Energy Conversion and Management 124 (2016) 598–606

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Energy Conversion and Management

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

Quality criteria for phase change materials selection

Nuno Vitorino a,⇑, João C.C. Abrantes a,b, Jorge R. Frade a
a
CICECO – Aveiro Institute of Materials, University of Aveiro, 3810 Aveiro, Portugal
b
UIDM, ESTG, Polytechnic Institute of Viana do Castelo, 4900 Viana do Castelo, Portugal

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

Article history: Selection guidelines are primary criterion for optimization of materials for specific applications in order
Received 11 November 2015 to meet simultaneous and often conflicting requirements. This is mostly true for technologies and prod-
Received in revised form 22 July 2016 ucts required to meet the main societal needs, such as energy. In this case, gaps between supply and
Accepted 23 July 2016
demand require strategies for energy conversion and storage, including thermal storage mostly based
Available online 28 July 2016
on phase change materials. Latent heat storage is also very versatile for thermal management and
thermal control by allowing high storage density within narrow temperature ranges without strict
Keywords:
dependence between stored thermal energy and temperature. Thus, this work addressed the main issues
Quality criteria
PCM selection
of latent heat storage from a materials selection perspective, based on expected requirements of
Thermal energy storage applications in thermal energy storage or thermal regulation. Representative solutions for the kinetics
PCM applications of latent heat charge/discharge were used to derive optimization guidelines for high energy density, high
power, response time (from fast response to thermal inertia), etc. The corresponding property relations
were presented in graphical forms for a wide variety of prospective phase change materials, and for wide
ranges of operating conditions, and accounting for changes in geometry and mechanisms.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction transient loading and unloading of sensible heat in heavy struc-

Limitations of fossil fuels and other primary energy sources
combined with their environmental impact have stimulated
increasing emphasis on renewable energies in order to sustain
the development and quality of life in modern societies, without
excessive environmental impact. Emphasis on renewable energies
also imply ability to develop strategies of conversion and storage to
bridge gaps between energy harvesting and consumption. This is
the case of solar heat stored as latent heat in phase change
materials for heating or cold storage for air conditioning, which
represent important fractions of total energy needs for domestic,
office and industrial levels, often relying on combustion of fossil
fuels or valuable electricity, due to its widespread distribution.
Consumption of these energies may be minimized by alternative
concepts of storage, regulation and management.
Though solar heat represents about 50% of the solar spectrum,
its effective use is limited by gaps between daytime and night,
often varying from heat excess in daytime hours to cold nights.
Classical concepts to overcome these deviations from the comfort
range have relied on thermal isolation with highly porous
materials, double or multiple windows, or thermal inertia, with
⇑ Corresponding author.
E-mail address: nuno.vitorino@ua.pt (N. Vitorino).
tures (e.g. thick stone walls). Still, these strategies have limited
heat storage flexibility if one seeks minimum temperature
fluctuations for precise thermal regulation and management. Thus,
representative applications of phase change materials include
thermal management in buildings, by incorporation of phase
change materials in bricks [1] or as a component of composites
[2]. Other identified applications can be found in relevant reviews
[3] and are summarized in Table 1, often based on encapsulated
phase change materials [4] to minimize undue interaction with
the surrounding media. In this case, the dynamics of heat transfer
may include limitations imposed by low thermal conductivity of
paraffins [5] and most organic phase change materials, in series
with additional limitations imposed by encapsulating materials
and/or heat transfer to a cooling fluid or surrounding medium, as
discussed below. Attempts to enhance performance also comprise
a variety of experimental developments combined with modelling
[6], as often used for applications of PCM materials in cold storage
[7]. Prospective application of latent heat storage materials has
also been proposed for cooking in developing countries with hot
climate, to extend the versatility of solar kilns [8].
Phase change materials also find applicability in thermal
management, as required for pharmaceutical products [9] or heat
sensitive electronics [10], and to sustain other exothermic
processes. In these cases, requirements of fast heat dissipation lead

