Renewable and Sustainable Energy Reviews 48 (2015) 79–87

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Review on shell materials used in the encapsulation of phase change

materials for high temperature thermal energy storage
Rhys Jacob n, Frank Bruno
Barbara Hardy Institute, University of South Australia, Mawson Lakes, SA 5095, Australia

art ic l e i nf o a b s t r a c t

Article history: This paper presents a detailed review of shell materials that have the potential to be used for high
Received 12 August 2014 temperature thermal energy storage (TES) applications, particularly in conjunction with concentrated
Received in revised form solar power (CSP) plants. This paper considers shell materials that are thermally stable at more than
4 March 2015
300 1C and have successfully been used to encapsulate a phase change material (PCM). The current
Accepted 8 March 2015
review does not consider the thermal performance of the shell material and PCM combinations that have
been studied. Using these constraints several feasible materials were identified including: steel (carbon
Keywords: and stainless), nickel (and nickel alloy), sodium silicate, silicon dioxide, calcium carbonate and titanium
Encapsulation shell material dioxide. These materials have the potential to encapsulate high temperature PCMs and thus provide a
Phase change material suitable method of high temperature TES.
Thermal energy storage
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2. Encapsulation shell materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.1. Material selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.1.1. Desirable characteristics of encapsulation material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.1.2. Fabrication of encapsulated phase change materials (EPCMs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2. Type of materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2.1. Macroencapsulation (MEPCM) materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2.2. Microencapsulation (mEPCM) materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.2.3. Comparison of shell materials and their potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

1. Introduction gases have to be reduced globally, up to 50% in the next 50–100

years, for irreversible damage to the environment to be avoided
Energy production and consumption continues to be a deba- [2]. In an effort to prevent this from occurring, efforts have been
table topic when discussing the future. Currently the majority of made to help develop, commercialize and deploy renewable
energy produced comes from fossil fuels (coal, oil and gas) [1]. This energy technologies. Of the renewable technologies currently
is viewed as a problem as these sources of energy generate large being investigated, solar energy is one of the more promising.
amounts of greenhouse gases, mainly CO2, and fossil fuels are Solar energy is abundant and freely available which makes it an
finite. Experts around the world have warned that greenhouse attractive alternative to fossil fuels. In particular concentrated solar

Abbreviations: PCM, phase change material; TES, thermal energy storage; CSP, concentrated solar power
n
Corresponding author. Fax þ61 08 83023380.
E-mail address: [email protected] (R. Jacob).

http://dx.doi.org/10.1016/j.rser.2015.03.038
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
80 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87

