Energy 162 (2018) 1169e1182

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Energy
journal homepage: www.elsevier.com/locate/energy

A comprehensive study of properties of paraffin phase change

materials for solar thermal energy storage and thermal management
applications
Samer Kahwaji a, Michel B. Johnson b, Ali C. Kheirabadi c, Dominic Groulx b, c,
Mary Anne White a, b, *
a
Department of Chemistry, Dalhousie University, PO Box 15000, Halifax, Nova Scotia B3H 4R2, Canada
b
Clean Technologies Research Institute, Dalhousie University, PO Box 15000, Halifax, Nova Scotia B3H 4R2, Canada
c
Department of Mechanical Engineering, Dalhousie University, PO Box 15000, Halifax, Nova Scotia B3H 4R2, Canada

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

Article history: Paraffins are useful as phase change materials (PCMs) for thermal energy storage (TES) via their melting
Received 3 April 2018 transition, Tmpt. Paraffins with Tmpt between 30 and 60
C have particular utility in improving the effi-
Received in revised form ciency of solar energy capture systems and for thermal buffering of electronics and batteries. However,
13 July 2018
there remain critical knowledge gaps concerning the properties of paraffin PCMs, including their long-
Accepted 8 August 2018
Available online 13 August 2018
term reliability and chemical compatibility. Therefore, we have undertaken a thorough, comprehen-
sive study of the thermophysical properties, long-term stability and chemical compatibility of six widely
useful paraffin PCMs. The PCMs investigated include three pure alkanes, nonadecane, eicosane, docosane,
Keywords:
Phase change material
and three commercial blends of paraffin waxes. For each PCM, we accurately determined Tmpt, the latent
PCM heat of fusion, the density of the solid phase and the temperature dependences of the heat capacity and
Paraffin thermal conductivity. For the first time, we show the thermal stability of the PCMs after 3000 melt-freeze
Thermal properties cycles, and their chemical compatibilities with 17 different metallic and plastic materials used for
Thermal energy storage encapsulation and in composites and fillers. These results provide necessary information to improve
energy modeling and analysis for existing and emerging TES applications, and guide the selection of
reliable paraffin PCMs and encapsulation materials for such applications.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction melting volume change [1,22e25]. Paraffin PCMs can be classified

The high latent heats of phase change materials (PCMs) can
greatly improve solar thermal energy storage (TES) in conventional
solar energy capture systems [1e4] and reduce energy costs by
effective thermal management in the built environment [5e12].
Paraffins can also fulfill a need for new methods to cool electronic
devices [13e17] and high-power batteries [14,18e21]. Paraffins are
exceptional PCMs for energy storage and passive cooling due to
many favourable factors: high latent heat of fusion; availability in a
wide transition temperature range; low cost; and desirable physical
and chemical properties, including congruent melting with little or
no thermal hysteresis, relatively low vapour pressure and small
* Corresponding author. Department of Chemistry, Dalhousie University, PO Box
15000, Halifax, Nova Scotia B3H 4R2, Canada.
E-mail address: mawhite@dal.ca (M.A. White).
in two categories according to their chemical composition: pure
straight chain alkanes (with the general formula CnH2nþ2), or
blends of alkanes and other hydrocarbons, commonly referred to as
“paraffin wax” [26]. Blends are most commonly used in TES appli-
cations because they are less expensive than pure alkanes and their
transition temperatures can be tailored to a given application by
mixing alkanes of different chain lengths. In general, both the heats
of fusion and melting temperatures of paraffins increase as the
number of carbon atoms in the alkyl chain is increased.
Given their broad range of melting temperatures, paraffins have
been explored for various TES applications. The present work
focusses on paraffin PCMs with melting temperatures between 30
and 60
C, with significant applications in two different fields of
TES: in residential solar thermal systems [1e4,23,24,27,28], and in
passive thermal management systems and heat sinks [14,29e38].
In both areas, paraffins are among the most-investigated PCMs but
there remain significant gaps in knowledge concerning their

