage 2019;26(March):100793. https://doi.org/10.1016/j.
est.2019.100793.
[335] Fu Z, et al. Experimental investigation on the enhanced performance of a solar
PVT system using micro-encapsulated PCMs. Energy 2021;228:120509. https://
doi.org/10.1016/j.energy.2021.120509.
[336] Drissi S, Eddhahak A, Caré S, Neji J. Thermal analysis by DSC of Phase Change
Materials, study of the damage effect. J. Build. Eng. 2015;1:13–9. https://doi.org/
10.1016/j.jobe.2015.01.001.
[337] Zhang L, et al. Graphene oxide-modified microencapsulated phase change
materials with high encapsulation capacity and enhanced leakage-prevention
performance. Appl. Energy 2017;197:354–63. https://doi.org/10.1016/j.
apenergy.2017.04.041.
[338] Shi X, Yazdani MR, Ajdary R, Rojas OJ. Leakage-proof microencapsulation of
phase change materials by emulsification with acetylated cellulose nanofibrils.
Carbohydr. Polym. 2021;254(August 2020):117279. https://doi.org/10.1016/j.
carbpol.2020.117279.
[339] Chen F, Wolcott M. Polyethylene/paraffin binary composites for phase change
material energy storage in building: a morphology, thermal properties, and
paraffin leakage study. Sol. Energy Mater. Sol. Cells 2015;137:79–85. https://doi.
org/10.1016/j.solmat.2015.01.010.
[340] Karaipekli A, Erdoğan T, Barlak S. The stability and thermophysical properties of
a thermal fluid containing surface-functionalized nanoencapsulated PCM.
Thermochim. Acta 2019;682(May):1–11. https://doi.org/10.1016/j.
tca.2019.178406.
[341] Fu W, et al. Thermophysical properties of n-tetradecane@polystyrene-silica
composite nanoencapsulated phase change material slurry for cold energy
storage. Energy Build 2017;136:26–32. https://doi.org/10.1016/j.
enbuild.2016.12.001.
[342] Joseph M, Sajith V. An investigation on heat transfer performance of polystyrene
encapsulated n-octadecane based nanofluid in square channel. Appl. Therm. Eng.
2019;147(August 2018):756–69. https://doi.org/10.1016/j.
applthermaleng.2018.10.120.
[343] Liu C, Ma Z, Wang J, Li Y, Rao Z. Experimental research on flow and heat transfer
characteristics of latent functional thermal fluid with microencapsulated phase
change materials. Int. J. Heat Mass Transf. 2017;115:737–42. https://doi.org/
10.1016/j.ijheatmasstransfer.2017.07.107.
[344] Cingarapu S MM, Singh D, Timofeeva EV. Nanofluids with encapsulated tin
nanoparticles for advanced heat transfer and thermal energy storage. Int J Energy
Res 2014;(4):23–40. https://doi.org/10.1002/er.
[345] Lin Z, Wei Z, Shuang L, Xiangyu J. Experimental study on improving stability of
PCM and MEPCM slurry with different surfactants. Int. J. Low-Carbon Technol.
2018;13(3):272–6. https://doi.org/10.1093/ijlct/cty027.
[346] Zheng L, Zhang W, Liang F, Lin S, Jin X. Experimental studies of phase change and
microencapsulated phase change materials in a cold storage/transportation
system with solar driven cooling cycle. Energies 2017;10(11). https://doi.org/
10.3390/en10111867.
[347] Zhang GH, Zhao CY. Thermal and rheological properties of microencapsulated
phase change materials. Renew. Energy 2011;36(11):2959–66. https://doi.org/
10.1016/j.renene.2011.04.002.
[348] Delgado M, Lázaro A, Peñalosa C, Zalba B. Experimental analysis of the influence
of microcapsule mass fraction on the thermal and rheological behavior of a PCM
slurry. Appl. Therm. Eng. 2014;63(1):11–22. https://doi.org/10.1016/j.
applthermaleng.2013.10.011.
[349] Dutkowski K, Kruzel M. Experimental investigation of the apparent thermal
conductivity of microencapsulated phase-change-material slurry at the phase-
transition temperature. Materials (Basel) 2021;14(15). https://doi.org/10.3390/
ma14154124.
[350] Ho CJ, Chang PC, Yan WM, Amani M. Microencapsulated n-eicosane PCM
suspensions: Thermophysical properties measurement and modeling. Int. J. Heat
Mass Transf. 2018;125:792–800. https://doi.org/10.1016/j.
ijheatmasstransfer.2018.04.147.
[351] Barlak S, Sara ON, Karaipekli A, Yapıcı S. Thermal Conductivity and Viscosity of
Nanofluids Having Nanoencapsulated Phase Change Material. Nanoscale
Microscale Thermophys. Eng. 2016;20(2):85–96. https://doi.org/10.1080/
15567265.2016.1174321.
[352] Ma X, Liu Y, Liu H, Zhang L, Xu B, Xiao F. Fabrication of novel slurry containing
graphene oxide-modified microencapsulated phase change material for direct
absorption solar collector. Sol. Energy Mater. Sol. Cells 2018;188(September):
73–80. https://doi.org/10.1016/j.solmat.2018.08.021.
[353] Xu B, Chen C, Zhou J, Ni Z, Ma X. Preparation of novel microencapsulated phase
change material with Cu-Cu2O/CNTs as the shell and their dispersed slurry for
direct absorption solar collectors. Sol. Energy Mater. Sol. Cells 2019;200(June):
109980. https://doi.org/10.1016/j.solmat.2019.109980.
[354] Chen Y, Zhang Q, Wen X, Yin H, Liu J. A novel CNT encapsulated phase change
material with enhanced thermal conductivity and photo-thermal conversion
S.A. Albdour et al.
performance. Sol. Energy Mater. Sol. Cells 2018;184(May):82–90. https://doi.
org/10.1016/j.solmat.2018.04.034.
[355] Liu J, Chen L, Fang X, Zhang Z. Preparation of graphite nanoparticles-modified
phase change microcapsules and their dispersed slurry for direct absorption solar
collectors. Sol. Energy Mater. Sol. Cells 2017;159:159–66. https://doi.org/
10.1016/j.solmat.2016.09.020.
[356] Xiaochun Ma FX, Liu Han, Chen Chen, Liu Yanjun, Zhang Lin, Xu Bin. Synthesis of
novel microencapsulated phase change material with SnO2/CNTs shell for solar
energy storage and photo-thermal conversion. J. Phys. Energy 2020;2(1):0–31.
[357] Dutkowski K, Kruzel M, Zajaczkowski˛ B. Determining the heat of fusion and
specific heat of microencapsulated phase change material slurry by thermal delay
method. Energies 2021;14(1). https://doi.org/10.3390/en14010179.
[358] Yang R, Xu H, Zhang Y. Preparation, physical property and thermal physical
property of phase change microcapsule slurry and phase change emulsion. Sol.
Energy Mater. Sol. Cells 2003;80(4):405–16. https://doi.org/10.1016/j.
solmat.2003.08.005.
[359] H. T. Yamagishi ATPY, Sugeno T, Ishige T. An evaluation of microencapsulated
PCM for use in cold energy transportation medium IECEC 96. Proc. 31st Intersoc.
Energy Convers. Eng. Conf. 1960;3(2):2077–83. https://doi.org/10.1080/
01619566009536968.
[360] Alvarado JL, Marsh C, Sohn C, Phetteplace G, Newell T. Thermal performance of
microencapsulated phase change material slurry in turbulent flow under constant
heat flux. Int. J. Heat Mass Transf. 2007;50(9–10):1938–52. https://doi.org/
10.1016/j.ijheatmasstransfer.2006.09.026.
[361] Dutkowski K, Fiuk JJ. Experimental investigation of the effects of mass fraction
and temperature on the viscosity of microencapsulated PCM slurry. Int. J. Heat
Mass Transf. 2018;126:390–9. https://doi.org/10.1016/j.
ijheatmasstransfer.2018.05.158.