power (CSP) is of great interest to researchers and governments 2. Increase the thermal conductivity of the PCM system: Consider-
[3,4] and provides a workable solution to this problem. CSP able work has been conducted to improve the thermal
technologies use mirrors to reflect and concentrate sunlight onto conductivity of PCM systems. Examples of thermal conductivity
receivers that collect solar energy and convert it to heat. enhancement on a PCM system can be found in Refs. [8–14].
This thermal energy can then be used to produce electricity via These references present investigations on the use of extended
a steam turbine or heat engine that drives a generator [5]. surfaces, employing multiple PCMs, enhancement of the ther-
However, one challenge facing the widespread use of solar energy mal conductivity of the PCM directly by adding highly thermal
is reduced or curtailed energy production when the sun sets or is conductive materials and dynamic melting and encapsulation
blocked by clouds. of the PCM.
Thermal energy storage (TES) provides a workable solution to
this challenge. TES allows the storage of heat and cold for later use. Encapsulation of PCMs serves as a way to increase the surface
TES can aid in the efficient use and provision of thermal energy area for heat transfer therefore increasing the thermal conductivity of
whenever there is a mismatch between energy generation and the latent heat thermal storage (LHTS) system [15]. Encapsulation
use. This mismatch can be in terms of time, temperature, power, or also has the benefit of protecting the PCM from environmental
site. An added benefit of TES is that a CSP plant with storage has factors, increasing the compatibility of the PCM with storage materi-
shown that the levelized energy cost (LEC) can improve the als, reduced corrosion and the ability to control volume change
economy of parabolic trough plants, provided that the storage is during phase change. Classification of encapsulation is dependent on
big enough. Herrmann et al. [6] has found that storage of 12 h full the size of encapsulation. Macroencapsulation, microencapsulation
load capacity reduces the LEC by about 10%. To achieve a and nanoencapsulation are encapsulated PCMs with diameters 1 mm
competitive LEC of CSP investigation is required into methods of to greater than 1cm, 1 μm to 1 mm and less than 1 μm, respectively.
TES. Of particular interest in this field is the use of phase change Due to the many advantages of encapsulating the PCM, work is being
materials (PCMs) as a thermal storage media. done to investigate the possibility of using encapsulated PCMs for
Latent heat is the amount of energy in the form of heat released or TES, energy saving building materials and thermo-regulated fibers
absorbed by a material during a change of state or phase transition and foams [16]. This paper only investigates encapsulation materials
such as solid to liquid (melting) or liquid to gas (vaporization). Phase to be used for high temperature (above 300 1C) TES applications.
change materials (PCMs) are those that exhibit a large amount of Shell composition for encapsulation for high temperature
stored latent heat in molecular bonds. These bonds can be broken applications continues to be an area needing further technical
when sufficient heat is applied, storing energy. Conversely when the investigation. Most work is focused on the PCM rather than the
molecular bonds are restored, large amounts of energy are released. encapsulation material.
The main advantages of PCMs is that they can store a relatively large Previous studies have investigated the use of high temperature
amount of energy in a small volume, they have low flammability and PCMs in TES [7,17,18], encapsulation fabrication [19,20], encapsu-
low cost. However the major drawback for most PCMs is that they lation applications [21] and the effect of encapsulation on the
have very low thermal conductivity. This leads to undesirably long system [22]. Reviews have also been undertaken to investigate
charge/discharge times, which in CSP applications negatively affect improvements of latent heat storage systems [23–26]. However a
dispatchability of power [7]. To compensate for the inefficiency of review of materials with high thermal stability for use as a shell
PCM TES systems it is desirable to: material in PCM capsules has not been undertaken.
This paper investigates and provides a list of encapsulation
1. Operate the system at higher temperatures: High operating shell materials with high thermal stability (i.e. the material does
temperatures are desirable for TES in CSP plants as the efficiency not appreciatively physically degrade and whose properties do not
of the system is directly related to the operating temperature, i.e. significantly change when under high temperatures), which could
the higher the operating temperature of the system, the higher the provide a workable solution for high temperature TES, particularly
thermal efficiency. Therefore a high operating temperature is in conjunction with a CSP system. The encapsulation material is an
desirable to generate the largest amount of power from a given important factor to consider when designing a latent heat storage
system. Operation at high temperatures would also enable the use system as the encapsulation material plays a key part in the
of Brayton cycle gas turbines enabling much higher efficiencies. efficient heat transfer from the heat transfer fluid (HTF) to the

Table 1
Macroencapsulation materials with high thermal stability.

Year Author(s) Shell material Core material Thermal stability temp in test, 1C Theoretical melting point, Reference
1C

2014 Vicente and Silva Steela Paraffin wax 36b 1370 [28]
2014 Zhang et al. Chromium–nickel Copper 4 1150 [29]
2013 Zhao et al. Stainless steel 304L Magnesium 4 750 – [30]
chloride
2013 Zheng et al. Stainless steel 304/carbon steel Molten salt 4 470 – [31]
1018
2012 Nath Sodium silicate Molten salt 300b 1088 [32]
2012 Nath Carbon steela Molten salt 800 1370 [32]
2012 Pendayla Silicon dioxide Sodium nitrate 300–500b 1600 [33]
2011 Terrafore© Metallic–ceramica Molten salt 300–800 – [34]
2005 Wei et al. Stainless steela Paraffin wax – 1400 [35]
2003 Maruoka and Nickel Lead 400b 1455 [36]
Akiyama
2002 Maruoka et al. Nickel Copper 4 1100c – [38]

a
Exact material specification not given.
b
Due to breakdown of PCM or max temperature tested.
c
Stability for Ni–C and Ni–Ru shell.
 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87 81