https://doi.org/10.1016/j.energy.2018.08.068
0360-5442/© 2018 Elsevier Ltd. All rights reserved.
1170 S. Kahwaji et al. / Energy 162 (2018) 1169e1182
Nomenclature
as thermal diffusivity of solid phase
Cp heat capacity at constant pressure
Cp,l heat capacity at constant pressure of liquid phase
Cp,s heat capacity at constant pressure of solid phase
CR corrosion rate
DfusH latent heat of fusion
DSC differential scanning calorimetry
kl thermal conductivity of the liquid phase
ks thermal conductivity of the solid phase
rl mass density of the liquid phase
rs mass density of the solid phase
PCM phase change material
PPMS physical property measurement system
TES thermal energy storage
Tmpt melting temperature
Tonset onset of DSC thermal anomaly
thermophysical properties, including cyclability and chemical
compatibility, thus motivating the present work.
In residential thermal applications, PCMs with melting tem-
peratures Tmpt ¼ 30e60
C are particularly useful for solar water
heating systems and for integration with heat pumps [2,4,39e46].
In solar water heating systems, paraffins in storage tanks provide a
high density of thermal energy and improve the system perfor-
mance while reducing the size and cost. For example, a study
showed that paraffin with Tmpt ¼ 55
C filled in a jacketed shell-
type tank can increase the stored thermal energy of the solar wa-
ter heating system by up to 39%, increasing its efficiency by 16% and
extending the solar heater hot water supply time by up to 25% [4].
In another study, the addition of commercial grade paraffin wax
with Tmpt ~55
C to an evacuated tube collector/storage (ETC/S)
system helped to regulate the temperature of the heating medium,
and to extend the operating time of the solar system by increasing
the amount of useful heat by up to 79% [45]. Similarly, PCMs with
Tmpt ¼ 30e60
C can improve the efficiency of heat pumps used for
space and water heating and of air conditioners, as well as reducing
their costs of operation by peak-load shifting [44,47,48]. Paraffin
wax with Tmpt ¼ 39e42
C added to the water tank of a prototype
heat recovery room air-conditioner system increased the heat
retention time by 21% and increased the coefficient of performance
of the air conditioner by up to 9.8% [48].
In addition to TES applications in the built environment, several
recent studies propose paraffin PCMs with Tmpt ¼ 30e60
C for
passive cooling of electronics, photovoltaics and batteries
[14,30e38,49]. Most investigations related to passive cooling of
electronics with PCMs focus on the incorporation of a PCM in heat
sinks and the influence on the transient thermal performance of
electronic devices, using both experimental and numerical ap-
proaches [30e37,49,50]. A heat sink fabricated from a form-stable
composite consisting of sintered copper powder and paraffin
(with Tmpt ~ 53
C) was shown to be more efficient than a conven-
tional aluminum heat sink in regulating the temperature and
improving the brightness of high-power LEDs [51]. A PCM-based
TES system is particularly favourable for portable electronics
where the size of the cooling system is greatly restricted by the
dimensions of the device. In a recent study, the influence of eico-
sane (Tmpt ~ 36
C) on the thermal performance of a commercial
tablet computer was investigated experimentally, showing that
eicosane can reduce the temperature of the back cover hotspot by
up to 20
C [38].
Passive cooling with PCMs can also improve the efficiency of
photovoltaic panels; their efficiency and power output is consid-
erably reduced as the operational temperature of the cells increases
[52]. A PCM integrated into the photovoltaic panels absorbs the
excess heat generated from solar radiation and reduces the tem-
perature of the cells, therefore providing an effective passive
thermal buffering method and improving their efficiency. Since
1978 [53], many numerical and experimental studies have inves-
tigated the influence of PCMs on the temperature control and on
the efficiency of photovoltaic panels [53e63]. Paraffin PCMs and
their composites (e.g. graphite-infused paraffin [61] or copper ox-
ide (CuO) nanoparticles-enhanced paraffin [63]) have been shown
to improve the efficiency of the photovoltaics, sometimes by more
than 10% [61]. When integrating the PCMs into the photovoltaic
panels, paraffins were filled in containers made of materials such as
aluminum and Perspex (cast acrylic) [62], or containers 3D-printed
using ABS plastic [63].
PCMs are also useful for thermal buffering of high-power bat-
teries [14,18,19,21,64,65]. With the development of high energy-
density batteries to power electric vehicles and electrical power
storage devices, there is an increasing interest in efficient thermal
management systems to regulate the temperature of batteries to
prevent overheating. Several studies have shown that paraffins
with Tmpt ¼ 30e60
C can potentially maintain the temperature of
batteries below the upper operational limit (50e60
C for NiMH
and Li-ion batteries [21]), therefore improving their performance
and extending their lifetime. For example, a thermal management
system based on a nickel foam-paraffin composite reduced the
surface temperature of a high powered lithium-ion battery by
about 31% as compared to natural air cooling [66]. A comparison
between the performance of paraffin-expanded graphite compos-
ites with different melting temperatures [67] demonstrated that a
composite with Tmpt ¼ 40e45
C has the best performance in
regulating the temperature of the battery.
Overall, studies based on numerical simulations and experi-
ments performed on prototypes or small-scale systems demon-
strate that paraffin PCMs with Tmpt ¼ 30e60
C hold promise for
improving the performance of existing solar thermal systems and
for developing efficient thermal management units. To our
knowledge, commercial PCM-based solar thermal systems and heat
sinks are not yet available. To advance to the stage where these
PCMs are reliably implemented in such applications, three key is-
sues regarding the properties of paraffins themselves remain to be
addressed. (1) It is important to assess the long-term thermal sta-
bility of paraffins to ensure that their thermal properties, specif-
ically their Tmpt and latent heat of fusion, remain unchanged when
they undergo thousands melt-freeze cycles, as they are expected to
do in the designated applications. (2) Equally important is the long-
term chemical stability of the paraffins with materials used both for
their containment, and as fillers to enhance their thermal con-
ductivities. Reports to date of such experiments are, typically, based
on short-term investigations and it is not possible to elucidate the
long-term behavior of the PCMs from these studies. (3) Accurate
and comprehensive knowledge of the thermophysical properties of
the PCMs is also needed to improve the reliability of numerical
studies: while energy modeling and analysis of systems containing
PCMs is very common in this field, the confidence in the modeling
of PCMs behavior remains at a very low level [68,69]. One key
parameter that can improve this confidence is the use of accurate
values for the PCMs thermophysical properties in these models
[69].
Although paraffins are the most-used organic PCMs, the three
issues highlighted above remain largely overlooked in the available
literature. For instance, the long-term thermal stability of paraffins
has not been explicitly investigated. Thermal stability studies of
 S. Kahwaji et al. / Energy 162 (2018) 1169e1182
pure alkanes have focused on composites and microencapsulated