[362] Latibari ST, Eversdijk J, Cuypers R, Drosou V, Shahi M. Preparation of phase
change microcapsules with the enhanced photothermal performance. Polymers
(Basel) 2019;11(9). https://doi.org/10.3390/polym11091507.
[363] Yuan S, et al. Robust, double-layered phase-changing microcapsules with superior
solar-thermal conversion capability and extremely high energy storage density for
efficient solar energy storage. Renew. Energy 2021;180:725–33. https://doi.org/
10.1016/j.renene.2021.08.128.
[364] Carreau PJ. Rheological Equations From Molecular Network Theories. Trans Soc
Rheol 1972;16(1):99–127. https://doi.org/10.1122/1.549276.
[365] Dutkowski K, Fiuk JJ. Experimental research of viscosity of microencapsulated
PCM slurry at the phase change temperature. Int. J. Heat Mass Transf. 2019;134:
1209–17. https://doi.org/10.1016/j.ijheatmasstransfer.2019.02.036.
[366] Gao G, Zhang T, Jiao S, Guo C. Preparation of reduced graphene oxide modified
magnetic phase change microcapsules and their application in direct absorption
solar collector. Sol. Energy Mater. Sol. Cells 2020;216(February):110695. https://
doi.org/10.1016/j.solmat.2020.110695.
[367] Khan MMA, Ibrahim NI, Mahbubul IM, Muhammad. Ali H, Saidur R, Al-
Sulaiman FA. Evaluation of solar collector designs with integrated latent heat
thermal energy storage: a review. Sol. Energy 2018;166(March 2017):334–50.
https://doi.org/10.1016/j.solener.2018.03.014.
[368] Thirugnanasambandam M, Iniyan S, Goic R. A review of solar thermal
technologies. Renew. Sustain. Energy Rev. 2010;14(1):312–22. https://doi.org/
10.1016/j.rser.2009.07.014.
[369] Gorji TB, Ranjbar AA. A review on optical properties and application of
nanofluids in direct absorption solar collectors (DASCs. Renew. Sustain. Energy
Rev. 2017;72(January):10–32. https://doi.org/10.1016/j.rser.2017.01.015.
[370] Sharaf OZ, et al. Radiation stability and photothermal performance of surface-
functionalized plasmonic nanofluids for direct-absorption solar applications. Sol.
Energy Mater. Sol. Cells 2021;227(February):111115. https://doi.org/10.1016/j.
solmat.2021.111115.
[371] Sharaf OZ, et al. Thermal stability and plasmonic photothermal conversion of
surface-modified solar nanofluids: Comparing prolonged and cyclic thermal
treatments. Energy Convers. Manag. 2021;244(April):114463. https://doi.org/
10.1016/j.enconman.2021.114463.
[372] Taylor RA, et al. Applicability of nanofluids in high flux solar collectors. J. Renew.
Sustain. Energy 2011;3(2). https://doi.org/10.1063/1.3571565.
[373] He Q, Wang S, Zeng S, Zheng Z. Experimental investigation on photothermal
properties of nanofluids for direct absorption solar thermal energy systems.
Energy Convers. Manag. 2013;73:150–7. https://doi.org/10.1016/j.
enconman.2013.04.019.
[374] Tyagi H, Phelan P, Prasher R. Predicted efficiency of a Low-temperature
Nanofluid-based direct absorption solar collector. J. Sol. Energy Eng. Trans.
ASME 2009;131(4):0410041–7. https://doi.org/10.1115/1.3197562.
[375] Dutkowski T, Kruzel K, Bohdal M. Experimental Studies of the Influence of
Microencapsulated Phase Change Material on Thermal Parameters of a Flat Liquid
Solar Collector. Energies 2021;14:1–14.
[376] Huang MJ, Eames PC, McCormack S, Griffiths P, Hewitt NJ. Microencapsulated
phase change slurries for thermal energy storage in a residential solar energy
system. Renew. Energy 2011;36(11):2932–9. https://doi.org/10.1016/j.
renene.2011.04.004.
[377] Minardi JE, Chuang HN. Performance of a ‘black’ liquid flat-plate solar collector.
Sol. Energy 1975;17(3):179–83. https://doi.org/10.1016/0038-092X(75)90057-
2.
[378] Li F, Wang X, Wu D. Fabrication of multifunctional microcapsules containing n-
eicosane core and zinc oxide shell for low-temperature energy storage,
photocatalysis, and antibiosis. Energy Convers. Manag. 2015;106:873–85.
https://doi.org/10.1016/j.enconman.2015.10.026.
83
Progress in Energy and Combustion Science 93 (2022) 101037
[379] Yu S, Wang X, Wu D. Microencapsulation of n-octadecane phase change material
with calcium carbonate shell for enhancement of thermal conductivity and
serving durability: Synthesis, microstructure, and performance evaluation. Appl.
Energy 2014;114:632–43. https://doi.org/10.1016/j.apenergy.2013.10.029.
[380] Ma X, et al. Synthesis of novel microencapsulated phase change material with
SnO2/CNTs shell for solar energy storage and photo-thermal conversion. Mater.
Res. Express 2020;7(1). https://doi.org/10.1088/2053-1591/ab657e.
[381] Liu H, Wang X, Wu D. Tailoring of bifunctional microencapsulated phase change
materials with CdS/SiO2 double-layered shell for solar photocatalysis and solar
thermal energy storage. Appl. Therm. Eng. 2018;134(January 2017):603–14.
https://doi.org/10.1016/j.applthermaleng.2018.02.027.
[382] Pornea AM, Kim H. Design and synthesis of SiO2/TiO2/PDA functionalized phase
change microcapsules for efficient solar-driven energy storage. Energy Convers.
Manag. 2021;232(October 2020):113801. https://doi.org/10.1016/j.
enconman.2020.113801.
[383] Lin Q, Wang S, Zhang L. Multi-scale modeling and investigation of thermo-fluidic
performance of microencapsulated phase-change material slurry. J. Energy
Storage 2021;37(November 2020):102502. https://doi.org/10.1016/j.
est.2021.102502.
[384] Xu L, Pu L, Zhang S, Ma Z. Thermo-fluidic performance of microencapsulated
phase change material slurry in thermal energy storage. J. Energy Storage 2021;
43(July):103247. https://doi.org/10.1016/j.est.2021.103247.
[385] Ma F, Zhang P, Shi XJ. Investigation of thermo-fluidic performance of phase
change material slurry and energy transport characteristics. Appl. Energy 2018;
227(August 2017):643–54. https://doi.org/10.1016/j.apenergy.2017.08.146.
[386] Liu H, Wang X, Wu D, Ji S. Morphology-controlled synthesis of microencapsulated
phase change materials with TiO2 shell for thermal energy harvesting and
temperature regulation. Energy 2019;172:599–617. https://doi.org/10.1016/j.
energy.2019.01.151.
[387] Roy SK, Sengupta S. An evaluation of phase change microcapsules for use in
enhanced heat transfer fluids. Int. Commun. Heat Mass Transf. 1991;18(4):
495–507. https://doi.org/10.1016/0735-1933(91)90064-B.
[388] Ohtsubo T, Tsuda S, Tsuji K. A study of the physical strength of fenitrothion
microcapsules. Polymer (Guildf) 1991;32(13):2395–9. https://doi.org/10.1016/
0032-3861(91)90080-3.
[389] Vérez D, et al. Experimental study on two pcm macro-encapsulation designs in a
thermal energy storage tank. Appl. Sci. 2021;11(13). https://doi.org/10.3390/
app11136171.
[390] Sari A, Alkan C, Karaipekli A, Uzun O. Microencapsulated n-octacosane as phase
change material for thermal energy storage. Sol. Energy 2009;83(10):1757–63.
https://doi.org/10.1016/j.solener.2009.05.008.