http://dx.doi.org/10.1016/j.enconman.2016.07.063
0196-8904/Ó 2016 Elsevier Ltd. All rights reserved.
 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606
Table 1
Summary of main requirements for different PCM applications.
Application Requirements
Amount of stored energy/thermal inertia
Climatization/thermal comfort in:
(i) Buildings [1,2];
(ii) Vehicles [3,4];
(iii) Greenhouse [5,6];
(iv) Air conditioning [7]
Solar kiln [8,9]
Thermal protection of:
(i) Food [4,10];
(ii) Medical products/equipment [9,10];
(iii) Electronic devices [9,10].
Energy storage for:
(i) Solar systems [11,12];
(ii) Sanitary hot water [11–13];
(iii) Ice banks [4,14];
(iv) Central solar for energy production [4,10].
Power dissipation in:
(i) Electronic systems [15,16];
(ii) Exothermic chemical reactions [9,10].
to different strategies to enhance thermal conductivity, based on
incorporation of conducting phases with different geometries
[11]. Other applications depend mainly on high storage ability, as
required to support hot water systems [12], and to minimize tem-
perature decrease at night [13]. In fact, latent heat storage in phase
change materials offers advantages in terms of power density and
prospects for heat discharge under nearly isothermal conditions.
Applicability in sub-zero or even cryogenic conditions [14]
includes prospects to sustain power failures or intermittent renew-
able electricity in refrigeration. These applications also require
high storage ability and differ from the requirement of fast dissipa-
tion of short heat peaks in electronics, which may rely on additions
of lightweight conducting phases such as carbon foams [15] and/or
carbon nanotubes [16] to enhance thermal conductivity of phase
change materials.
The representative applications listed in Table 1 are classified
for their main requirements of (i) stored energy or thermal inertia,
(ii) discharge power and (iii) discharge time. This must be taken
into account for the purpose of materials selection in the develop-
ment of engineering concepts and commercial products, to seek
high efficiency, robustness and viability of the products. Selection
is based on previous identification of relevant thermophysical
properties, such as latent heat, thermal conductivity and melting
temperature, and their interactions in representative quality
criteria. Thermophysical properties may also be optimized in order
to minimize size or weight of storage systems, and to lower
charge/discharge times in high power appliances. Other applica-
tions require thermal inertia (e.g. transportation of temperature
sensitive products such as food and blood), or PCM materials for
temperature regulation upon temporary failure of the normal
supporting equipment (e.g. refrigerators with frequent power
cuts). Selection of PCM materials may also be extended to account
for differences in unit cost, encapsulation and other processing
costs, as well as other relevant issues of durability, safety, corro-
sion, environmental impact, etc.
Quality criteria of phase change materials for specific
requirements should also be as simple as possible to ensure facile
implementation. Still, these criteria must be based on sound
descriptions of the dynamics of solidification and melting, as
known for the classical heat conduction solution for planar geom-
etry [17]. This model behavior does not account for slow nucle-
ation of the transformed phase causing undercooling on freezing
or overheating on melting, and also fails to describe the impact
of encapsulation with poorly conducting materials, or limited heat
599
Discharge power Discharge time
U
U
U
U U
U
transfer coefficients to heat transfer fluids. These conditions of
mixed control require alternative numerical methods [14].
Reliable numerical methods are needed for other representative
geometries, as shown by the schematic representations in Fig. 1,
with emphasis on spherical symmetry, as commonly utilized for
encapsulated PCM materials [15], or cylindrical symmetry. Still,
these numerical solutions are ill-suited for ready applicability in
selection procedures, thus requiring simpler approximate solutions
for charge/discharge rate, such as quasi-steady-state solutions for
discharge time, as summarized in Table 2. These are expressed as
a function of relevant physical properties (density, latent heat
and thermal conductivity), combined with a representative encap-
sulation size, the temperature difference acting as the driving-
force. A scaling factor is also introduced for differences in geometry
of encapsulation which depends on dimensionality, and also to
account for mixed control, as shown below.
The kinetics of charge/discharge of latent heat is the basis for
materials selection based on suitable combinations of thermophys-
ical properties of PCM materials, as proposed by Ashby [18] and
guided by sound kinetic models of latent heat charge/discharge
for different geometries, such as flat slab geometry [19] or spheri-
cal encapsulation [19,20]. Information on relevant physical proper-
ties for a wide variety of PCM materials is available online [21], and
may be used to generate the required quality maps for PCM selec-
tion intended for applications with specific requirements of high
energy density, high power or response time.
The main objective of this work is, thus, focused on guidelines
for selection of PCM materials. Selection criteria are based on
sound solutions for the dynamics of latent heat charge or dis-
charge, under conditions imposed by representative types of appli-
cations. These criteria are the basis to compile performance maps
containing a wide variety of PCM materials; this is quite diverse
from recent reviews, which were focused on general decision
making in energy conversion and managements, without corre-
sponding selection maps [22].
Performance maps may be designed to assist selection of PCM
materials for established applications requiring high energy den-
sity, such as residential thermal management, as well proposals
to enhance the efficiency of other solar energy-based processes
such as desalination in dry hot climates [23].
Similarly, performance maps for fast discharge time or high
power provide selection guidelines to extend the applicability of
phase change materials to novel energy conversion systems [24].
These maps were designed to be user friendly, accounting for
600 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606

(A) L – container thickness; X – solid PCM (B) Rw – container external radius; R – Reservoir
thickness; Xmax – maximun solid PCM radius; r – radial distance from the center of the
thickness. spherical reservoir, rSL – solid/liquid radial distance.
Fig. 1. Schematic representation of a PCM solidification in planar (A) and spherical (B) capsule.

