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Phase Change Material Selection in the Design of a Latent Heat Energy Storage
System Coupled with a Domestic Hot Water Solar Thermal System

Conference Paper in ASHRAE Transactions · January 2011

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Phase Change Material Selection in the
Design of a Latent Heat Energy Storage
System Coupled with a Domestic Hot Water
Solar Thermal System

Louis Desgrosseilliers Robynne Murray

Alex Sefati Gina Marin Jeremy Stewart

Nicolas Osbourne Mary Anne White, PhD Dominic Groulx, PhD, P.Eng

Abstract
Home and business users of solar domestic hot water (SDHW) heating systems are able to reduce the energy costs and
greenhouse gas emissions associated with domestic hot water use. However, the level of deployment of solar thermal
technologies, as retrofits and new installations, is limited by the space and weight imposed on the structures for storing the
collected energy. Phase change materials (PCMs) are advantageous for daily energy storage with SDHW systems due to
their high energy storage density, and mainly isothermal operation. This paper summarizes the initial steps in the
development of an energy storage system using PCMs, with emphasis on the material selection and experimental studies used
for proof of concept and design optimization.
Lauric acid was selected as the PCM based on the melting temperature range that was targeted by studying solar data
from an existing solar hot water system in Halifax, Nova Scotia. The proof of concept experiment was done using a finned
tube to carry the thermal fluid; these extended surfaces were used due to the low thermal conductivity of PCMs. A validated
and optimized design will be built and installed by early 2011 for a pilot study in an existing large scale solar thermal system
on an apartment building in Halifax. The entire system will be instrumented in order to acquire continuous data
(temperatures, flow rates, pressure, etc.) to fully characterize the system and improve on this first tested prototype.

INTRODUCTION
Using phase change materials (PCMs) for latent heat energy storage with SDHW systems reduces the volume and
weight of thermal storage due to their high energy storage density (Agyenim, 2010). Latent heat energy storage systems
(LHESS) have preferable energy storage properties in comparison to sensible heat storage (Fernandez, 2010), and have been
shown to store 5-14 times more heat per unit volume than sensible heat storage materials such as water (Sharma et al., 2009;
Farid et al., 2004).

Louis Desgrosseilliers and Robynne Murray are Masters of Applied Science students in the Department of Mechanical Engineering,
Dalhousie University, Halifax, Nova Scotia. Alex Safatli is a undergraduate chemistry student in the Chemistry Department, Dalhousie
University. Gina Marin, Jeremy Stewart and Nicholas Osbourne are undergraduate mechanical engineering students in the Department of
Mechanical Engineering. Dalhousie University. Mary Anne White is a professor in the Chemistry Department, Dalhousie University. Dominic
Groulx is a professor in the Department of Mechanical Engineering, Dalhousie University.
 PCMs are the only materials that undergo melting and freezing in a desired temperature range to store and release
thermal energy. They are classified into two categories: organic and inorganic PCMs. Organic PCMs in practical use are
either fatty acids or waxes (e.g. olefins and alkanes), and in some cases polymers and aromatics. Inorganic PCMs are nearly
always salt hydrates, but can include other aqueous solutions or pure substances (e.g. ice). Organic PCMs usually have low
thermal conductivity and moderate latent heat of fusion; inorganic PCMs have typically higher heats of fusion and thermal
conductivity, but many suffer from cycling instabilities of these properties as well as supercooling. It is imperitive that PCM
selection for a LHESS addresess all of these issues.
Energy storage using PCMs in combination with solar collectors has been studied mathematically (Qarnia, 2009) and
experimentally (Sari, 2003) and shown to be advantageous; however, missing from previous works is a working prototype of
a SDHW system for a large scale application (Shukla, 2009).
Due to the low thermal conductivity of PCMs in general, design characteristics to enhance heat transfer need to be
identified in order to optimize LHESSs. Many different methods of enhancing heat transfer have been studied, and include
fins, multi-tube arrays, bubble agitation, metal rings, matrixes and brushes, encapsulation, etc. Fins are the most commonly
used, and various studies have compared different fin sizes and orientations. Castell et. al. (2008) used a cylindrical PCM
container with external (HTF side) 2mm thick vertical fins and showed that for vertical fins, the longer the fins offer better
heat transfer rates. Agyenim et. al. (2009) showed that longitudinal fins are advantageous over circular fins. Gharebaghi and
Sezai (2008) developed a mathematical model to compare circular fin spacing based on the finite volume method, and
concluded that the closer the fins were together, the larger the increase in heat transfer rate.
This paper presents the results of a study aimed at characterizing a short list of PCM candidates for a LHESS to be used
in Halifax, Nova Scotia, and experimentally study the performance of the selected PCM using a vertical fin arrangement for
the heat exchange. The selected design will be built and installed by early 2011 in an existing large scale solar thermal system
on an apartment building in Halifax.