[391] Sukhorukov G, Fery A, Möhwald H. Intelligent micro- and nanocapsules. Prog.
Polym. Sci. 2005;30(8–9):885–97. https://doi.org/10.1016/j.
progpolymsci.2005.06.008.
[392] Tsien HS. Superaerodynamics, Mechanics of Rarefied Gases. Collect. Work. Hsue-
Shen Tsien 2012:406–29. https://doi.org/10.1016/B978-0-12-398277-3.50020-
8.
[393] Zhang Y, Faghri A. Analysis of forced convection heat transfer in
microencapsulated phase change material suspensions. J. Thermophys. Heat
Transf. 1995;9(4):727–32. https://doi.org/10.2514/3.731.
[394] Chai L, Shaukat R, Wang L, Wang HS. A review on heat transfer and
hydrodynamic characteristics of nano/microencapsulated phase change slurry
(N/MPCS) in mini/microchannel heat sinks. Appl. Therm. Eng. 2018;135
(February):334–49. https://doi.org/10.1016/j.applthermaleng.2018.02.068.
[395] Qiu Z, Li L. Experimental and numerical investigation of laminar heat transfer of
microencapsulated phase change material slurry (MPCMS) in a circular tube with
constant heat flux. Sustain. Cities Soc. 2020;52(August 2019):101786. https://
doi.org/10.1016/j.scs.2019.101786.
[396] Charunyakorn P, Sengupta S, Roy SK. Forced convection heat transfer in
microencapsulated phase change material slurries: flow in circular ducts. Int. J.
Heat Mass Transf. 1991;34(3):819–33. https://doi.org/10.1016/0017-9310(91)
90128-2.
[397] Kuravi S, Kota KM, Du J, Chow LC. Numerical investigation of flow and heat
transfer performance of nano-encapsulated phase change material slurry in
microchannels. J. Heat Transfer 2009;131(6):1–9. https://doi.org/10.1115/
1.3084123.
[398] Ma ZW, Zhang P. Modeling the heat transfer characteristics of flow melting of
phase change material slurries in the circular tubes. Int. J. Heat Mass Transf.
2013;64:874–81. https://doi.org/10.1016/j.ijheatmasstransfer.2013.05.026.
[399] Zhang Y, Du K, He JP, Yang L, Li YJ. 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. 2014;
65(1):66–83. https://doi.org/10.1080/10407782.2013.811153.
[400] Zeng R, et al. Heat transfer characteristics of microencapsulated phase change
material slurry in laminar flow under constant heat flux. Appl. Energy 2009;86
(12):2661–70. https://doi.org/10.1016/j.apenergy.2009.04.025.
[401] Huang H, Xiao Y, Lin J, Zhou T, Liu Y, Zhao Q. Improvement of the efficiency of
solar thermal energy storage systems by cascading a PCM unit with a water tank.
J. Clean. Prod. 2020;245:118864. https://doi.org/10.1016/j.
jclepro.2019.118864.
[402] Iten M, Liu S, Shukla A. Experimental validation of an air-PCM storage unit
comparing the effective heat capacity and enthalpy methods through CFD
simulations. Energy 2018;155:495–503. https://doi.org/10.1016/j.
energy.2018.04.128.
[403] Amidu MA, Addad Y, Riahi MK, Abu-Nada E. Numerical investigation of
nanoparticles slip mechanisms impact on the natural convection heat transfer
S.A. Albdour et al.
characteristics of nanofluids in an enclosure. Sci. Rep. 2021;11(1):1–24. https://
doi.org/10.1038/s41598-021-95269-z.
[404] Bahiraei M. A Comprehensive Review on Different Numerical Approaches for
Simulation in Nanofluids: Traditional and Novel Techniques. J. Dispers. Sci.
Technol. 2014;35(7):984–96. https://doi.org/10.1080/01932691.2013.825210.
[405] Pouraria H, Park KH, Seo Y. Numerical modelling of dispersed water in oil flows
using eulerian-eulerian approach and population balance model. Processes 2021;
9(8). https://doi.org/10.3390/pr9081345.
[406] Ma F, Zhang P. Heat Transfer Characteristics of a Volumetric Absorption Solar
Collector using Nano-Encapsulated Phase Change Slurry. Heat Transf. Eng. 2018;
39(17–18):1487–97. https://doi.org/10.1080/01457632.2017.1369827.
[407] Hao YL, Tao YX. A numerical model for phase-change suspension flow in
microchannels. Numer. Heat Transf. Part A Appl. 2004;46(1):55–77. https://doi.
org/10.1080/10407780490457545.
[408] Xing KQ, Tao YX, Hao YL. Performance evaluation of liquid flow with PCM
particles in Microchannels. J. Heat Transfer 2005;127(8):931–40. https://doi.
org/10.1115/1.1929783.
[409] Ge W, et al. Discrete simulation of granular and particle-fluid flows: From
fundamental study to engineering application. Rev. Chem. Eng. 2017;33(6):
551–623. https://doi.org/10.1515/revce-2015-0079.
[410] Mahian O, et al. Recent advances in modeling and simulation of nanofluid
flows—Part II: applications. Phys. Rep. 2019;791:1–59. https://doi.org/10.1016/
j.physrep.2018.11.003.
[411] Babaei H, Keblinski P, Khodadadi JM. Thermal conductivity enhancement of
paraffins by increasing the alignment of molecules through adding CNT/
graphene. Int. J. Heat Mass Transf. 2013;58(1–2):209–16. https://doi.org/
10.1016/j.ijheatmasstransfer.2012.11.013.
[412] Tafrishi H, Sadeghzadeh S, Ahmadi R, Molaei F, Yousefi F, Hassanloo H.
Investigation of tetracosane thermal transport in presence of graphene and carbon
nanotube fillers––A molecular dynamics study. J. Energy Storage 2020;29
(March):101321. https://doi.org/10.1016/j.est.2020.101321.
[413] Yu Y, Tao Y, He YL. Molecular dynamics simulation of thermophysical properties
of NaCl-SiO2 based molten salt composite phase change materials. Appl. Therm.
Eng. 2020;166:114628. https://doi.org/10.1016/j.applthermaleng.2019.114628.
[414] Rao Z, Wang S, Wu M, Zhang Y, Li F. Molecular dynamics simulations of melting
behavior of alkane as phase change materials slurry. Energy Convers. Manag.
2012;64:152–6. https://doi.org/10.1016/j.enconman.2012.05.013.
[415] Wang Y, Chen Z, Ling X. A molecular dynamics study of nano-encapsulated phase
change material slurry. Appl. Therm. Eng. 2016;98:835–40. https://doi.org/
10.1016/j.applthermaleng.2015.12.124.
[416] Earl DJ, Deem MW. Monte Carlo simulations. Methods Mol. Biol. 2008;443:
25–36. https://doi.org/10.1007/978-1-59745-177-2_2.
[417] Shu C, Mao XH, Chew YT. Particle number per cell and scaling factor effect on
accuracy of DSMC simulation of micro flows. Int. J. Numer. Methods Heat Fluid
Flow 2005;15(8):827–41. https://doi.org/10.1108/09615530510625101.
[418] Sun ZX, Tang Z, He YL, Tao WQ. Proper cell dimension and number of particles
per cell for DSMC. Comput. Fluids 2011;50(1):1–9. https://doi.org/10.1016/j.
compfluid.2011.04.013.
[419] Lattuada M, Wu H, Morbidelli M. A simple model for the structure of fractal
aggregates. J. Colloid Interface Sci. 2003;268(1):106–20. https://doi.org/
10.1016/j.jcis.2003.07.027.
[420] Bin Wang Z, Chen R, Wang H, Liao Q, Zhu X, Li SZ. An overview of smoothed
particle hydrodynamics for simulating multiphase flow. Appl. Math. Model. 2016;
40(23–24):9625–55. https://doi.org/10.1016/j.apm.2016.06.030.