Table 2 10000
Organics Inorganics
Quasi steady state solutions for discharge time in planar, cylindrical and spherical Commercial Climator and Rubitherm
Eutetic mixtures
λ / MJ m-3

configurations, including mixed control. Commercial Eutetic "EPSLTD"

Commercial hydrated salts"EPSLTD"
Commercial high temperature "EPSLTD"
Commercial Organics "EPSLTD"
Discharge time Metals



2 
Planar qk X
tdisch
0:5 þ kkL þ hX
k
Volumetric latent heat, ρλ

wX k DT 1000
h i

2 
Cylindrical qk
tdisch
0:25 þ Rkw lnð1þL=RÞ
0:5kL
þ hRð1þL=RÞ
0:5k
k
R
DT
h i

2 
Spherical qk
tdisch
0:1667 þ kw0:333k
ð1þR=LÞ
þ 0:333k R
DT
hRð1þL=RÞ2 k

100

diverse combinations of operating conditions, geometry, and dif-

ferent regimes of heat transfer from control by heat conduction
to mixed control [25], while retaining relatively simple depen-
10
dence on a minimum number of truly relevant parameters. Though 200 400 1000 2000
this is not designed for selection based on cost [26], this may also Melting temperature, Tm / K
be assessed by combining energy density maps with up to date
unit costs. Fig. 2. Volumetric energy density as a function of melting temperature, for some
PCM groups.

2. Selection of materials for high energy density requirements

One of the main advantages of PCM is their high latent heat
storage ability with minimum temperature changes; this is most
relevant for applications with energy density requirements, such
as thermal buffers. In these cases, one may still distinguish
selection criteria for applications with preferential conditions for
minimum mass, (i.e. maximum latent heat per unit mass (k) or
minimum volume qk), while meeting also a required range of
working temperatures. For example, cold storage temperatures
are very different from high temperature thermal management
and also significantly different from heating requirements. Thus,
maps of qk vs melting temperature Tm, Fig. 2, are required for gen-
eric selection purposes. Fig. 2 also distinguishes the energy density
as a function of melting temperature for different PCM types, to be
able to include guidelines for additional constraints, such as ther-
mochemical stability, which may be a critical issue mostly for
specific types of materials (e.g. organic PCM). Other specific issues
may be related to compatibility with encapsulating materials and
highly heat conducting inclusions (e.g. salt PCM in contact with
metallic containers or fins), or degradation on attempting direct
contact of PCM with heat transfer fluids (e.g. metallic PCM in
contact with humidity or with traces of oxidizing gases). Note also
that the highest heat storage ability of metallic and inorganic PCMs
can be related to their high densities, and does not represent a true
advantage if one seeks high storage per unit mass. In this case,
selection should be based on maps of latent that versus melting
temperature, as shown in Fig. 3, which is more suitable if one seeks
minimum weight.
Data in the selection maps (Figs. 2 and 3) may also be readily
adjusted if one seeks cost minimization, except possibly for condi-
tions when high power requirements impose increasing encapsu-
lation costs, as emphasized below. In addition, unit costs are
often very dependent on purity and/or scale of production of com-
mercial PCM. Thus, cost minimization is not taken as a primary
selection criterion in this work, mainly because current unit costs
may be misleading at early stages of PCM-based technologies.
A representative application with energy density requirements
is the stabilization of building temperature against high thermal
amplitudes, by incorporating a PCM inclusions inside building
walls. The melting temperature of the PCM material may be
adjusted to a target comfort temperature with the ability to store
incoming heat while the external temperature remains above the