materials [70e73], whereas thermal cycling studies of commercial
waxes, limited to just 1500 cycles, showed that some blends are not
reliable for long-term applications [74e76]. If PCMs are to be used
in energy storage applications or other consumer products
[1,33,77,78] where they will undergo many melt-freeze cycles per
day, it is critical to know their thermal stability over thousands of
cycles [69].
It is equally important for successful applications to know the
chemical compatibility of a potential PCM with containment ma-
terials, or with materials in the surroundings of the TES unit in case
of accidental leakage. Corrosion immersion tests are normally
performed to determine the chemical compatibility, but most of the
available PCM results are limited to salt hydrates [79e84] and fatty
acid PCMs [81,85e87]. One limited study [88] investigated the
compatibility of paraffin waxes with Tmpt ¼ 20e26
C with four
different types of industrial plastics and another with one com-
mercial paraffin product [86]; there are no comprehensive reports
of the compatibility of paraffin PCMs with containment materials.
Moreover, as new and unconventional materials are being used in
paraffin PCMs containers, such as Al laminated foil [38], cast acrylic
[62] and ABS plastic [63], it is important to evaluate the compati-
bility of these materials with the PCMs. Furthermore, knowledge of
chemical compatibility is important for the development of
paraffin-based composites. As reported above, a large number of
studies explored paraffin-metal composites as a means to improve
the thermal conductivity and heat transfer of the PCM. Paraffins
impregnated into copper, aluminum and nickel foams, or mixed
with fibers and fillers of these metals are typical examples of such
composites and show promise for increasing heat transfer
[17,66,89e91]. Studies on these composites usually report on their
preparation methods, on the fraction of absorbed PCM and on the
effect of metallic structures on the thermal conductivity or heat
transfer rate. A critical parameter not considered is the chemical
compatibility of the paraffin PCM with the metals of the foam or the
fibers. This is especially important if the composites are used in
long-term TES applications: if paraffins react with these materials,
even at slow rates, this could be detrimental to the thin fibers or
thin network wires of the metal foams. Consequently, knowledge of
the chemical compatibility and corrosion rates of the PCM with
potential materials of foams and fillers is imperative for the
development of reliable composites.
Concerning the thermophysical properties: extensive reports of
the transition temperature, Tmpt, and latent heat of fusion (or so-
lidification), DfusH, of pure alkane paraffins and many commercial
paraffin waxes PCMs exist [22,23,26,92e94], but discrepancies
abound, especially for commercial waxes for which properties are
often quoted within a range of values. Other properties, such as the
temperature dependence of the heat capacity and of the thermal
conductivity have not been reported for most paraffin PCMs. Pre-
cise knowledge of these thermophysical properties is particularly
important to improve the reliability of numerical simulations
which are commonly performed to optimize the design of a TES
system and assess the effectiveness of the PCM [69]. A recent study
on the performance of a PCM floor investigated the effect of using
inaccurate values of latent heat of fusion and melting temperature
on the outcome of the numerical simulations [95], showing that the
simulated surface temperature of the PCM floor changes consid-
erably when a more accurate value of Tmpt of the fatty acid PCM is
used [95]. Compared to fatty acids which, in general, have a sharp
solid-liquid transition [87], paraffins and especially commercial
blends have a broader solid-liquid transition and possibly a solid-
solid transition close to the melting point. Therefore, Tmpt of
paraffin PCMs can be especially prone to misinterpretation. In
addition to errors in Tmpt, errors in other PCM parameters, such as
1171
DfusH and the heat capacity, can increase the deviations between
simulation and reality. Consequently, when a given PCM is
considered for a given application, a complete characterization of
its thermal properties is imperative.
Therefore, the main objective of this work is to address the is-
sues related to the properties of paraffin PCMs to provide infor-
mation that improves the accuracy of numerical modeling and
thereby bridge the gaps between research and implementation of
these PCMs in actual TES systems. The present work presents a
comprehensive and accurate study of the thermophysical proper-
ties, long-term reliability and chemical compatibility of six impor-
tant paraffin PCMs. In particular, we indicate shortcomings in
ignoring chemical compatibility with some materials and in taking
data for commercial paraffin blends at face value. The PCMs
investigated include three pure alkanes, namely nonadecane
(C19H40), eicosane (C20H42), docosane (C22H46), and three paraffin
waxes (CnH2nþ2 with n ¼ 24e36) with different melting tempera-
tures. The selected paraffins are potentially useful for solar thermal
and thermal management applications, as discussed above. For
each PCM, we report Tmpt, DfusH, and sort out origins of discrep-
ancies for literature values. We also determined the density and
thermal diffusivity of the solid phase, and the temperature de-
pendences of the heat capacity and thermal conductivity, both in
the solid and liquid phases. Knowledge of these properties is
essential for accurate design and numerical modeling of a TES
system [6,21,69,96]. For the first time, the thermal conductivities of
solid and liquid paraffin PCMs are reported over a broad tempera-
ture range. In addition, the thermal stability of relatively large
samples of PCMs (~2 g, compared to a few mg as usually used when
cycling is done with a differential scanning calorimeter) after 3000
melt-freeze cycles was determined using a custom-built thermal
cycler [97]. The chemical compatibilities with seventeen different
metallic and plastic materials, covering a wide range of applications
and including materials found in modern electronic devices (e.g.
magnesium alloy) and in composites, were also determined. The
results of this study complement our previous comprehensive
study of fatty acid PCMs in a similar Tmpt range [87]. The results
provide essential information to facilitate the selection of a PCM
suitable for a specific application, as well as recommendations on
compatible materials and data necessary to accurately evaluate the
viability and effectiveness of incorporating the selected PCM in TES
systems, especially for residential and passive cooling applications.
2. Experimental methods
2.1. Phase change materials
The paraffin PCMs investigated in this study are listed in Table 1,
along with the supplier and their stated purity. The PCMs investi-
gated include three pure alkanes, viz. nonadecane, eicosane and
docosane, and three commercial blends of alkanes (CnH2nþ2 where
n ¼ 24e36) with different melting temperatures. Samples were
used as-supplied without additional purification.
2.2. Determination of thermophysical properties
A TA Instruments Q200 differential scanning calorimeter (DSC)
was used to determine the latent heat of fusion, DfusH, the melting
temperature, Tmpt, and the heat capacity at constant pressure as a
function of temperature for each PCM. Prior to each set of experi-
ments, the DSC was calibrated by measuring DfusH and Tmpt of a
high-purity indium standard (DfusH ¼ 28.71 J g1 and