[421] Farrokhpanah A, Bussmann M, Mostaghimi J. New smoothed particle
hydrodynamics (SPH) formulation for modeling heat conduction with
solidification and melting. Numer. Heat Transf. Part B Fundam. 2017;71(4):
299–312. https://doi.org/10.1080/10407790.2017.1293972.
[422] Archibold AR, Rahman MM, Goswami DY, Stefanakos EK. Analysis of heat
transfer and fluid flow during melting inside a spherical container for thermal
energy storage. Appl. Therm. Eng. 2014;64(1–2):396–407. https://doi.org/
10.1016/j.applthermaleng.2013.12.016.
[423] Lin Q, Wang S, Ma Z, Wang J, Zhang T. Lattice Boltzmann simulation of flow and
heat transfer evolution inside encapsulated phase change materials due to natural
convection melting. Chem. Eng. Sci. 2018;189:154–64. https://doi.org/10.1016/
j.ces.2018.05.052.
[424] J. Li et al., “Meso-scale phenomena from compromise,” pp. 1–7.
[425] He YL, Tao WQ. Multiscale simulations of heat transfer and fluid flow problems.
J. Heat Transfer 2012;134(3):1–13. https://doi.org/10.1115/1.4005154.
[426] He YL, Tao WQ. Numerical solutions of nano/microphenomena coupled with
macroscopic process of heat transfer and fluid flow: a brief review. J. Heat
Transfer 2015;137(9). https://doi.org/10.1115/1.4030239.
[427] Saunders MG, Voth GA. Coarse-graining methods for computational biology.
Annu. Rev. Biophys. 2013;42(1):73–93. https://doi.org/10.1146/annurev-
biophys-083012-130348.
[428] Seiferth D, Sollich P, Klumpp S. Coarse graining of biochemical systems described
by discrete stochastic dynamics. Phys. Rev. E 2020;102(6):1–42. https://doi.org/
10.1103/PhysRevE.102.062149.
[429] Hoogerbrugge PJ, Koelman JMVA. Simulating microscopic hydrodynamic
phenomena with dissipative particle dynamics. Epl 1992;19(3):155–60. https://
doi.org/10.1209/0295-5075/19/3/001.
[430] Abu-Nada E. Dissipative particle dynamics simulation of natural convection using
variable thermal properties. Int. Commun. Heat Mass Transf. 2015;69:84–93.
https://doi.org/10.1016/j.icheatmasstransfer.2015.10.008.
84
Progress in Energy and Combustion Science 93 (2022) 101037
[431] Abu-Nada E. Heat transfer simulation using energy conservative dissipative
particle dynamics. Mol. Simul. 2010;36(5):382–90. https://doi.org/10.1080/
08927020903515337.
[432] Abu-Nada E. Modeling of various heat transfer problems using dissipative particle
dynamics. Numer. Heat Transf. Part A Appl. 2010;58(8):660–79. https://doi.org/
10.1080/10407782.2010.516681.
[433] Abu-Nada E. Application of dissipative particle dynamics to natural convection in
differentially heated enclosures. Mol. Simul. 2011;37(2):135–52. https://doi.org/
10.1080/08927022.2010.533272.
[434] Abu-Nada E. Natural convection heat transfer simulation using energy
conservative dissipative particle dynamics. Phys. Rev. E - Stat. Nonlinear, Soft
Matter Phys. 2010;81(5):1–14. https://doi.org/10.1103/PhysRevE.81.056704.
[435] Abu-Nada E, Pop I, Mahian O. A dissipative particle dynamics two-component
nanofluid heat transfer model: application to natural convection. Int. J. Heat Mass
Transf. 2019;133:1086–98. https://doi.org/10.1016/j.
ijheatmasstransfer.2018.12.151.
[436] Ng KC, Sheu TWH. Refined energy-conserving dissipative particle dynamics
model with temperature-dependent properties and its application in solidification
problem. Phys. Rev. E 2017;96(4):1–12. https://doi.org/10.1103/
PhysRevE.96.043302.
[437] F. Durst, D. Milojevic, and B. Schoenung, “Eulerian and Lagrangian predictions of
particulate two-phase flows.,” vol. 8, pp. 101–115, 1983.
[438] Apostolou K, Hrymak AN. Discrete element simulation of liquid-particle flows.
Comput. Chem. Eng. 2008;32(4–5):841–56. https://doi.org/10.1016/j.
compchemeng.2007.03.018.
[439] Garoosi F, Shakibaeinia A, Bagheri G. Eulerian-Lagrangian modeling of solid
particle behavior in a square cavity with several pairs of heaters and coolers
inside. Powder Technol 2015;280:239–55. https://doi.org/10.1016/j.
powtec.2015.04.048.
[440] Balakin B, Hoffmann AC, Kosinski P. The collision efficiency in a shear flow.
Chem. Eng. Sci. 2012;68(1):305–12. https://doi.org/10.1016/j.ces.2011.09.042.
[441] El-Askary WA, Eldesoky IM, Saleh O, El-Behery SM, Dawood AS. Behavior of
downward turbulent gas-solid flow through sudden expansion pipe. Powder
Technol 2016;291:351–65. https://doi.org/10.1016/j.powtec.2016.01.002.
[442] O. Z. Sharaf, “Modeling and Simulation Techniques of Nanofluid-Based Systems
for Applications in Solar Energy PhD . Thesis,” no. March, 2020.
[443] Mirzaei M, Saffar-Avval M, Naderan H. Heat transfer investigation of laminar
developing flow of nanofluids in a microchannel based on Eulerian-Lagrangian
approach. Can. J. Chem. Eng. 2014;92(6):1139–49. https://doi.org/10.1002/
cjce.21962.
[444] Dong S, Zheng L, Zhang X, Wu S, Shen B. A new model for Brownian force and the
application to simulating nanofluid flow. Microfluid. Nanofluidics 2014;16(1–2):
131–9. https://doi.org/10.1007/s10404-013-1213-x.
[445] Deepak Selvakumar R, Dhinakaran S. Heat transfer and particle migration in
nanofluid flow around a circular bluff body using a two-way coupled Eulerian-
Lagrangian approach. Int. J. Heat Mass Transf. 2017;115:282–93. https://doi.
org/10.1016/j.ijheatmasstransfer.2017.07.103.
[446] Ernst M, Sommerfeld M. On the volume fraction effects of inertial colliding
particles in homogeneous isotropic turbulence. J. Fluids Eng. Trans. ASME 2012;
134(3). https://doi.org/10.1115/1.4005681.
[447] Liu Z, Zhu Y, Clausen JR, Lechman JB, Rao RR, Aidun CK. Multiscale method
based on coupled lattice-Boltzmann and Langevin-dynamics for direct simulation
of nanoscale particle/polymer suspensions in complex flows. Int. J. Numer.
Methods Fluids 2019;91(5):228–46. https://doi.org/10.1002/fld.4752.
[448] Ermak DL, McCammon JA. Brownian dynamics with hydrodynamic interactions.
J. Chem. Phys. 1978;69(4):1352–60. https://doi.org/10.1063/1.436761.
[449] Brady J. Stokesian Dynamics. Annu. Rev. Fluid Mech. 1988;20(1):111–57.
https://doi.org/10.1146/annurev.fluid.20.1.111.
[450] Rostami J. Convective heat transfer by micro-encapsulated PCM in a mini-duct.
Int. J. Therm. Sci. 2021;161(October 2020):106737. https://doi.org/10.1016/j.
ijthermalsci.2020.106737.
[451] Shabgard H, Hu H, Boettcher PA, McCarthy M, Sun Y. Heat transfer analysis of
PCM slurry flow between parallel plates. Int. J. Heat Mass Transf. 2016;99:
895–903. https://doi.org/10.1016/j.ijheatmasstransfer.2016.04.020.
[452] Alisetti EL, Roy SK. Forced convection heat transfer to phase change material
slurries in circular ducts. J. Thermophys. heat Transf. 2000;14(1):115–8. https://
doi.org/10.2514/2.6499.