PCM. Efficient conduction requires a material with high thermal 2.2. Type of materials
conductivity. The encapsulation material must also be compatible
with the PCM and the storage materials and be durable as it must Materials that can be considered as suitable shell materials for
provide a barrier to the outside environment [22]. The current high temperature applications are investigated in the following
review does not consider the thermal performance of the shell sections. They are grouped as to materials that have been used in
material and PCM combinations that have been studied. The macrocapsules and microcapsules with a PCM. The results of this
review also does not include materials used for nanocapsules. investigation are summarized in Tables 1 and 2.
This is due to the research on nanoencapsulation still being at the
laboratory level. As such, more research is required to bring
nanoencapsulation into commercial applications. 2.2.1. Macroencapsulation (MEPCM) materials
Vicente and Silva [28] recently investigated the use of steel
macrocapsules impregnated in a brick masonry wall, using paraf-
fin wax as the core material. Successful thermal testing at low
2. Encapsulation shell materials
temperatures (o40 1C) show the ability of this type of system at
storing and releasing energy as needed. Although the thermal
2.1. Material selection
stability at high temperatures was not investigated in this study,
the successful encapsulation of a PCM with steel warrants further
2.1.1. Desirable characteristics of encapsulation material
study for high temperature applications. Zhang et al. [29] inves-
When designing a TES system using encapsulated PCMs it is
tigated the use of copper as a PCM by encapsulating it in a
important to ensure that the encapsulation or containment of PCM
chromium–nickel shell, (see Fig. 1). Due to the high melting points
should:
of the materials involved, it is reasonable to assume that this type
of encapsulation would be suitable for high temperature applica-
 meet the requirements of strength, flexibility, corrosion resis-
tions. To confirm this, charging/discharging tests were carried out
tance and thermal stability;
from 1050 1C to 1150 1C and then allowed to cool back to 1050 1C
 act as a barrier to protect the PCM from harmful interaction
with the environment;
 provide sufficient surface for heat transfer; the PCM has a low
thermal conductivity so to increase the heat transfer rate, it is
encapsulated in conducting materials to increase the heat
transfer area to enhance the melting and solidification process;
 provide structural stability and easy handling [27].

2.1.2. Fabrication of encapsulated phase change materials (EPCMs)

Fabrication of EPCMs can be achieved via chemical or physical
methods. Physical methods employed are spray drying or centri-
fugal and fluidized bed processes. Chemical methods include
interfacial polymerization, in situ polymerization, the sample or
complex coacervation, phase separation and suspension-like poly-
merization. Chemical methods are usually preferred due to its
properties and applications. For a full review of all fabrication
methods, readers are directed to recent work published by Fig. 1. SEM image of the cross-sectional morphology of the copper capsule after
Jamekhorshid et al. [20]. thermal cycling [29].

Table 2
Microencapsulation materials with high thermal stability.

Year Author(s) Shell material Core material Thermal stability temp in test, 1C Theoretical melting point, 1C Reference

2014 Cao et al. Titanium dioxide Paraffin wax 240a 1843 [39]
2014 He et al. Sodium silicate n-Octadecane 4375 1088 [40]
2014 Khakzad et al. M–F Hexadecane 388 – [41]
2014 Li W et al. VTMS n-Octadecane 318.2 – [43]
2014 Li et al. UFR Stearyl-alcohol 250–350 – [44]
2014 Yu et al. Calcium carbonate n-Octadecane 215a 825 [47]
2013 Qiu et al. BA–DVB n-Octadecane 380 – [48]
2012 Ma et al. P(MMA-co-DVB) Butyl stearate and paraffin 375–475 – [49]
2012 Qiu et al. BMA–MMA copolymer n-Octadecane 385 – [50]
2011 Salüan et al. Poly(urethane–urea) Xylitol 350 – [51]
2010 Fang et al. Silicon dioxide Paraffin wax 292a 1600 [52]
2010 Sánchez et al. St–MMA Paraffin wax 320 (pure) – [54]
325 (capsule)
2010 Zhang et al. Silica n-Octadecane 325 – [55]
2009 Yu et al. M–F n-Dodecanol 404 (pure) – [42]
371 (capsule)
2007 Sánchez et al. Polystyrene Paraffin wax 340 – [57]

a
Due to breakdown of PCM or max temperature tested.
82 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87

Fig. 3. TerraCaps macrocapsules with molten salt PCM [34].