10000
Organics
Eutetic mixtures
Commercial Eutetic "EPSLTD"
Latent heat, λ / kJ kg-1
Commercial Organics "EPSLTD"
Metals
1000
100
10
200 400
Melting temperature, Tm / K
Fig. 3. Energy density maps as a function of melting temperatures.
target temperature, and to discharge latent heat as the external
temperature falls below the target value. Representative ranges
may be assessed by considering an external building area of
200 m2, with a heat transfer coefficient of 0.35–0.45 W m2 K1.
Power requirements to sustain external thermal amplitudes from
about 15 °C below the comfort temperature to 15 °C above comfort
temperature may also be assumed in the range 1000–1400 W,
which corresponds to storage of about 38–48 MJ to ensure thermal
stabilization for up to 10 h. Thus, the PCM energy density should be
at least 20 MJ m3 to fulfill the stated requirements, if one assumes
incorporation of a 1 cm thick PCM layer along the building wall.
Though comfort temperatures inside the building may still be
set in a relatively wide range (i.e., 15–25 °C [3,10,27]), this is still
much narrower than the range of melting temperatures of PCM
materials presented in Figs. 2 and 3. Thus, this reduces the range
of prospective PCM materials for stabilization of room tempera-
tures, and their diversity. Organic compounds are most promising,
as shown in Fig. 4. These PCMs retain high chemical stability at
room temperatures and are also highlighted by their low corrosive
nature [9,28]. Many of these compounds (e.g. paraffins) are also
susceptible of mass production at relatively low cost, thus raising
good prospects as PCM for thermal regulation or other applications
based on latent heat storage [9].
Volumetric or mass restrictions may also need a revision for
specific requirements of other concerns such as encapsulation or
incorporation in building wall materials or structures, as found
for a variety of different approaches, such as:
1000
λ / MJ m-3
Volumetric latent heat, ρλ
100
10
285 295
Melting temperature, Tm / K
Fig. 4. Volumetric energy density as a function of melting point of some PCM
groups, with melting temperature limited to 15–25 °C.
N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606 601
(i) Impregnation of gypsum [27,29], concrete [27], wood
Inorganics
Commercial Climator and Rubitherm
[27,30] and porous materials with a suitable PCM in liquid
Commercial hydrated salts "EPSLTD" phase, which may be affected by severe interactions
between the PCM and its porous container;
Commercial high temperature "EPSLTD"
(ii) Incorporation of micro-encapsulated PCM in a building con-
struction materials [27,29,31], usually with relatively low
fraction of encapsulated PCM (<20%) [32];
(iii) shape-stabilization in the form of a gel, containing a liquid
mixture of PCM and a supporting material such as high den-
sity polyethylene (HDPE) or styrene-butadiene-styrene (SBS)
[33,34], with corresponding decrease in the effective fraction
of PCM and its heat storage ability;
(iv) Incorporation in aluminium or polyvinyl chloride (PVC) con-
tainers [27], to retain high thermal storage, possibly with
1000 2000 impact on rate of latent heat charge and discharge.
These solutions are not included in Fig. 4 due to the lack of sys-
tematic information on thermophysical properties of encapsulat-
ing materials. However, encapsulation should affect mainly the
dynamics of heat transfer rather than the storage ability. Thus,
materials selection for high thermal storage ability may still be
based on maps shown in Figs. 2–4.
3. Selection criteria for power requirements
The dynamics of phase changes and corresponding charge/dis-
charge of latent heat is also often limited by the low thermal con-
ductivity of most PCM. Thus, one must consider different
optimization guidelines to select PCM intended for applications
with high discharge power requirements. Selection must be based
on sound solutions describing the kinetics of latent heat charge/
discharge, for relevant geometries (planar, cylindrical and spheri-
cal). One should also seek extension of basic methods to account
for mixed control, rather than heat conduction only. Yet, this must
rely on relatively simple relations for facile implementation of per-
formance maps. These guidelines are based on clear physical crite-
ria, with emphasis on relevant dimensionless parameters [27], as
demonstrated below.
3.1. Basic selection criteria for control by heat conduction
A criterion for relevant factors on the dynamics of latent heat
discharge with planar geometry may be the approximate quasi
steady state solution of discharge time [19]:
X 2 qk
tdisch
0:5 ð1Þ
kDT
where X is the thickness, k thermal conductivity, DT temperature
difference, k latent heat and q density. This shows that discharge
time combines effects of PCM thermophysical properties, geometry
and operating conditions. Note also that the inverse of the discharge
time corresponds to a (discharge power)/(stored latent heat) ratio,
as given by:
    
k@T
@x
 k DT 1


ð2Þ
X qk qk X 2 t disch
Organics Thus, k=ðqkÞ corresponds to the power/storage ratio per unit tem-
Inorganics
Eutetic Mixtures perature difference and per unit encapsulation size; This yields a
Commercial"Climator" suitable selection map based on logðkÞ vs logðqkÞ, if one considers
storage per unit volume, or logðk=qÞ vs logðkÞ for storage per unit
Commercial hydrated salts"EPSLTD"
Commercial Organics "EPSLTD"
mass (Fig. 5).
305 315 325
Meanwhile, the time required for complete discharge is mis-
leading during earlier stages because the rate decays sharply in
the final stage. Thus, PCM selection criteria should be based on
time required to attain half discharge of latent heat, which is best
602 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606

approximations were assumed to lead to these solutions, implying

10-5 10-6 10-7 that sensible heat should remain much smaller than latent heat,
10-8 i.e., C p DT  k; this is expected for most PCM with relatively low
-1
temperature differences (e.g. DT 6 10  C). Otherwise, one may
use a correction factor
1 þ ðC p DT=kÞ=3 which is related to the
log [(k/ρ)/(Wm2K-1kg-1)]