[453] Chen B, et al. An experimental study of convective heat transfer with
microencapsulated phase change material suspension: Laminar flow in a circular
tube under constant heat flux. Exp. Therm. Fluid Sci. 2008;32(8):1638–46.
https://doi.org/10.1016/j.expthermflusci.2008.05.008.
[454] Ghalambaz M, Chamkha AJ, Wen D. Natural convective flow and heat transfer of
Nano-Encapsulated Phase Change Materials (NEPCMs) in a cavity. Int. J. Heat
Mass Transf. 2019;138:738–49. https://doi.org/10.1016/j.
ijheatmasstransfer.2019.04.037.
[455] Haddad Z, Iachachene F, Abu-Nada E, Pop I. Investigation of the novelty of latent
functionally thermal fluids as alternative to nanofluids in natural convective
flows. Sci. Rep. 2020;10(1):1–16. https://doi.org/10.1038/s41598-020-77224-6.
[456] Mohib Ur Rehman M, Qu ZG, Fu RP. Three-dimensional numerical study of
laminar confined slot jet impingement cooling using slurry of nano-encapsulated
phase change material. J. Therm. Sci. 2016;25(5):431–9. https://doi.org/
10.1007/s11630-016-0881-8.
[457] Seyf HR, Zhou Z, Ma HB, Zhang Y. Three dimensional numerical study of heat-
transfer enhancement by nano-encapsulated phase change material slurry in
microtube heat sinks with tangential impingement. Int. J. Heat Mass Transf.
S.A. Albdour et al.
2013;56(1–2):561–73. https://doi.org/10.1016/j.
ijheatmasstransfer.2012.08.052.
[458] Maxwell JC. A Treatise on Electricity & Magnetism. New York: Dover
Publications, INC; 1954. p. 560. - Volume 1[Online]. Available: https://archive.
org/stream/ATreatiseOnElectricityMagnetism-Volume1/Maxwell-ATreatiseOn
ElectricityMagnetismVolume1#page/n15/mode/2up/search/electromagnetic+
radiation.
[459] Hamilton RL. Thermal conductivity of heterogeneous two-component systems.
Ind. Eng. Chem. Fundam. 1962;1(3):187–91. https://doi.org/10.1021/
i160003a005.
[460] McMillen TJ, Leal LG. The effect of deformation on the effective conductivity of a
dilute suspension of drops in the limit of low particle peclet number. Int. J.
Multiph. Flow 1975;2(2):105–12. https://doi.org/10.1016/0301-9322(75)
90002-6.
[461] Nir A, Acrivos A. The effective thermal conductivity of sheared suspensions.
J. Fluid Mech. 1976;78(1):33–48. https://doi.org/10.1017/
S0022112076002310.
[462] M. M. Chen, “MicroconvectiveThermal Conductiwity in Disperse Two-Phase
Mixtures as Observed in a Low Velocity Couette Flow Experiment,” vol. 103, no.
February 1981, pp. 47–51, 2016, [Online]. Available: http://heattransfer.as
medigitalcollection.asme.org/.
[463] Zhang Y, Hu X, Wang X. Theoretical analysis of convective heat transfer
enhancement of microencapsulated phase change material slurries. Heat Mass
Transf. und Stoffuebertragung 2003;40(1–2):59–66. https://doi.org/10.1007/
s00231-003-0410-7.
[464] Woolard EW, Einstein A, Furth R, Cowper AD. Investigations on the Theory of the
Brownian Movement. Am. Math. Mon. 1928;35(6):318. https://doi.org/10.2307/
2298685.
[465] BATCHELOR GK. The effect of Brownian motion on the bulk stress in a suspension
of spherical particles. J. Fluid Mech. 1945;83(127):364–5.
[466] V. VAND, “Theory of viscosity of concentrated suspensions,” 364-365, vol. 120, p.
853, 1945.
[467] Wang X, et al. Flow and heat transfer behaviors of phase change material slurries
in a horizontal circular tube. Int. J. Heat Mass Transf. 2007;50(13–14):2480–91.
https://doi.org/10.1016/j.ijheatmasstransfer.2006.12.024.
[468] Bock Choon Pak YIC. Hydrodynamic and Heat Transfer Study of Dispersed Fluids
With Submicron Metallic Oxide. Exp. Heat Transf. A J., Therm. Energy Transp.,
Storage, Convers 2013;(January 2013):37–41.
[469] Wu S, Yan T, Kuai Z, Pan W. Thermal conductivity enhancement on phase change
materials for thermal energy storage: a review. Energy Storage Mater 2020;25
(October 2019):251–95. https://doi.org/10.1016/j.ensm.2019.10.010.
[470] Mehra N, et al. Thermal transport in polymeric materials and across composite
interfaces. Appl. Mater. Today 2018;12:92–130. https://doi.org/10.1016/j.
apmt.2018.04.004.
[471] Lv W, Henry A. Examining the Validity of the Phonon Gas Model in Amorphous
Materials. Sci. Rep. 2016;6:1–8. https://doi.org/10.1038/srep37675.
[472] R. W. Clark, “Heat Conductivity of Non-Metallic Crystals,” Science (80-.)., vol. 36,
no. 926, p. 415, 1912, doi: 10.1126/science.36.926.415.
[473] W. C. Kim, “Thermal Transport in Nano structured Materials,” 2005.
[474] Shanker A, Li C, Kim GH, Gidley D, Pipe KP, Kim J. High thermal conductivity in
electrostatically engineered amorphous polymers. Sci. Adv. 2017;3(7). https://
doi.org/10.1126/sciadv.1700342.
[475] Zhao AZ, Wingert MC, Chen R, Garay JE. Phonon gas model for thermal
conductivity of dense, strongly interacting liquids. J. Appl. Phys. 2021;129(23):
1–18. https://doi.org/10.1063/5.0040734.
[476] S. Siegert, “Thermal properties of phase-change materials - From lattice dynamics
to thermoelectricity,” PhD Thesis, vol. 125, no. October, pp. 1–5, 2011.
[477] Cheng P, et al. Different dimensional nanoadditives for thermal conductivity
enhancement of phase change materials: Fundamentals and applications. Nano
Energy 2021;85(August 2020):105948. https://doi.org/10.1016/j.
nanoen.2021.105948.
[478] Yang F, Dames C. Mean free path spectra as a tool to understand thermal
conductivity in bulk and nanostructures. Phys. Rev. B - Condens. Matter Mater.
Phys. 2013;87(3). https://doi.org/10.1103/PhysRevB.87.035437.
[479] Callaway J. Model for lattice thermal conductivity at low temperatures. Phys.
Rev. 1959;113(4):1046–51. https://doi.org/10.1103/PhysRev.113.1046.
[480] Holland MG. Analysis of lattice thermal conductivity. Phys. Rev. 1963;132(6):
2461–71. https://doi.org/10.1103/PhysRev.132.2461.
[481] Allen PB, Feldman JL, Fabian J, Wooten F. Diffusons, locons and propagons:
Character of atomie yibrations in amorphous Si. Philos. Mag. B Phys. Condens.
Matter; Stat. Mech. Electron. Opt. Magn. Prop. 1999;79(11–12):1715–31. https://
doi.org/10.1080/13642819908223054.
[482] Cahill DG, Watson SK, Pohl RO. Lower limit to the thermal conductivity of
disordered crystals. Phys. Rev. B 1992;46(10):6131–40. https://doi.org/10.1103/
PhysRevB.46.6131.
[483] Bridgeman Pw. The thermal conductivity of liquids under pressure. Physics
(College. Park. Md). 1923;59(7):141–69.
[484] Xi Q, et al. A Ubiquitous Thermal Conductivity Formula for Liquids, Polymer
Glass, and Amorphous Solids. Chinese Phys. Lett. 2020;37(10). https://doi.org/
10.1088/0256-307X/37/10/104401.