Tmpt ¼ 156.6 C [98]). A PCM sample of mass between 5 and 10 mg
was sealed in a standard DSC aluminum pan, placed inside the DSC
cell and measured. Helium was used as the purging gas inside the
1172 S. Kahwaji et al. / Energy 162 (2018) 1169e1182
Table 1
Paraffin PCMs investigated in this work.
PCM Paraffin type/Chemical Formula
Nonadecane Pure/C19H40
Eicosane Pure/C20H42
Docosane Pure/C22H46
Paraffin wax 48 (PW48) Blend/CnH2nþ2 n ¼ 24e36
Paraffin wax 52 (PW52) Blend/CnH2nþ2 n ¼ 24e36
Paraffin wax 58 (PW58) Blend/CnH2nþ2 n ¼ 24e36
DSC cell, with a flow rate of 25 mL min1. The melting point, Tmpt,
was determined from scans at 2 K min1 whereas DfusH was
determined from measurements performed at heating and cooling
rates of 10 K min1, as recommended for high-accuracy determi-
nation of these properties [99]. (In each case, the indium standard
was determined at that same heating rate). For DH, five melt-freeze
cycles were performed for each PCM and the averages (from
melting peak areas) are reported here for DfusH. The melting point
temperatures were generally measured after the five cycles for
measurement of DfusH. Typical uncertainties for this DSC system are
±10% for DfusH and ±1.5
C for Tmpt.
The heat capacity at constant pressure as a function of tem-
perature, Cp(T), was measured using the same TA Instruments Q200
DSC following published methodology [87] and the guidelines of
ASTM Standard E1269-11 [100] for measuring heat capacity by DSC.
The heat capacities of both the solid (Cp,s) and liquid (Cp,l) phases
were measured, and the estimated uncertainty of the values re-
ported here is ±10% [97].
The temperature-dependent thermal conductivity, k(T), of each
PCM was determined from the thermal conductance measured
with the thermal transport option (TTO) of a Quantum Design
Physical Property Measurement System (PPMS). All measurements
were carried out in vacuum, in steady-state conditions [87,97,99].
The PCM sample was filled in a custom-built fluid cell [87,97] and
the thermal conductance of the assembly, Ktotal, was measured
through the solid-liquid phase transition of the PCM, within the
temperature range 0e100
C. The thermal conductance of the
empty cell was then subtracted from Ktotal to give the thermal
conductance of the PCM, KPCM. The thermal conductivities of the
solid, ks, and liquid, kl, phases were calculated from KPCM and the
known dimensions of the sample. The uncertainties in the
measured values of the thermal conductivities are within 15% at
room temperature, as determined from measurements of standard
materials with known thermal conductivities [97].
In addition to the thermal properties, the densities of solid
PCMs, rs, at room temperature (23
C) were measured, using a
10 mL glass pycnometer filled with distilled water with a small
amount of surfactant (less than 50 mL) to prevent the formation of
bubbles. Since paraffins do not dissolve in water, the density was
determined from the volume of the solid PCM sample, equal to the
volume of the water displaced, and the mass of the PCM as
measured with a high-accuracy balance (±0.02 mg).
2.3. Thermal reliability and chemical compatibility
The long-term thermal stability of the paraffins was determined
here using a custom-built thermal cycler [97] that was pro-
grammed to heat and cool a sample (ca. 2 g) of each PCM through
its phase transition, typically from 10 to 90
C (i.e., well above the
melting point) and back. A holding time of about 10 min was used
when the sample cell reached 10
C and ensured complete solidi-
fication of the PCM. Each PCM was cycled for a total of 3000 melt-
freeze cycles, exceeding the recommended minimum of 1000 cy-
cles [22,39]. After a given number of cycles, aliquots were taken for
Supplier Purity
Alfa-Aesar 99%
Sigma-Aldrich 99%
Sigma-Aldrich 99%
Sigma-Aldrich N/A
Sigma-Aldrich N/A
Sigma-Aldrich N/A
measurements of Tmpt and DfusH by DSC.
To check the chemical compatibility of the PCMs, 17 potential
encapsulating/contact materials were immersed in liquid PCMs and
their corrosion rates were evaluated gravimetrically, following the
procedures described elsewhere [87] and the recommendations of
ASTM G1 Standard [101]. The materials selected for the chemical
compatibility studies, listed in Table S1 of Supplementary Materials,
include 9 metals and metal alloys, 7 plastics and an aluminum
laminated foil. The Al laminated foil consists of a thin Al foil
sandwiched between two layers of nylon and cast polypropylene
using adhesive, with a total approximate thickness of 100 mm. The
materials chosen cover a wide range of materials that can be used
for PCM containment and found in different applications, particu-
larly in solar heating systems (Cu, Al, stainless steel) and portable
electronics (e.g. Cu, Mg AZ91D, polycarbonate). The list also in-
cludes metals (Cu, Al, Ni) used in paraffin-based composites or as
fillers for thermal conductivity enhancement [66,89e91,102].
Coupons from the selected materials were cut (length ~ 2 cm,
width ~ 0.5 cm, thickness between 0.1 and 1.6 mm) and cleaned as
described elsewhere [87]. The total surface area was calculated
from the dimensions of each coupon measured with a Vernier
caliper (uncertainty ± 0.02 mm) and the coupon's mass was deter-
mined with a high-accuracy balance (±0.02 mg). Each coupon was
immersed in liquid PCM contained in a screw-cap glass vial and
placed in an oven at 75
C. Corrosion tests in liquid PCMs provide
corrosion rates for more extreme conditions than in most thermal
energy storage applications, where the PCM cycles between solid
and liquid and does not remain at high temperatures for long times.
The corrosion rate, CR, for each material was calculated after 1, 6
and 12 weeks of immersion from the change in mass of the
immersed coupon, Dm, according to [101]:
Dm
CR ¼ (1)
A$Dt
where A is the total surface area of the coupon and Dt is the time
period since the prior mass measurement. The corrosion rates re-
ported here are in units of mg cm2 yr1. In addition to measuring
the mass loss, each coupon was inspected at the different immer-
sion times to look for visible changes such as corrosion, pitting,
surface oxidation or coloration, bubbling and swelling.
3. Results and discussion
3.1. Thermophysical properties
The measured melting temperatures, Tmpt, and latent heats of
fusion, DfusH, of all PCMs investigated are listed in Table 2. The
melting temperatures were determined from the onset points of
the endothermic peaks of the DSC thermograms (Fig. 1). For all
paraffins except eicosane, two endothermic peaks were observed
upon heating (Fig. 1): the peak at the lower temperature with lower
intensity corresponds to a solid-solid (ordered-rotator) phase
transformation [103]. Eicosane only exhibited an abrupt solid-solid
 S. Kahwaji et al. / Energy 162 (2018) 1169e1182 1173