f X2/(t0.5ΔT); m2s-1K-1
actual value of the Stefan number / ¼ C p DT=k, as demonstrated
10-9
also in APPENDIX A.
-2
The selection criteria in Fig. 5 combines data for a wide variety
of PCM materials. In addition, inclined lines show expected
requirements to operate under representative conditions, i.e. for
typical combinations of encapsulation size X, half discharge time
-3 10-10 t0.5 and temperature difference, as illustrated in Table 4. Note that
X2/t0.5 is a measure of thermal diffusivity requirements for the
specified conditions of size and discharge time, with unit temper-
ature difference DT = 1 K. Note also that the required thermal dif-
-4
fusivity, for a specified energy density, increases with
4 5 6 7 encapsulation size X, which corresponds to increasing volume/area
log [λ/(J/kg)] ratio of PCM capsules, allowing decrease in encapsulation cost. In
Organics Inorganics this case, cost optimization may be a compromise between
Eutetic mixtures C.Climator and Rubitherm
decrease in encapsulation costs, and higher cost expected for mate-
C. Hydrated Salts "EPS LTD" C. Organics "EPS LTD"
C. High temperature "EPS LTD" Literature composites
rials with enhanced thermal conductivity, as required to upgrade
Our recent results Metals thermal properties of existing materials or to replace low cost
materials by higher grade PCM materials. Note also that the quad-
Fig. 5. Discharge power vs latent heat storage. The secondary vertical axis stands ratic dependence of size implies that thermal conductivity should
for combined requirements of time at half discharge, encapsulation size X and
increase by a factor of 100 if one seeks increased encapsulation size
temperature difference, f  X2/(t0.5DT) , where the scaling factor f accounting for
different geometries and different mechanisms (Table 3). from the millimetre to the centimetre range.
An alternative strategy may be based on PCM materials with
greater difference between their melting point and the required
suited to describe performance. This is also related to the same operating temperature, thus allowing increase in encapsulation
combination of thermophysical properties k=ðqkÞ, temperature dif- size. However, this is also likely to imply other risks such as ther-
ference and encapsulation size, as emphasized also by revising mal degradation, or disadvantages such as negative impact on effi-
quasi steady state solutions for half discharge: ciency of charging, by requiring higher temperature heat sources or
by lowering the temperature difference relative to the heat source,
X 2 qk thus affecting the rate of charging.
t 0:5
f ð3Þ
kDT Fig. 5 is also ill-suited to adjust the melting temperature to the
where f is a scaling factor which depends on geometry, with typical required range of operating temperatures. Thus, an alternative map
values f = 0.125 for flat slab, f = 0.03837 for cylindrical symmetry is shown in Fig. 6, to allow selection based on simultaneous
and f = 0.01837 for spherical symmetry, when discharge is con- requirements of fast discharge rate, while matching also specific
trolled by heat conduction, as detailed in APPENDIX A. Thus, one requirements of operating temperatures. In this case, one may
may rearrange Eq. (3) to obtain a generic selection map for PCM use the dependence of discharge power/storage ratio k=ðqkÞ (per
materials: unit size and unit temperature difference) vs melting temperature
  ! as a selection map for PCM materials intended to operate under
k X2 specific temperature ranges, i.e.:
log
logðkÞ þ log f ð4Þ
q t 0:5 DT   !
k X2
log
log f ð5Þ
The generic scaling factor f also allows one to account for other qk t 0:5 DT
constraints such as mixed control, as shown in Table 3; this may be
due to insufficient heat transfer coefficient to the surrounding heat The previous selection map is also suitable to emphasize alter-
transfer fluid (h), and/or low conductivity of encapsulating native guidelines for selection based on either high energy density
materials (kw), except possibly for very small wall thickness (L), requirements (along the horizontal direction in Fig. 5), high power
as detailed in APPENDIX A. Note also that quasi steady state requirements (along the vertical direction in Fig. 5) or simultane-
ous energy and power requirements, along diagonal lines in
Fig. 5, or at the top of Fig. 6. These maps can support the analysis
Table 3 of representative study cases, such as integration of PCM materials
Scaling factors for the generic solution to compute time at half discharge
t0:5
f  ðqk=kÞðX 2 =DTÞ where X denotes half thickness for flat slab configuration or
in hot water appliances, namely if one considers a thermal energy
radius (X = R) for cylindrical or spherical symmetries. L denotes the thickness of wall storage unit to suppress the transient initial regime. This may be
material, kw its thermal conductivity, h the heat transfer coefficient to the surround-
ing heat transfer fluid and e
ðC p DT=kÞ=3 is correction for quasi steady state Table 4
deviations. Representative ranges of conditions for discharge of latent heat.
Scaling factors (f) for half discharge X (mm) t0.5 (s) DT (K) X2/t0.5(m2 s1) X2/(t0.5DT) (m2 s1 K1)
Heat conduction Mixed control 10 103 10 107 108
Planar 0.125(1 + e) 0:125ð1 þ eÞ þ 0:5kL þ 0:5k 10 103 1 107 107
kw X hX
10 102 10 106 107
Cylindrical 0.03835(1 + e) 0:03835ð1 þ eÞ þ Rkw 0:25kL
lnð1þL=RÞ
þ hRð1þL=RÞ
0:25k 10 102 1 106 106
3.16 103 10 108 109
Spherical 0.01837(1 + e) 0:01837ð1 þ eÞ þ kw0:1667k
ð1þR=LÞ
þ 0:1667k
1 103 10 109 1010
hRð1þL=RÞ2
 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606 603