[485] and H. E. R. E. Powell, W. E. Roseveare, “Diffusion, Thermal Conductivity, and
Viscous Flow of Liquids,” pp. 430–435, 1941.
[486] Paredes X, Lourenço MJ, de Castro CN, Wakeham W. Thermal conductivity of
ionic liquids and ionanofluids. Can molecular theory help? Fluids 2021;6(3).
https://doi.org/10.3390/fluids6030116.
85
Progress in Energy and Combustion Science 93 (2022) 101037
[487] E. Mclaughlin, “Thermal conductivity of simple molecules,” vol. 206, no. 1, pp.
206–212, 1959.
[488] P. Taylor, “MOLECULAR DYNAMICS SIMULATION IN NANOSCALE,” no.
December 2014, pp. 37–41, 2010, doi: 10.1080/10893950390219047.
[489] H. Search, C. Journals, A. Contact, M. Iopscience, and I. P. Address, “The
fluctuation-dissipation theorem,” vol. 255, 1966.
[490] Manjunatha L, Takamatsu H, Cannon JJ. Atomic-level breakdown of Green–Kubo
relations provides new insight into the mechanisms of thermal conduction. Sci.
Rep. 2021;11(1):1–11. https://doi.org/10.1038/s41598-021-84446-9.
[491] Andritsos EI, et al. The heat capacity of matter beyond the Dulong-Petit value.
J. Phys. Condens. Matter 2013;25(23). https://doi.org/10.1088/0953-8984/25/
23/235401.
[492] Qiu L, et al. A review of recent advances in thermophysical properties at the
nanoscale: From solid state to colloids. Phys. Rep. 2020;843:1–81. https://doi.
org/10.1016/j.physrep.2019.12.001.
[493] Lilley D, Menon AK, Kaur S, Lubner S, Prasher RS. Phase change materials for
thermal energy storage: a perspective on linking phonon physics to performance.
J. Appl. Phys. 2021;130(22). https://doi.org/10.1063/5.0069342.
[494] You A. Be, and I. In, “Normal-mode analysis of liquid-state dynamics 1998;5581
(August).
[495] Lin ST, Blanco M, Goddard WA. The two-phase model for calculating
thermodynamic properties of liquids from molecular dynamics: Validation for the
phase diagram of Lennard-Jones fluids. J. Chem. Phys. 2003;119(22):11792–805.
https://doi.org/10.1063/1.1624057.
[496] Bolmatov D, Brazhkin VV, Trachenko K. The phonon theory of liquid
thermodynamics. Sci. Rep. 2012;2:1–6. https://doi.org/10.1038/srep00421.
[497] M. F. Modest, RADIATIVE HEAT TRANSFER, no. January 2010. 2014.
[498] Tapimo R, Kamdem HTT. A spherical harmonic formulation for radiative heat
transfer analysis. Am. J. Heat Mass Transf. 2016;3(4):280–95. https://doi.org/
10.7726/ajhmt.2016.1016.
[499] Thynell ST. Discrete-ordinates method in radiative heat transfer. Int. J. Eng. Sci.
1998;36(12–14):1651–75. https://doi.org/10.1016/s0020-7225(98)00052-4.
[500] Ebrahimi H, Zamaniyan A, Soltan Mohammadzadeh JS, Khalili AA. Zonal
modeling of radiative heat transfer in industrial furnaces using simplified model
for exchange area calculation. Appl. Math. Model. 2013;37(16–17):8004–15.
https://doi.org/10.1016/j.apm.2013.02.053.
[501] Howell JR. Application of Monte Carlo to Heat Transfer Problems. Adv. Heat
Transf. 1969;5(C):1–54. https://doi.org/10.1016/S0065-2717(08)70128-X.
[502] Radiative_Transfer(BookFi.org).
[503] Oubre C, Nordlander P. Optical properties of metallodielectric nanostructures
calculated using the finite difference time domain method. J. Phys. Chem. B 2004;
108(46):17740–7. https://doi.org/10.1021/jp0473164.
[504] Duan H, Xuan Y. Enhanced optical absorption of the plasmonic nanoshell
suspension based on the solar photocatalytic hydrogen production system. Appl.
Energy 2014;114:22–9. https://doi.org/10.1016/j.apenergy.2013.09.035.
[505] Z. Huang, J. Bai, and P. Luo, “Investigation on optical theoretical models of SiO2
nanofluids,” vol. 134, no. Ismems 2017, pp. 108–113, 2018, doi: 10.2991/
ismems-17.2018.26.
[506] G. Ellison, “Thermal Radiation Heat Transfer,” Thermal Computations for
Electronics. pp. 219–262, 1992, doi: 10.1201/b12772-12.
[507] Hottel HC, Sarofim AF, Dalzell WH, Vasalos IA. Optical properties of coatings.
Effect of pigment concentration. AIAA J 1971;9(10):1895–8. https://doi.org/
10.2514/3.49999.
[508] Brewster Q. Volume scattering of radiation in packed beds of large, opaque
spheres. J. Heat Transfer 2004;126(6):1048–50. https://doi.org/10.1115/
1.1795247.
[509] Jing D, Song D. Optical properties of nanofluids considering particle size
distribution: Experimental and theoretical investigations. Renew. Sustain. Energy
Rev. 2017;78(March):452–65. https://doi.org/10.1016/j.rser.2017.04.084.
[510] M. Quinten, Optical Properties of Nanoparticle Systems: Mie and beyond. 2011.
[511] Bohren CF. Absorption and scattering of light by small particles. Absorpt. Scatt.
Light by small Part. 1983. https://doi.org/10.1088/0031-9112/35/3/025.
[512] Yazdanifard F, Ameri M, Taylor R. Parametric investigation of a nanofluid-
NEPCM based spectral splitting photovoltaic/thermal system. Energy Convers.
Manag. 2021;240(May):114232. https://doi.org/10.1016/j.
enconman.2021.114232.
[513] Barber P, Yeh C. Scattering of electromagnetic waves by arbitrarily shaped
dielectric bodies. Appl. Opt. 1975;14(12):2864. https://doi.org/10.1364/
ao.14.002864.
[514] Yee Kane. Numerical solution of initial boundary value problems involving
maxwell’s equations in isotropic media. Theory Appl. Transp. Porous Media 1966;
30:141–7. https://doi.org/10.1007/978-3-319-61185-3_17.
[515] Goodman JJ, Flatau PJ, Draine BT. Application of fast-Fourier-transform
techniques to the discrete-dipole approximation. Opt. Lett. 1991;16(15):1198.
https://doi.org/10.1364/ol.16.001198.
[516] Draine BT, Flatau PJ. Discrete-Dipole Approximation For Scattering Calculations.
J. Opt. Soc. Am. A 1994;11(4):1491. https://doi.org/10.1364/josaa.11.001491.
[517] B. T. Draine and P. J. Flatau, “User Guide for the Discrete Dipole Approximation
Code DDSCAT 6.1,” 2004, [Online]. Available: http://arxiv.org/abs/astro-ph
/0409262.
[518] Donald JMc, Golden A, Jennings SG. Opendda: a novel high-performance
computational framework for the discrete dipole approximation. Int. J. High
Perform. Comput. Appl. 2009;23(1):42–61. https://doi.org/10.1177/
1094342008097914.
[519] Du M, Tang GH. Optical property of nanofluids with particle agglomeration. Sol.
Energy 2015;122:864–72. https://doi.org/10.1016/j.solener.2015.10.009.
S.A. Albdour et al.
[520] lin Xu Y. Radiative scattering properties of an ensemble of variously shaped small
particles. Phys. Rev. E - Stat. Physics, Plasmas, Fluids, Relat. Interdiscip. Top.
2003;67(4):9. https://doi.org/10.1103/PhysRevE.67.046620.