Table 2
Measured values of Tmpt and DfusH, along with comments, for the paraffin PCMs. The ranges of values of Tmpt and DfusH reported in the literature for the pure paraffins are
shown in parentheses [26,93,105]. For the blends, the ranges of Tmpt as specified from the supplier (Sigma-Aldrich) are shown in parentheses.

PCM Tmpt (
C) DfusH (J g1) Comments

Nonadecane 31.8 ± 1.5 (30.8e32) 181 ± 18 (163e222) The solid-solid transition is at T ~ 22
C and is clearly discernible from the solid-liquid
transition.
Eicosane 37.5 ± 1.5 (35.4e36.9) 246 ± 25 (217e251) The solid-solid transition was only observed as an abrupt exothermic peak upon cooling.
Docosane 43.8 ± 1.5 (42.9e44.1) 234a ± 23 (154e253) Up to 40% of DfusH is a contribution from the solid-solid transition.
PW48 48.2 ± 1.5 (53e57) 156 ± 16 Tmpt is well below the melting temperature range specified by the supplier.
PW52 51.8 ± 1.5 (58e62) 171 ± 17 Tmpt is well below the melting temperature range specified by the supplier.
PW58 57.7 ± 1.5 (65) 197a ± 20 DfusH includes contribution from solid-solid transition. Tmpt is well below the melting
temperature range specified by the supplier.
a
Includes contribution from solid-solid transition very close to the melting point.

Fig. 1. The DSC thermograms measured on heating at a rate of 2 K min1 show two endothermic peaks for all investigated PCMs except eicosane. Where present, the peak at the
lower temperature for each PCM corresponds to a solid-solid transition. The melting temperatures, Tmpt, were determined from the onset temperatures of the higher-temperature
peak, which is the melting transition.

transition on cooling the melt, at about 3 K below the liquid-solid
transition temperature, as also reported elsewhere [104]. In each
case, the main endothermic peak in the DSC thermogram on
heating corresponds to the solid-liquid transition. Since the solid-
solid transition is also endothermic upon heating, it contributes
to the thermal energy storage capacity of the PCM, although at a
temperature that might be different from the intended tempera-
ture of the application. It is possible that this contribution is
included in some of the reported values of DfusH of paraffin PCMs,
especially if the thermogram had been measured at a high heating
rate where two close endothermic peaks merge into one broad
peak. For example, for nonadecane, if the endothermic contribution
1174 S. Kahwaji et al. / Energy 162 (2018) 1169e1182

of the solid-solid transition around T ¼ 22
C (Fig. 1) is added to
DfusH, the total value would be 215 J g1, which is close to the re-
ported value of DfusH of 222 J g1 [26]. Table 2 reports only values of
DfusH, the latent heat of fusion found from the melting peak, for the
PCMs, except docosane and paraffin wax PW58 where the solid-
solid transition peaks were too close to the melting peaks to
objectively separate their contributions. The solid-solid contribu-
tions are estimated to be about 25% of DfusH for the commercial
waxes and up to 40% for docosane [105]. In general, the latent heats
of fusion of the PCMs studied here are high, and higher for the pure
alkanes than for the blends, with DfusH ~150e200 J g1 for the
blends and >200 J g1 for pure paraffins. As expected, the melting
transition of the blends is broader than for pure alkanes, with a full
width at half maximum (FWHM) of the peak almost double when
comparing, for example, PW52 (FWHM ~ 6
C) to nonadecane
(FWHM ~ 3
C; heating rate of 2 K min1). The values reported for
Tmpt and DfusH for the pure alkanes are within the range of values
reported in the literature [26,93,94,105], as shown in Table 2.
However, for the commercial waxes, the melting points specified by
the supplier (see Table 2) were higher than determined here: their
specified ranges are in good agreement with the measured peak
temperatures (see Fig. 1), although onset temperatures are more
representative of melting points [99]. This finding, along with the
observation that inclusion of solid-solid transitions in DH can
overestimate the thermal energy storage capacity of some paraffin
PCMs, indicates the importance of thorough measurements to
provide more accurate properties of PCMs for reliable numerical
simulations.
The densities of solid PCMs, rs, also were measured (~0.8 g cm3
for all; see below). Nonadecane, eicosane and docosane have
similar liquid densities, 0.76 g cm3 at 60
C, as reported elsewhere
[94]. The measured values of rs, along with values measured for Cp,s
and ks, were used to calculate the thermal diffusivities of the solid
phase, as, for each PCM (as ¼ ks/(Cp,s  rs)).
Fig. 2 shows the specific heat capacities as a function of tem-
perature, Cp(T), as measured by DSC through the transition points of
the PCMs. For comparison, Cp values reported for pure paraffins in
Refs. [26,105e108] are also included. The heat capacities of the solid

Fig. 2. Temperature-dependence of the specific heat capacities at constant pressure, Cp (T), of the six paraffin PCMs measured in the present work (solid line). Singularities are
observed in the regions of the transitions and data points in this region are not shown. The few available literature values of Cp for pure paraffins are also included: from Ref. [26],
from Ref. [105], △ from Ref. [106] and from Refs. [107,108].
 S. Kahwaji et al. / Energy 162 (2018) 1169e1182 1175