-5 10-5 10

-6 10-6 8
log {[(k/(ρλ)]/(m2s-1K-1)}

λ)]/(m2s-1K-1)
f X2/(tdischΔT)

= f X2/(t0.5ΔT)
-7 10-7 6

109 [(k/(ρλ
-8 10-8 4

-9 2
10-9

-10 0
0 200 400 600 800 20 40 60 80 100
Tm (ºC) Tm (ºC)
Organics Inorganics
Eutetic mixtures C.Climator and Rubitherm 300
C. Hydrated Salts "EPS LTD" C. Organics "EPS LTD"
C. High temperature "EPS LTD" Literature composites
B
Our recent results Metals

Fig. 6. Discharge power-storage selection maps vs melting temperature. The

secondary vertical axis shows combined requirements of half discharge time,
200
encapsulation size and temperature difference f  X2/(t0.5DT).
λ (kJ/kg)

located between the hot water appliance and the utilization point,
to minimize the initial transient time until the comfort tempera-
ture is reached, thus contributing to save energy and water. In this 100
example, typical requirements may be predicted for representative
values of half discharge time about 30 s, cold water inlet at 10 °C,
flow rate 10 L min1, and hot water delivered at 40 °C; this implies
requirements of latent heat storage is 1.26 MJ, and discharge
power of 21 kW. 0
On considering encapsulated PCM in cylindrical pipes with 1 cm 20 40 60 80 100
diameter and that latent heat discharge to flowing water occurs Tm (ºC)
under a typical temperature difference DT
10 °C one predicts Organics Inorganics
typical values of f R2 =ðt0:5 DTÞ in the range 108  109 m2 s1°C1. Eutetic mixtures C.Climator and Rubitherm
In addition, the melting temperature of the PCM materials should C. Hydrated Salts "EPS LTD" C. Organics "EPS LTD"
be in a typical range 45–55 °C, i.e. slightly above the body temper- C. High temperature "EPS LTD" Literature composites
ature and slightly below the safety limit of hot water (<60 °C), to Our recent results Metals
allow latent heat re-charging on reaching the normal operating
regime of the hot water appliance. PCM loads within the indicated Fig. 7. Selection map of PCM with properties in the range required for the starting
melting temperature range (45–55 °C) may also suppress sudden regime of hot water appliances. A – as a function of discharge time, B – as a function
of latent heat.
failures or undue hot peaks. Thus, suitable PCM materials for this
study case should be found in the operating range shown dashed
in Fig. 7, which also shows latent heat data (Fig. 7 B) as a guideline runaway by increasing ohmic losses. Thus, selection criteria must
to minimize mass, by lowering the (stored heat):(latent heat) ratio be based on latent heat charging (i.e. melting), and this may rely
1.26  106/k). In addition, one may seek decrease in encapsulation on the time required for half charging. Note that time dependence
costs by increasing the diameter of piping, provided that thermal on latent heat charging is nearly symmetrical to the dependence on
conductivity may be enhanced without undue additional cost. discharging, except for the fact that the temperature difference is
For example, the low thermal conductivity of paraffin may be reverted and possibly also due to differences in thermal diffusivity
enhanced by incorporation of highly conducting phases such as between the liquid and solid phases.
graphite (Table 5). Thus, one also considers generic quasi steady state solutions for
half charging:
3.2. Applications with response time requirements X 2 qk
t0:5
f ð6Þ
kðT up  T m Þ
Other prospective applications of PCMs are intended for protec-
tion of electronic components or devices, with fast response time where the driving-force is determined by the differences
requirements [40,41], rather than energy storage. In this case, DT = Tup  Tm between the upper temperature limit Tup for safe
power requirements are less important, and PCM must be selected operation of the intended device, and melting temperature; this
mainly by their ability to ensure fast heat dissipation before must be located in the range Tamb < Tm < Tup, i.e. slightly above the
temperature rises above a safety limit, to prevent temperature expected ambient temperature Tamb, to ensure spontaneous
604 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606

Table 5
Summary of literature composite materials with ability to be used in the presented application with response time requirements.