[521] Egel A, Pattelli L, Mazzamuto G, Wiersma DS, Lemmer U. CELES: CUDA-
accelerated simulation of electromagnetic scattering by large ensembles of
spheres. J. Quant. Spectrosc. Radiat. Transf. 2017;199:103–10. https://doi.org/
10.1016/j.jqsrt.2017.05.010.
[522] Mosaffa AH, Garousi Farshi L, Infante Ferreira CA, Rosen MA. Energy and exergy
evaluation of a multiple-PCM thermal storage unit for free cooling applications.
Renew. Energy 2014;68:452–8. https://doi.org/10.1016/j.renene.2014.02.025.
[523] Yu Q, et al. Numerical study on energy and exergy performances of a
microencapsulated phase change material slurry based photovoltaic/thermal
module. Energy Convers. Manag. 2019;183(February):708–20. https://doi.org/
10.1016/j.enconman.2019.01.029.
[524] Eisapour M, Eisapour AH, Hosseini MJ, Talebizadehsardari P. Exergy and energy
analysis of wavy tubes photovoltaic-thermal systems using microencapsulated
PCM nano-slurry coolant fluid. Appl. Energy 2020;266(March):114849. https://
doi.org/10.1016/j.apenergy.2020.114849.
[525] Du X, Wang S, Du Z, Cheng X, Wang H. Preparation and characterization of flame-
retardant nanoencapsulated phase change materials with poly
(methylmethacrylate) shells for thermal energy storage. J. Mater. Chem. A 2018;6
(36):17519–29. https://doi.org/10.1039/c8ta07086e.
[526] Zhang XX, Fan YF, Tao XM, Yick KL. Crystallization and prevention of
supercooling of microencapsulated n-alkanes. J. Colloid Interface Sci. 2005;281
(2):299–306. https://doi.org/10.1016/j.jcis.2004.08.046.
[527] Sami S, Sadrameli SM, Etesami N. Thermal properties optimization of
microencapsulated a renewable and non-toxic phase change material with a
polystyrene shell for thermal energy storage systems. Appl. Therm. Eng. 2018;
130:1416–24. https://doi.org/10.1016/j.applthermaleng.2017.11.119.
[528] Ni J, Tai Q, Lu H, Hu Y, Song L. Microencapsulated ammonium polyphosphate
with polyurethane shell: Preparation, characterization, and its flame retardance
in polyurethane. Polym. Adv. Technol. 2010;21(6):392–400. https://doi.org/
10.1002/pat.1441.
[529] Sun K, Liu H, Wang X, Wu D. Innovative design of superhydrophobic thermal
energy-storage materials by microencapsulation of n-docosane with
nanostructured ZnO/SiO2 shell. Appl. Energy 2019;237(August 2018):549–65.
https://doi.org/10.1016/j.apenergy.2019.01.043.
[530] Gao F, Wang X, Wu D. Design and fabrication of bifunctional microcapsules for
solar thermal energy storage and solar photocatalysis by encapsulating paraffin
phase change material into cuprous oxide. Sol. Energy Mater. Sol. Cells 2017;168
(October 2016):146–64. https://doi.org/10.1016/j.solmat.2017.04.026.
[531] Zhang Y, Wang X, Wu D. Microencapsulation of n-dodecane into zirconia shell
doped with rare earth: Design and synthesis of bifunctional microcapsules for
photoluminescence enhancement and thermal energy storage. Energy 2016;97:
113–26. https://doi.org/10.1016/j.energy.2015.12.114.
[532] Latibari ST, Mehrali M, Mehrali M, Mahlia TMI, Metselaar HSC. Fabrication and
performances of microencapsulated palmitic acid with enhanced thermal
properties. Energy and Fuels 2015;29(2):1010–8. https://doi.org/10.1021/
ef502840f.
[533] Zhao D, et al. Rapid Preparation of TiO2- x and Its Photocatalytic Oxidation for
Arsenic Adsorption under Visible Light. Langmuir 2020;36(14):3853–61. https://
doi.org/10.1021/acs.langmuir.9b02444.
[534] Wu X, Jiang Q, Ghim D, Singamaneni S, Jun YS. Localized heating with a
photothermal polydopamine coating facilitates a novel membrane distillation
process. J. Mater. Chem. A 2018;6(39):18799–807. https://doi.org/10.1039/
c8ta05738a.
[535] Fan X, Qiu X, Lu L, Zhou B. Full-spectrum light-driven phase change
microcapsules modified by CuS-GO nanoconverter for enhancing solar energy
conversion and storage capability. Sol. Energy Mater. Sol. Cells 2021;223
(January):110937. https://doi.org/10.1016/j.solmat.2020.110937.
[536] Tang B, Wang Y, Qiu M, Zhang S. A full-band sunlight-driven carbon nanotube/
PEG/SiO2 composites for solar energy storage. Sol. Energy Mater. Sol. Cells 2014;
123:7–12. https://doi.org/10.1016/j.solmat.2013.12.022.
[537] Zhang Y, Li X, Li J, Ma C, Guo L, Meng X. Solar-driven phase change
microencapsulation with efficient Ti4O7 nanoconverter for latent heat storage.
Nano Energy 2018;53(August):579–86. https://doi.org/10.1016/j.
nanoen.2018.09.018.
[538] Stankovich S, et al. Synthesis of graphene-based nanosheets via chemical
reduction of exfoliated graphite oxide. Carbon N. Y. 2007;45(7):1558–65.
https://doi.org/10.1016/j.carbon.2007.02.034.
[539] Peng Q, De S. Mechanical properties and instabilities of ordered graphene oxide C
6O monolayers. RSC Adv 2013;3(46):24337–44. https://doi.org/10.1039/
c3ra44949a.
[540] Nair RR, Wu HA, Jayaram PN, Grigorieva IV, Geim AK. Unimpeded permeation of
water through helium-leak-tight graphene-based membranes. Science 2012;335
(6067):442–4. https://doi.org/10.1126/science.1211694 (80-.).
[541] Kim J, Cote LJ, Kim F, Yuan W, Shull KR, Huang J. Graphene oxide sheets at
interfaces. J. Am. Chem. Soc. 2010;132(23):8180–6. https://doi.org/10.1021/
ja102777p.
[542] Maithya OM, et al. High-energy storage graphene oxide modified phase change
microcapsules from regenerated chitin Pickering Emulsion for photothermal
conversion. Sol. Energy Mater. Sol. Cells 2021;222(May 2020):110924. https://
doi.org/10.1016/j.solmat.2020.110924.
[543] Goel N, Taylor RA, Otanicar T. A review of nanofluid-based direct absorption
solar collectors: Design considerations and experiments with hybrid PV/Thermal
86
Progress in Energy and Combustion Science 93 (2022) 101037
and direct steam generation collectors. Renew. Energy 2020;145(2020):903–13.
https://doi.org/10.1016/j.renene.2019.06.097.
[544] Zain M, et al. Performance Investigation of a Solar Thermal Collector Based on
Nanostructured Energy Materials. Front. Mater 2021;7(January):1–9. https://doi.
org/10.3389/fmats.2020.617199.
[545] Sharaf OZ, Al-Khateeb AN, Kyritsis DC, Abu-Nada E. Direct absorption solar
collector (DASC) modeling and simulation using a novel Eulerian-Lagrangian
hybrid approach: Optical, thermal, and hydrodynamic interactions. Appl. Energy
2018;231(July):1132–45. https://doi.org/10.1016/j.apenergy.2018.09.191.
[546] Kapsalis V, Karamanis D. Solar thermal energy storage and heat pumps with
phase change materials. Appl. Therm. Eng. 2016;99:1212–24. https://doi.org/
10.1016/j.applthermaleng.2016.01.071.
[547] Imenes AG, Mills DR. Spectral beam splitting technology for increased conversion
efficiency in solar concentrating systems: a review. Sol. Energy Mater. Sol. Cells
2004;84(1–4):19–69. https://doi.org/10.1016/j.solmat.2004.01.038.