phase, Cp,s, of the pure alkanes are between 1.7 and 2.0 J K1 g1,
and are generally lower than the heat capacities of the liquid phase,
Cp,l (2.2e2.5 J K1 g1). For the commercial paraffin waxes, there is a
smaller difference between Cp,s and Cp,l, and their values are similar
to those of the pure alkanes, ca. 2.0 J K1 g1. The specific heat ca-
pacities of the paraffin PCMs are comparable to those of fatty acids
[87].
The thermal conductivities of the PCMs measured between ~0
and 90
C are shown in Fig. 3 for both the solid and liquid phases.
The transition between the two phases can be clearly seen with the
drop in the thermal conductivity as the paraffin melts, and is
generally in agreement with the Tmpt determined from DSC ex-
periments (indicated by the arrows in Fig. 3). Among the six PCMs
investigated, eicosane and docosane have the highest thermal
conductivities in the solid phase, with ks between 0.40 and
0.50 W K1 m1. The values of ks for nonadecane and eicosane are
comparable to those measured by the hot-wire technique [107,108].
The thermal conductivities of the liquid phase, kl, are similar for all
PCMs, around 0.20 W K1 m1. However, there are some differences
between our values of kl and the values reported for the three pure
alkanes [94,106e108], likely due to differences in techniques. In
general, our results show that neither ks nor kl has a strong
temperature-dependence within the range of temperature
considered here. As expected for organic PCMs, the values of k are
generally low. Therefore, in applications using large quantities of
paraffin PCMs where rapid charging and discharging are required,
the TES system must be designed to enhance the heat transfer, or
else high-thermal conductivity fillers must be added, as discussed
above and elsewhere [109]. For smaller-scale TES units, such
measures might not be necessary [110].
3.2. Thermal stability
To determine the long-term stability of the thermophysical
properties of the PCMs, the influence of thermal cycling on DfusH
and Tmpt was investigated. A total of 3000 melt-freeze cycles were
performed for each PCM. This is the first report of longer-term
thermal cycling (exceeding 1500 cycles) for paraffins. After a
given number of cycles, values of DfusH and Tmpt were determined
and compared to DfusH and Tmpt of a virgin sample. The cycling
results in Fig. 4 show that all six PCMs are thermally stable, with no
significant variations in DfusH and Tmpt over 3000 cycles. Here, we

Fig. 3. Thermal conductivity, k, as a function of temperature for the solid ( ) and liquid ( ) PCMs measured by PPMS. The arrows indicate Tmpt of the PCM. Where reported, thermal
conductivity values for pure paraffins from other studies are also included: from Ref. [107], from Ref. [106], from Ref. [108], from Ref. [94] and from Ref. [111].
1176 S. Kahwaji et al. / Energy 162 (2018) 1169e1182

Fig. 4. Thermal stability of the PCMs after 3000 melt-freeze cycles. The values of DfusH ( ) and Tmpt ( ) are shown as a function of thermal cycle number. The solid lines correspond
to DfusH and Tmpt of a virgin sample, and the dashed lines show the range of their uncertainties: ±10% for DfusH and ±1.5
C for Tmpt.

assessed the thermal stability by thermally cycling the paraffins up
to 90
C, well above their melting point. Such a procedure is
important because in applications such as in solar thermal collec-
tors or in passive cooling of photovoltaics, the rise in PCM tem-
perature is usually uncontrolled and might exceed the melting
temperature for extended periods. Previous reports on commercial
paraffins with Tmpt ¼ 40e60
C showed that some waxes can
withstand thermal cycling, with no significant changes to their
thermal properties after 1500 cycles, while other technical grade
paraffins were reported to be unstable after 900 thermal cycles
[74e76]. The results obtained here show that the selected paraffin
waxes, in addition to being cost-effective, are also reliable for long-
term use in TES systems given that there are no significant varia-
tions or noticeable trends in the values of DfusH and Tmpt up to 3000
cycles. Based on typical frequency of melt-freeze cycles, the paraffin
waxes would be stable for at least eight years in solar thermal
heating systems (1 daily cycle), and likely much longer.
3.3. Chemical compatibility
The chemical compatibility of the paraffin PCMs with the 17
selected contact materials was determined from the corrosion rate
values, CR, calculated after 1, 6 and 12 weeks of immersion in the
liquid PCM at 75
C. As in the case of thermal stability tests, the
temperature at which the chemical compatibility studies were
conducted is well above the melting temperature, as a good rep-
resentation of the temperature at which the PCMs might be oper-
ating in actual applications. Based on the recommendations
adapted from Ref. [112] and outlined in Table S2 (Supplementary
Materials), a material is suitable for long-term use in contact with
a PCM if jCRj due to degradation is less than 10 mg cm2 yr1. Note
that some plastic materials absorb a significant amount of PCM
during the immersion tests. Consequently, the masses of these
materials increased due to PCM absorption and their CR values were
negative. As indicated in Table S2, a material with CR between 50
and 10 mg cm2 yr1 should only be used with caution, and a
material is not recommended for contact with the PCM use under
swelling conditions if its CR is < 50 mg cm2 yr1 due to major
deformation.
In general, all metals and metallic alloys tested in this work
show good chemical compatibility with the six paraffin PCMs
investigated. As shown in Fig. 5, the CR values of the stainless-steel
alloys (304 and 316), aluminum alloys (Al 5052, Al 6061, Al 6063),
Ni C7521 and Cu 110 samples are within the recommended range
for long-term usage. Moreover, no significant changes or reactions
at the surface of the coupons were observed after 12 weeks of
 S. Kahwaji et al. / Energy 162 (2018) 1169e1182 1177

Fig. 5. Corrosion rates, CR, of metallic samples in each PCM. Materials recommended for long-term service have jCRj < 10 mg cm2 yr1 (within the solid boundary lines) whereas for
jCRj > 50 mg cm2 yr1, the materials are not recommended for use with the PCM. The small negative CR values for metallic specimens are due to experimental uncertainty.