PCM Conductive phase Graphite content (wt.%) Tm/°C k/W m1 K1 q/kg m3 k/J g1 Ref.
Paraffin Graphite 55 16.6 789 185 [35]
8 54 10 1004 144 [36]
17 54 35 1121 130 [36]
26 54 66 1238 126 [37]
10 58 4.4 1030 190 [38]
15 58 6.5 1095 174 [38]
20 58 8.0 1160 161 [38]
Carbon nanofibers 30 67 3 1160 150 [39]

solidification, and below the upper limit. Thus, this range slab with volumetric energy density in the order of 108 J/m3,
determines also the maximum driving-force for heat dissipation, requires a 2 mm thick PCM layer and:
i.e.: DT < DTmax = Tup  Tm.For consumer electronics one often finds   
specified upper limits of about 70 °C, slightly higher limits for k C p ð125  T m Þ X2
¼f P 5  107 m2 =s ð9Þ
industrial applications and of the order of 125 °C for military appli- qC p k t 0:5
cations. In addition, most electronic components can sustain higher
temperature peaks for short periods. Thus, one assumes a target As expected, this would require PCM with high thermal diffusivities
upper temperature of 125 °C, and PCM with meting temperatures (e.g. metallic PCM). However, melting temperatures is much higher
in the range 40–125 °C, to account for relatively high ambient tem- that the target upper temperature. On the contrary, organic PCM
peratures in hot climates, yielding the actual range of driving-forces materials met the required temperature range but fail to reach
considered in Fig. 8, i.e., DT = 125  Tm, and the corresponding the required combination of thermal diffusivity and the Stefan
impact on the actual values of the Stefan number of PCM included number, i.e., a/ P 5  107 m2 =s. Still, some of the best performing
in this map, i.e.: composite materials might be promising for this type of application,
as shown also in Fig. 8. The success of these composites when com-
C p DT C p ð125  T m Þ pared with a variety of other materials reported in literature relies
/¼ ¼ ð7Þ
k k on microstructural organization of the conductive phase, enhancing
On inserting this in the expression for half charging (Eq. (6)), one the thermal conductivity by at least one order of magnitude relative
obtains the relevant selection criterion to sustain sudden tempera- to pure PCM or composites with random orientation of conductive
ture rise: phase [38,43].

  ! 
k X2
log
log f  log
qC p t0:5
Note that materials with highest melting temperatures are located
on the left of Fig. 8, as the values of the Stefan number decrease as
the melting temperature converges to the target upper tempera-
ture. Thus, the selection map also shows inclined lines for represen-
tative values of f X 2 =t 0:5 , to emphasize that the required values of
thermal diffusivity decrease with increasing the Stefan number.
One can assume typical electronic devices with area of the order
of 0.1–10 cm2, and power up to 10 W [40–42]. Thus, an abnormal
2 W/cm2 surge for about 10 s, to be charged in a typical PCM flat
100
Organics
λ x 106 / m2s -1

C p ð125  T m Þ 4. Conclusions
ð8Þ
k
Selection guidelines were proposed for commercial PCM avail-
able in market, as well as additional PCM reported in recent
research studies. The present guidelines for materials selection
were derived from the dynamics of melting or solidification of
phase changes materials, assuming that the effects of undercooling
or overheating remain negligible, and considering the most com-
mon geometries of flat slabs, and cylindrical or spherical reservoirs.
A scaling factor is proposed to adjust a generic model behavior to
those different geometries. This model behavior could also be
extended to account for limitations of heat transfer across the
encapsulating materials and/or transfer to (or from) the surround-
ing fluid. Although the main models were derived mainly on
Inorganics assuming quasi steady state solutions, implying a negligible contri-
bution of sensible heat and low values of the Stefan number, one

Eutetic mixtures C. Climator and Rubitherm

C. Eutetic "EPS Ltd."
10 C. Organics "EPS Ltd."
Metals
Our recent results
αφ x 106 = kΔT / ρλ
C. Hydrated salts "EPS Ltd." also proposed a simple correction to account for increasing (sensi-
C. High temperature "EPS Ltd." ble heat)/(latent heat) ratio. Expected requirements were analyzed
Literature Composites for representative applications, and corresponding selection guide-
lines were established on combining materials thermophysical

properties, operating conditions, and geometrical factors. One con-

1 firmed that energy density requirements are met by some of the
commercial PCM products available in the market, whereas com-
mercial PCM products were found to fall behind requirements of
0.1
high power and short response time. Still, recent research progress
shows good prospects to overcome these limitations.