[548] Yazdanifard F, Ameri M, Ebrahimnia-Bajestan E. Performance of nanofluid-based
photovoltaic/thermal systems: a review. Renew. Sustain. Energy Rev. 2017;76
(July):323–52. https://doi.org/10.1016/j.rser.2017.03.025.
[549] An W, Wu J, Zhu T, Zhu Q. Experimental investigation of a concentrating PV/T
collector with Cu9S5 nanofluid spectral splitting filter. Appl. Energy 2016;184:
197–206. https://doi.org/10.1016/j.apenergy.2016.10.004.
[550] Crisostomo F, Hjerrild N, Mesgari S, Li Q, Taylor RA. A hybrid PV/T collector
using spectrally selective absorbing nanofluids. Appl. Energy 2017;193:1–14.
https://doi.org/10.1016/j.apenergy.2017.02.028.
[551] Su D, Jia Y, Alva G, Liu L, Fang G. Comparative analyses on dynamic
performances of photovoltaic–thermal solar collectors integrated with phase
change materials. Energy Convers. Manag. 2017;131:79–89. https://doi.org/
10.1016/j.enconman.2016.11.002.
[552] Goia F, Zinzi M, Carnielo E, Serra V. Spectral and angular solar properties of a
PCM-filled double glazing unit. Energy Build 2015;87:302–12. https://doi.org/
10.1016/j.enbuild.2014.11.019.
[553] Manz H, Egolf PW, Suter P, Goetzberger A. TIM-PCM external wall system for
solar space heating and daylighting. Sol. Energy 1997;61(6):369–79. https://doi.
org/10.1016/S0038-092X(97)00086-8.
[554] Yazdanifard F, Ameri M, Taylor RA. Numerical modeling of a concentrated
photovoltaic/thermal system which utilizes a PCM and nanofluid spectral
splitting. Energy Convers. Manag. 2020;215(May):112927. https://doi.org/
10.1016/j.enconman.2020.112927.
[555] Bell S, Steinberg T, Will G. Corrosion mechanisms in molten salt thermal energy
storage for concentrating solar power. Renew. Sustain. Energy Rev. 2019;114
(July):109328. https://doi.org/10.1016/j.rser.2019.109328.
[556] Zhou WJ, Luan HB, Sun J, He YL, Tao WQ. A molecular dynamics and lattice
Boltzmann multiscale simulation for dense fluid flows. Numer. Heat Transf. Part B
Fundam 2012;61(5):369–86. https://doi.org/10.1080/10407790.2012.666144.
[557] Tao YB, He YL. A review of phase change material and performance enhancement
method for latent heat storage system. Renew. Sustain. Energy Rev. 2018;93
(May):245–59. https://doi.org/10.1016/j.rser.2018.05.028.
[558] Liu C, Rao Z, Zhao J, Huo Y, Li Y. Review on nanoencapsulated phase change
materials: Preparation, characterization and heat transfer enhancement. Nano
Energy 2015;13:814–26. https://doi.org/10.1016/j.nanoen.2015.02.016.
[559] Lee J, Jo B. Surfactant-free synthesis protocol of robust and sustainable molten
salt microcapsules for solar thermal energy storage. Sol. Energy Mater. Sol. Cells
2021;222(September 2020):110954. https://doi.org/10.1016/j.
solmat.2020.110954.
[560] Zhang H, Shin D, Santhanagopalan S. Microencapsulated binary carbonate salt
mixture in silica shell with enhanced effective heat capacity for high temperature
latent heat storage. Renew. Energy 2019;134:1156–62. https://doi.org/10.1016/
j.renene.2018.09.011.
[561] Li J, Li L, Wang H, Zhu X, Chen Y, Jia L. Microencapsulation of Molten Salt in
Titanium Shell for High-Temperature Latent Functional Thermal Fluid. Energy
Technol 2020;8(12). https://doi.org/10.1002/ente.202000550.
[562] Ganzenmüller GC, Hiermaier S, Steinhauser MO. Consistent Temperature
Coupling with Thermal Fluctuations of Smooth Particle Hydrodynamics and
Molecular Dynamics. PLoS One 2012;7(12). https://doi.org/10.1371/journal.
pone.0051989.
[563] Werder T, Walther JH, Koumoutsakos P. Hybrid atomistic-continuum method for
the simulation of dense fluid flows. J. Comput. Phys. 2005;205(1):373–90.
https://doi.org/10.1016/j.jcp.2004.11.019.
[564] X. Y. Jie Sun HW, He Yaling, Tao Wenquan. Roughness effect on flow and thermal
boundaries in microchannel/nanochannel flow using molecular dynamics-
continuum hybrid simulation Int. J. Numer. Methods Eng. 2011;(February):
1102–19. https://doi.org/10.1002/nme.
[565] ABRAHAM FARID F. DYNAMICALLY SPANNING THE LENGTH SCALES FROM
THE QUANTUM TO THE CONTINUUM. Int. J. Mod. Phys. 2000;11(6):1135–48.
[566] Dupuis A, Kotsalis EM, Koumoutsakos P. Coupling lattice Boltzmann and
molecular dynamics models for dense fluids. Phys. Rev. E - Stat. Nonlinear, Soft
Matter Phys. 2007;75(4). https://doi.org/10.1103/PhysRevE.75.046704.
Ms. Samah Albdour is a PhD candidate in Mechanical Engineering at Khalifa University
working under supervision of Dr. Abu-Nada and Dr. Alazzam. She got her MSc from
Kyungpook National University in South Korea. Her research topic in the PhD is in the area
of phase change material and numerical simulation/modeling.
Dr. Zoubida Haddad is an associate professor at the Superior National School of Marine
Science and Coastal Planning (ENSSMAL) in Algeria. She is an alumna of Ecole
S.A. Albdour et al. Progress in Energy and Combustion Science 93 (2022) 101037

Polytechnique, Université d’Aix-Marseille, France. Her recent research interests are in international patents. His research expertise in microfluidics, nanofluids, Dielectropho­
phase change materials, energy storage, heat transfer, porous media, nanofluids and nu­ resis, graphene, and healthcare applications of microdevices. His research in the BioMEMS
merical simulations. area has received substantial recognition in the form of awards and media appearance. He
has been the Principal Investigator of numerous research projects with budgets exceeding
$2 million. He has served as the advisor to numerous PhD and MSc students and post­
Dr. Omar Sharaf is a Post-Doc fellow at Khalifa Univesity. His research includes solar
doctoral fellows. Dr. Alazzam is a member of the editorial board of Micromachines and
photothermal conversion, colloidal dispersions, particle-laden flow, hybrid continuum-
PLOS ONE Journals.
discrete modeling, integrated energy systems, CSP and solar polygeneration systems,
concentrated photovoltaic-thermal (CPVT) solar collectors, hydrogen systems and fuel-
cells, and thermoelectric generators. Dr. Eiyad Abu-Nada is a Full Professor of Mechanical Engineering in the Department of
Mechanical Engineering at Khalifa University in Abu Dhabi, UAE. He joined Khalifa
University in 2013. Prior to that, he worked as a Full Professor at King Faisal University in
Dr. Anas Alazzam is an alumna of Concordia University – Montreal. After a brief Post-
Saudi Arabia and Associate Professor at Hashemite University in Jordan. Dr. Abu-Nada is
Doctoral Fellow appointment with the Canadian Space Agency, he joined Khalifa Uni­
an Alexander von Humboldt Fellow and a recipient of Abdul-Hameed Shoman Award in
versity in 2012. He is currently an associate professor of Mechanical Engineering and the
Jordan. Also, he received the Distinguished Scholar Award from the Arab Fund in Kuwait.
head of the microfluidics lab at Khalifa University. In addition, he is a visiting associate
His recent research interests are in nanofluid heat transport and microfluidics simulations.
professor in the department of electrical engineering at École de technologie supérieure
ÉTS. Dr. Alazzam has more than one hundred peer-reviewed publications and a number of

87