immersion. For comparison, stainless steel, Al and Cu samples
tested with the commercial paraffin PCM Micronal®
(Tmpt ¼ 21e26
C) at 45
C also had low CR values, below 2 mg cm2
yr1 [86]. Scanning electron microscope images, however, showed
early stage pitting corrosion on the surface of Cu samples and more
extensive pitting on Al after 540 days of immersion [86]. However,
given that the CR values of highly conductive copper Cu 101 with
eicosane and docosane are between 10 and 50 mg cm2 yr1,
caution is recommended for long-term use of Cu 101 with these
two paraffins. After 12 weeks of immersion in eicosane and doco-
sane, the originally colorless PCMs changed to light green and the
polished Cu 101 coupons appeared darker in color (Fig. 6). In
contrast, CR values of multipurpose copper Cu 110 remained well
below 10 mg cm2 yr1 after 12 weeks of immersion in eicosane
and docosane (Figs. 5 and 6 b)), so Cu 110 is more suitable than Cu
101 for use with these two PCMs. Similarly, the magnesium alloy
Mg AZ91D samples immersed in the commercial waxes PW52 and
PW58 also oxidized. The oxide layer that formed increased the
mass of the Mg AZ91D samples, which resulted in negative CR
values. Note that the small, negative CR values measured for the
other metallic samples (Fig. 5) are due to small changes in mass
(within experimental uncertainty) over a short period of time [87].
In contrast with fatty acids [87], Cu 101, Cu 110 and Mg AZ91D
have better chemical compatibility with the paraffin PCMs tested in
this study. For instance, for an application that requires the use of
an organic PCM with Tmpt ~32
C in contact with copper, non-
adecane is more suitable than decanoic acid.
Amongst the tested plastic materials (Table S1), polycarbonate
1178 S. Kahwaji et al. / Energy 162 (2018) 1169e1182
Fig. 6. (a) Cu 101 sample after 12 weeks of immersion in docosane at 75
C. The
originally colorless docosane became green and the Cu 101 sample was oxidized. (b) In
comparison, no change was observed for docosane and Cu 110 after 12 weeks of
immersion.
and Type I PVC showed good compatibility with all the paraffins
and their CR values (Fig. 7) indicate that they can be used for long-
term TES applications with any of the tested PCMs. The ABS plastic
also showed good compatibility with all the PCMs. However, the CR
values measured after 1 week of immersion in nonadecane and in
the paraffin wax PW52 were 15.7 and 10.6 mg cm2 yr1,
respectively (Fig. 7). Although these values are not within the
recommended range for long-term use (Table S2), the corre-
sponding changes in mass (see eq. (1)) were too small to be
considered significant: in nonadecane, the mass of ABS plastic
specimen increased by 0.4% during the first week whereas in PW52
the mass increased by about 0.3%. Note that some discoloration
started to appear at the edges of the ABS plastic sample after 12
weeks of immersion in nonadecane. The good compatibility of ABS
plastic with paraffins is encouraging, given that this material can be
conveniently used for 3D-printing PCM containers [63].
The corrosion rates of cast acrylic after one week were between
10 and 50 mg cm2 yr1 (Fig. 7) for all PCMs except paraffin wax
PW58 (CR ¼ 0.55 mg cm2 yr1 at week 1). Therefore, caution is
recommended when using cast acrylic with these five PCMs, such
as in cooling of photovoltaics [62]. In contrast, corrosion tests at
45
C on the cast acrylic material Perspex showed that it has very
good compatibility with the paraffin Micronal®, with a reported CR
value of 0 mg cm2 yr1 after 722 days of immersion [86]. The
difference in CR values is likely due to the different testing tem-
peratures (45
C compared with the more severe 75
C used in this
study). Indeed, in another corrosion test conducted at 100
C (un-
published), we found that the CR of cast acrylic in eicosane was
about 10 times the value measured at 75
C.
As for cast acrylic, the CR values of wear-resistant nylon were
high, ~50 mg cm2 yr1 for eicosane and docosane and close to
50 mg cm2 yr1 for all other PCMs. Consequently, it is preferable to
avoid wear-resistant nylon in long-term applications with paraf-
fins. Neither polypropylene nor silicone rubber are compatible with
any of the paraffin PCMs. This is due to an excessive absorption of
the PCMs by the two materials, as deduced from the large negative
values of CR (Fig. 7). Within the first week of the immersion tests,
the mass of silicone rubber increased by up to 23% and the mass of
polypropylene increased by up to 9%. However, it appears that most
of the PCM absorption occurred during the first week and that the
amount absorbed was less for the PCMs with higher melting
temperatures.
Unlike the tested metals, not all selected plastic materials
showed good compatibility with the PCMs. However, besides PCM
absorption, there was no clear evidence of chemical reaction be-
tween the plastics and the paraffin PCMs. The relatively high
temperature (75
C) at which the corrosion tests were conducted
certainly accelerated the degradation of the plastic samples
immersed in the PCMs and eased the diffusion of PCM into some of
the plastic materials. Consequently, the plastic samples swelled and
deformed, which led to high and negative CR values, as discussed
above. PCM absorption is detrimental in the use of plastics as PCM
encapsulation materials because the absorbed PCM can leak to the
surroundings. Moreover, in small-scale applications, where size is a
limiting factor, the deformation or expansion of the PCM contain-
ment material can be problematic for the TES system.
The compatibility of the Al foil laminate requires special
mention. This sample consists of a thin Al foil and two plastic films:
polypropylene and nylon. The Al laminate foil was cut into strips for
the corrosion tests, and the PCM diffused between the layers; after
the first week all samples showed an increase in mass that led to CR
values significantly higher than the recommended range. After 6
weeks in the PCM, most samples started to separate into their
layers. In general, the delaminated plastic films were disintegrating
over time but the Al foil was resistant to corrosion and its mass did
not change. Keeping the thin plastic film in hot PCM (75
C) for
extended periods of time contributes to a faster degradation.
However, despite these results, it is still possible to use the Al foil
laminate with the tested PCMs: although the plastic films disinte-
grate, there is no chemical reaction with the Al foil and there is little
risk of leakage if this material is used to make a pouch for PCM
encapsulation. The nylon and polypropylene laminations used in
this material are mostly for improving the heat-sealing. Heat-
sealed pouches made from the same Al laminate foil and containing
eicosane were shown to withstand repeated testing in a tablet
computer [38].
The results of the chemical compatibility studies performed in
the present work are summarized in Fig. 8. In the only published
report that can be used for comparison, our results for stainless
steel, Al and Cu are in good agreement with the results obtained for
the same materials with the commercial paraffin Micronal® [86].
Overall, our extensive compatibility study provides a vast choice for
materials that can be selected for the appropriate encapsulation of
any of the six paraffin PCMs.
4. Conclusions
In this work, paraffin PCMs that are potentially useful for TES in
building solar thermal and passive cooling applications were
investigated in detail. Motivated by the need for accurate properties
of useful paraffin PCMs, this work provides a comprehensive
evaluation of thermophysical properties, thermal stability and
chemical compatibility for six paraffins with melting points be-
tween 30 and 60
C. For each PCM, Tmpt, DfusH, as, Cp(T), the thermal
conductivities of the solid and liquid phases, and the density of the
solids were determined: the physical property results are sum-
marized in Table 3. All PCMs examined have high values of DfusH,
between 150 and 200 J g1 for the commercial paraffin waxes and
greater than 200 J g1 for the pure alkanes. The long-term cycling
results confirmed that both the pure paraffins and the blends are
thermally stable, with no noticeable changes to Tmpt and DfusH after
3000 melt-freeze cycles.
The chemical compatibilities of the PCMs with nine metal alloys
and seven plastics were determined from values of the corrosion
rates, CR, measured from corrosion immersion tests performed at
75
C. In addition, a laminated Al foil that has been used for PCM
encapsulation was also tested. In general, all tested metals were
compatible with the paraffins. However, some oxidation reactions
were observed for samples of Cu 101 and Mg AZ91D after 12 weeks
of immersion at 75
C in some paraffins. In contrast, not all the
plastic materials have good compatibility with the PCMs. The CR
 S. Kahwaji et al. / Energy 162 (2018) 1169e1182 1179