PHASE CHANGE MATERIAL SELECTION

Primary Selection
Data on solar heat collection in a glycol heat exchange SDHW system was obtained from our industry partner, Scotian
Windfield. Analysis of the system performance over one year determined that a suitable PCM must have a peak melting
temperature in the range of 42-48°C (108-113ºF). Also, freezing should at the minimum occur between 35°C and 40°C (95
and 104ºF). A short list of PCMs meeting the melting criterion is in Table 1. Glauber’s salt remained in the short list since it
has a high reported latent heat of fusion and thermal conductivity. In-house calorimetric testing would confirm whether the
melting/freezing ranges would be acceptable for the given application. The other desirable properties affecting the selection
were low toxicity and cost.
Table 1. PCM Short List
PCM Type Melting Latent Heat of Source
Temperature, °C Melting, kJ/kg
(ºF) (Btu/lb)
Na2SO4∙10H2O (Glauber's salt) Salt Hydrate 32 (89.6) 251 (108) Zalba et al., 2003
Na2S2O3∙5H2O (Sodium Thiosulfate Pentahydrate) Salt Hydrate 48 (118) 206 (88.7) Kenisarin and
Mahkamov, 2007
CH3(CH2)10COOH (Lauric acid) Fatty Acid 44 (111) 181 (77.9) Chemical
Properties
Handbook, 1999

Final Selection
The most promising materials were tested using a differential scanning calorimeter (DSC) to study their melting
temperature ranges and identify materials with significant supercooling 1.
The salt hydrates that were tested (Glauber’s salt and sodium thiosulfate pentahydrate) showed supercooling during
DSC testing, which is a common phenomenon for these materials (Sandnes, 2006). Figure 1a) shows the DSC curve for
Glauber’s salt, confirming its melting range (32 to 38°C [89.6-100.4ºF]) insufficient for the LHESS to be designed.
Supercooling was also far too great with more than 40°C (104ºF) of supercooling. Similar results were obtained for sodium
thiosulfate pentahydrate, eliminating both inorganic PCMs from further consideration. Furthermore, research is still
performed in order to determine their stability over the extended melt/freeze cycles, but reports indicate that most salt
hydrates have poor phase stability (hysterisis of the phases) and require additives for reduced supercooling and thickening
(Sandnes, 2006), and polymeric encapsulation to prevent metal corrosion (Kenisarin, 2007), making them more costly and
more difficult to incorporate into a LHESS design.
The DSC curve for lauric acid (crude, <80%, Fisher Scientific), shown in Figure 1b), has distinct peaks for melting
(blue curve) and solidification (red curve) and shows a melting temperature range of 43.32 to 45.7 oC (110 to 114.3ºF) and
freezing range of 35-38.8°C (95-102ºF). The DSC curve for this lower purity sample compared well with thermodynamic
data from literature for pure lauric acid (Chemical Properties Handbook, 1999).

a)

b)

Figure 1 (a) DSC curve for Glauber’s salt showing 40ºC supercooling; (b) DSC curve for lauric acid

1
Supercooling means freezing occurring at a temperature below the melting point of the material. Some supercooling is common in
differential scanning calorimetry because the specimen pans are very smooth and the technique uses non-equilibrium based
processes.
 These results made lauric acid an extremely interesting candidate PCM for this project based on its melting temperature
range, high heat of fusion and minimal supercooling, and inherent safety for human health and the environment (listed only
as a mild irritant (Alfa Aesar, 2009); the material properties are displayed in the Table 2 below.