Acknowledgements
0.01
40 60 80 100 120
This work was developed within the scope of the project CICECO-
Melting temperature, Tm / ºC
Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT
Fig. 8. Discharge factor as a function of the melting temperature of some PCM Ref. UID/CTM/50011/2013, PTDC/CTM-ENE/2073/2012 and Grant
groups with melting point range of 40–125 °C. SFRH/BPD/99367/2013), financed by national funds through the
 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606 605

FCT/MEC and when appropriate co-financed by FEDER under the values of the Stefan number / ¼ CpDT=k, where Cp denotes speci-
PT2020 Partnership Agreement. fic heat; this may be understood by taking into account that the
quasi steady state solutions neglect the contribution of sensible
Appendix A. Scaling factors for different geometries and mixed heat, which increases as CpDT (per unit mass), as emphasized
control in revised quasi steady state solutions [45]. Gradual deviations
are found on comparing the quasi steady state solution
A.1. Scaling factor for mixed control t0:5;qss
0:125X 2 qk=ðkDTÞ to the corresponding exact analytical
solution for flat slab configuration, under ideal conditions of con-
Eventhough one often assumes that latent heat discharge is trol by heat conduction [14]:
controlled by heat conduction across a PCM layer, this is only valid
X 2 qCp
when the expected values of thickness/conductivity ratio of the t0:5 ¼ 0:0625 ða9Þ
encapsulation wall L/kw and/or the reciprocal heat transfer coeffi- b2 k
cient (1/h) remain much smaller than the corresponding resistance where the exact solution for the kinetic constant b is obtained on
to heat conduction in the PCM, i.e., solving
L 1 X CpDT pffiffiffiffi
þ  ða1Þ /¼ ¼ pb expðb2 Þerf ðbÞ ða10Þ
kw h k k
Otherwise, one must account for mixed control or interfacial con- Thus, the relation between the correct analytical and quasi steady
trol, as described earlier [14] and the corresponding quasi steady state solutions may be described as follows:
state model yields the time to reach half discharge:
X 2 qCp X 2 qk
X 2 qk t0:5 ¼ 0:0625 ¼ 0:125 ð1 þ eÞ ða11Þ
t 0:5
f ða2Þ b k2 k DT
kDT
and on combining with Eq. (a10):
with a scaling factor pffiffiffiffi
/ p
0:5kL 0:5k ð1 þ eÞ ¼ ¼ b1 expðb2 Þerf ðbÞ ða12Þ
f
0:125 þ þ ða3Þ 2b2 2
kw X hX
This is the correction for the scaling factor, which is shown in
Thus, selection criteria (Eqs. (4) and (5)) are readily modified by cor-
Fig. a1, to emphasize that this converges to nearly linear depen-
recting the scaling factor, i.e.:
! dence for relatively low values of the Stefan number, i.e.:
 
k X2 f ð1 þ eÞ
0:125ð1 þ /=3Þ ða13Þ
log
logðkÞ þ log f ða4Þ
q t 0:5 DT
  ! Note that latent heat still prevails for most PCM materials
2
k X (i.e., / < 1), except possibly for high temperatures differences
log
log f ða5Þ
qk t 0:5 DT between melting and operating temperatures.
Corrections of scaling factor for spherical and cylindrical encap-
sulation were also determined based on the ratio between half dis-
A.2. Scaling factors for alternative geometries charge conditions predicted by numerical solutions [18,44] and
corresponding quasi steady state solutions. Numerical solutions
The applicability of selection maps may also be extended to for spherical symmetry [15] yield the half discharge scaling factor
other geometries such as spherical symmetry or cylindrical sym- which converges to the corresponding quasi steady state solution
metry, by relying on the applicability of corresponding steady state
solutions, which was confirmed for spherical symmetry under low
values of the Stefan number [44]. In this case, the generic quasi
steady state model yields:

R2 q k
t 0:5
f sph ða6Þ
k DT
φ/3) flat
where R denotes the inner radius of the spherical capsule, and the
scaling factor is:
" #
0:1667k 0:1667k
ε

f ¼ f sph ¼ 0:01837 þ þ ða7Þ

kw ð1 þ R=LÞ hRð1 þ L=RÞ2

Similarly, the quasi steady state approximations for cylindrical φ

symmetry may be extracted from corresponding analysis of the
Stefan-type problems [44] also yielding Eq. (a8) with a scaling fac-
tor for cylindrical symmetry
φ
 
0:25kL 0:25k
f ¼ f cyl
0:03835 þ þ ða8Þ
Rkw lnð1 þ L=RÞ hRð1 þ L=RÞ

A.3. Correction factors for deviations from quasi steady state

φ=CpΔT/λ
Previous selection criteria were based on quasi steady state Fig. a1. Corrected scaling factors for quasi steady state solutions with planar
assumptions which may find limited applicability with increasing geometry, cylindrical and spherical symmetry.
606 N. Vitorino et al. / Energy Conversion and Management 124 (2016) 598–606

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