Fig. 7. Corrosion rates, CR, determined for plastic materials in each PCM. Materials with jCRj < 10 mg cm2 yr1 (within the solid boundary lines) are recommended for long-term
service whereas for jCRj < 50 mg cm2 yr1, the materials are not recommended for use with the PCM. For plastics, the negative CR values are due to PCM absorption.

Fig. 8. Chemical compatibility chart for all tested materials (excluding Al laminate foil) with the six PCMs as determined from the corrosion rates measured at 75
C.
1180 S. Kahwaji et al. / Energy 162 (2018) 1169e1182

Table 3
Summary of the thermophysical properties of the six paraffin PCMs measured in this study.

PCM Tmpt (
C) DfusH (J g1) rs (g cm3) as (mm s2) Cp,s (J K1 g1) Cp,l (J K1 g1) ks (W K1 m1) kl (W K1 m1)
Nonadecane 31.8 ± 1.5 181 ± 18 0.78 ± 0.08 0.19 ± 0.05 1.7 ± 0.2 (15
C) 2.3 ± 0.2 (60
C) 0.26 ± 0.04 (19
C) 0.18 ± 0.03 (60
C)
Eicosane 37.5 ± 1.5 246 ± 25 0.83 ± 0.08 0.26 ± 0.06 2.0 ± 0.2 (22
C) 2.6 ± 0.3 (55
C) 0.44 ± 0.07 (19
C) 0.23 ± 0.03 (60
C)
Docosane 43.8 ± 1.5 234a ± 23 0.82 ± 0.08 0.27 ± 0.07 1.7 ± 0.2 (20
C) 2.2 ± 0.2 (55
C) 0.37 ± 0.06 (19
C) 0.24 ± 0.04 (60
C)
PW48 48.2 ± 1.5 156 ± 16 0.86 ± 0.09 0.13 ± 0.03 2.3 ± 0.2 (25
C) 2.3 ± 0.2 (70
C) 0.26 ± 0.04 (19
C) 0.20 ± 0.03 (70
C)
PW52 51.8 ± 1.5 171 ± 17 0.78 ± 0.08 0.14 ± 0.03 2.0 ± 0.2 (25
C) 2.1 ± 0.2 (70
C) 0.22 ± 0.03 (19
C) 0.20 ± 0.03 (70
C)
PW58 57.7 ± 1.5 197a ± 20 0.88 ± 0.09 0.13 ± 0.03 2.0 ± 0.2 (25
C) 2.3 ± 0.2 (75
C) 0.23 ± 0.03 (19
C) 0.15 ± 0.02 (70
C)
a
Includes contribution from solid-solid transition very near the melting point.

values of polycarbonate, Type I PVC and ABS plastic showed that
these materials are safe to use at up to 75
C with all paraffins. On
the other hand, silicone rubber and polypropylene are not recom-
mended for use with any of the tested paraffins due to an excessive
absorption of the PCM.
The results of our study showed that the measured Tmpt of
paraffins waxes can vary significantly from the values specified by
the supplier. In addition, DfusH of paraffin PCMs can be over-
estimated due to the contribution of the solid-solid transition to the
DSC endothermic peak. Such uncertainties in these properties can
have detrimental influence on the outcome of numerical simula-
tions of PCM-based thermal energy storage systems, as confirmed
in a recent investigation [95]. Therefore, the accurate determina-
tion of the thermophysical properties conducted in the present
work can improve the reliability of future numerical studies that
consider any of the six paraffin PCMs investigated here. With our
recommendations concerning the chemical compatibility with
materials, the results of this work reliably provide all the necessary
information needed for the selection of a paraffin PCM for TES
applications with melting points between 30 and 60
C.
Acknowledgements
The authors thank Intel Corporation for the financial and tech-
nical support that made this work possible, along with the Natural
Sciences and Engineering Research Council of Canada (NSERC) for
grants to M. A. W. and D. G. In addition, S. K. acknowledges support
for a postdoctoral fellowship from Dalhousie Research in Energy,
Advanced Materials and Sustainability (DREAMS), an NSERC
CREATE program. This study also was supported by the Canada
Foundation for Innovation, the Atlantic Innovation Fund and other
partners that fund the Facilities for Materials Characterization
managed by the Clean Technologies Research Institute at Dalhousie
University.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.energy.2018.08.068.
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