Table 2. Thermal and Physical Properties of Lauric Acid (Chemical Properties Handbook, 1999; Alfa
Aesar, 2009)
Molecular Weight, kg/kmol (lb/lb-mol) 200.31 (200.31)
Density of Powder at 20°C (68ºF) / Liquid at 45°C (113) 0.869/0.873
Fusion Temperature, ˚C (˚F) 45 (113)
Latent Heat of Fusion, kJ/kg (Btu/lb) 0 181.184 (77.960)
Heat Capacities Solid/Liquid, kJ/kgK (Btu/lbR)** 2.36/2.03 (0.564/0.485)
Thermal Conductivities Solid/Liquid, W/mK (Btu/sftR)** 0.150*/0.148 (2.41/2.38x10-5)
Viscosity, Pa s (psi s)** 0.00802 (1.16x10¸-6)
*
Experimentally measured value.
**
Nominal properties calculated near the melting point.

Lauric acid of a higher purity (98%, Alfa Aesar, CAD$16.50/kg) was used in the project for proof of concept and
prototyping, so the material properties were not expected to degrade significantly over time. To illustrate, Figure 2 compares
literature values for the heat of fusion and melting point with those obtained by DSC tests of crude lauric acid after 300
cycles of complete melt/freeze. The DSC tests were conducted with samples < 5 mg from 20 to 55ºC at 10ºC/min (68 to
131ºF at 18ºF/min). After 300 cycles, there were no obvious signs of degradation for the crude purity sample, despite reports
from Sari and Kaygusuz (2003) that latent heat decreased by 25.9% after 410 cycles (16.5% after only 40) using a technical
grade lauric acid (97%).

Figure 2 Measured melting temperatures and heats of fusion of lauric acid repeated phase transitions cycles

EXPERIMENTAL SETUP
Figure 3a) shows the experimental setup used to study the melting and solidification behavior of lauric acid in a
cylindrical container with vertical copper fins. A Solidworks 3D rendering of the container is shown in Fig. 3b. National
Instruments 16-channel thermocouple module (NI9213) CompactDAQ data acquisition system connects eight type T probe
thermocouples, and temperatures are recorded using LabView. Thermocouples are located inside the lauric acid (T2 to T7) as
well as on the inlet and outlet (T1 and T8), as seen in Fig. 3a). A counter/pulse generation module (NI9435) on the DAQ
system reads a pulse counter flowmeter from Omega using LabView. The container is made of ¼-inch acrylic plastic and is
un-insulated to allow visual study of the system.

Fig. 1. (a) Schematic of the experimental setup and (b) PCM container with vertical fins.

Table 3 summarizes the conditions used to perform the experiments:

Table 3. Experimental parameters.

Hot Water Inlet Velocity, m/s (ft/s) 1.5 (4.9)
Cold Water Inlet Velocity, m/s (ft/s) 3.5 (11.5)
Hot Inlet Temperature, ºC (ºF) 55 ± 1 (131 ± 1.8)
Cold Inlet Temperature, ºC (ºF) 12 (53.6)

Lauric acid was initially solid in the container at room temperature. The charging (melting process) began when hot
water from the constant temperature water bath was pumped through the copper tube to melt the lauric acid. The charging
portion of the experiment was completed when the system reached steady state, after which cold water from the municipal
water supply was pumped through the system to solidify the lauric acid and recover the stored thermal energy. When the
lauric acid returned to steady state at room temperature, the experiment was concluded and the temperature data analyzed.

EXPERIMENTAL RESULTS AND DISCUSSION

The first experiment for lauric acid inside the PCM container was run for melting. Figure 4 shows the temperature
progression at the thermocouple locations inside the PCM container during 10 hours of charging. The first thermocouples to
record phase change were the nearest to the fins and top of the container (T2, T3) after 2 hours, closely followed by T4 and
T6, between 2 and 3.5 hours. T5 was the last to melt at 5.25 hours, while some solid remained (liquid with solid film
remaining) in T7.
A closer analysis of the thermocouple set in Figure 5 illustrates the consistent appearance of an inflection point in each
of the curves near 42ºC (107.6ºF). This indicates the complete liquefaction of lauric acid at these thermocouples as the
change in temperature of the lauric acid becomes controlled by the smaller liquid heat capacity, as oppose to the much larger
heat of fusion. Natural convection is also present in the liquid phase, which speeds up the heat transfer rate and the melting
process even more.

Figure 4 Plot of the temperatures inside the PCM container during charging

Figure 5 Plot of the temperature progression in the radial direction inside the PCM during charging

The second experimental result was obtained from freezing the lauric acid inside the PCM container. Figure 6 shows
the temperature progression at the thermocouple locations inside the PCM container during the 10 hours of discharging. The
first thermocouples to record phase change were the T2 and T3 between 0.5 and 1.5 hours. T4, T5 and T6 recorded phase
change between 1 and 2.5 hours. Since the PCM remained solid at the location of thermocouple T7 from the previous melting
experiment, it steadily cooled.
 Figure 6 Plot of the temperatures inside the PCM container during discharging

Figure 7 illustrates the presence of constant temperature plateaus, where phase change is occurring near 43ºC (109.4ºF).

Figure 7 Plot of temperature progression in the radial distance inside the PCM during discharging

Observation from the experiment confirmed the pure substance phase change behaviour as noted in the DSC tests.
While the peak melting temperature of lauric acid in the DSC tests varied between 43 and 44ºC (109.4 and 111.2ºF), phase
changes in the experiment were between 42 and 43ºC (107.6 and 109.4ºF). This was acceptable and did not show incongruity
of the phase change of lauric acid in both systems since they are both prone to temperature error due to dynamic phase
change effects and averaging affects of the surrounding material; the thermocouple used also have a ±1ºC (±1.8ºF) accuracy.
Furthermore, thermocouple measurements in the experiment became affected by poor thermal contact with the solid PCM
due to volume change from freezing, but were restored when immersed in liquid PCM. This slowed thermocouple response
in the melting experiment and could not provide the necessary resolution to observe the phase transition plateaus as were
seen during freezing.
The ripples in the uppermost part of the curves in Figures 4 and 5 indicate a strong heat transfer relationship to the
temperature fluctuations (due to the on/off controller for the heater) observed in the hot water supplied to the PCM container
with the same frequency and period (T1 and T8 in Figure 4). The height of the ripples in the PCM thermocouple data is
inversely proportional to the distance from the centre tube and fins, dampening the relationship between the hot water
temperature and the PCM as the heat needed to permeate through larger areas with increasing radial distance in the container.
None were seen during freezing of the PCM since the cold water supply had no such fluctuations.
Despite the low thermal conductivity of lauric acid, the experiment was able to demonstrate a rudimentary LHESS
operating with modest heat exchange temperatures, akin to SDHW systems, requiring charging periods of less than 6 hours
and subsequent withdrawal in less than 3 hours. Proximity to fins and the central tube quickened phase transition in either
direction, but freezing also occurred more quickly in the areas between the fin ends and the container wall. The latter was an
effect of heat loss trough the wall to the room, since the plexiglass container was not insulated in order to make visual
observations of the phase change inside the container. The PCM container only required modest extended heat exchange area
(fins), so further effort into optimizing fin utilization could only benefit the usefulness of a similar LHESS.

CONCLUSION
Lauric acid was chosen from a short list of possible PCMs for study in a LHESS. Lauric acid only costs CAD$16.50/kg
for non-bulk quantities, is safe to use, and has desirable melting and freezing qualities (latent heat of fusion, melting point, no
 supercooling). However, lauric acid is a poor heat conductor, so the experimental set-up used to evaluate it’s usefulness in a
LHESS made use of four axially positioned fins, attached to a central heat exchange tube to enhance the heat exchange.
With hot water supplied at 55ºC (131ºF) and cool domestic water supplied at 12ºC (53.6ºF), the experimental LHESS
was able to store latent heat in less than 6 hours and withdraw it in less than 3 hours. Consistent phase change behaviour was
noted between the experiments, DSC tests, and the literature.
Needing only a thermally insulated PCM container and an optimized extended surface heat exchanger design (i.e. fin
number and spacing, and multiple passes), the rudimentary LHESS design using lauric acid is a promising choice for the
development of a full scale LHESS to be used in SDHW residential and commercial applications.

AKNOWLEGMENTS
We thank Scotian Windfields for their support and expertise, as well as for funding this project; Eco-Nova Scotia and
the Natural Sciences and Research Council of Canada for their financial support; and the Department of Mechanical
Engineering of Dalhousie for research space and some equipment.
The DSC is part of the Facilities for Materials Characterization managed by the Institute for Research in Materials at
Dalhousie University. We are also grateful for the assistance of Brian Miller, Department of Chemistry, in assembling the
melt/freeze cycling experiment.

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