showed that this method failed at temperatures greater than

300 1C due to moisture loss from the PCM through the porous
silicate layer. The porous PMMA layer had failed to prevent PCM
loss as was intended. Nath [32] then investigated the possibility of
using preformed carbon steel capsules to house the PCM.
By using preformed shells, capsule size can be more easily
Fig. 2. Cut-away photo of encapsulated phase change material (NaCl–MgCl2 controlled and they also take less time to fabricate. When tested at
eutectic) after thermal cycling [31]. high temperatures the carbon steel began to show signs of corrosion.
Sodium silicate and high temperature paints were used to prevent
by natural convection. Thermal cycling was performed 1000 times corrosion. Both methods were successful at high temperatures and at
and the capsules were checked for leakage. The tests concluded low numbers of thermal cycling (7). It should be noted that for
that after 1000 charge/discharge cycles, the chromium–nickel sodium silicate to be successfully used as a shell material a non-
shell was still intact and no leakage was observed. From this test porous intermediate layer is required. Research conducted by Pen-
it can be concluded that a chromium–nickel shell is a good dayla [33] provided the option of encapsulating sodium nitrate using
candidate for high temperature encapsulation applications. several shell materials. Several methods of fabrication were investi-
Zhao et al. [30] investigated the use of magnesium chloride as a gated including electroless (nickel and copper), using sodium silicates
PCM in a cylindrical stainless steel 304L shell for high temperature (N, K and RU), using a high temperature resin (polybenzimidazole
TES. A single thermal cycle was conducted on the EPCM where it (PBI)) and using sand (with sodium silicate as binder (5 wt% to wt
was heated from 745 1C and then allowed to cool back to ratio)). Each method was successful in encapsulating the PCM with
approximately 33 1C. The results show that agreement between varying degrees of success. Problems were identified with sodium
theoretical and measured values was better than 2%. Long term silicates as the silicon dioxide shell material condenses to form water
high temperature exposure tests were also conducted on the three at higher temperatures which results in defects and bubbling. The
samples. The samples were preheated to 750 1C and held at that addition of titanium dioxide minimized to a large extent the defects
temperature for 8 h. It was then cooled to 500 1C and then held at over glass substrates but no significant improvement was observed
this temperature for 2 h. This cycle constituted one thermal test. on salt substrates. The disadvantages of using sand as an encapsula-
Each sample had between 112 h and 480 h of exposure at 750 1C. tion material were identified such as high porosity and moisture
Again the results showed agreement between theoretical and absorbability. However, Pendayla [33] reports that by employing
measured values was better than 2% for all samples, further proper techniques these shortcomings can be overcome. Pendayla
underlining its suitability at high temperatures. Zheng et al. [31] was however able to successfully encapsulate the PCM using sand. To
investigated the use of encapsulated salts as a storage medium for be considered for high temperature applications further investigation
CSP plants. As these plants generally operate around 400 1C, it was must be done on this technique. PBI is shown to be thermally stable
important to select a PCM with a melting point close to the to a temperature of 400 1C. However a stable encapsulation was
operating temperature and a suitable encapsulating material. For unable to be achieved, even using multiple coatings. This led
this test two salts (sodium nitrate and a eutectic of sodium Pendayla to investigate using a metal oxide (SiO2) as an encapsula-
chloride and magnesium chloride) were encapsulated in stainless tion material. This method of encapsulation produced much more
steel 304 cylinders, (see Fig. 2). stable capsules; however achieving consistent pellets of shell thick-
To test whether this method of storage was suitable thermal ness, pellet size and void spacing proved difficult. Despite this if a
testing at 370 1C was undertaken. Results from this test indicated more consistent method of fabrication can be found using silicon
that the measured stored energy is within 72% of the theoretical, dioxide then high temperature applications could be investigated.
indicating that the EPCM behaved as anticipated. There were also Commercial methods of macroencapsulation are also available.
no signs of deterioration on any of the samples. To further prove Terrafore© [34] have successfully fabricated and thermally tested
their applicability thermal cycles were undertaken at 370 1C (50 macrocapsules filled with molten salt. Terrafore© use a patented
cycles) and high temperature cycling at 470 1C (50 cycles, eutectic method to fabricate the macrocapsule, (see Fig. 3).
only.) Results from these tests also showed no loss in energy Further investigation shows that a sacrificial polymer must be
stored in the PCM or deterioration of the encapsulating material. used to create a void in the capsule to prevent volume expansion
Nath [32] successfully encapsulated a molten salt using sodium related stresses, leakages and breakages. The shell material is not
silicate and a preformed carbon steel capsule. Initially sodium explicitly specified in the patent however it is mentioned that it is
silicate was used as a shell material. Thermal stability testing a combination of metallic and ceramic materials [34]. This method
 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87 83

Fig. 6. SEM image of (50/50) n-octadecane/sodium silicate mEPCM [40].

for high temperature applications assuming the correct diameter

and nickel layer thickness is used. Interestingly though the
Fig. 4. Cross section of a macrocapsule before heating [38]. measured tensile strength of the nickel capsule was less than
predicted from literature [37].
Kaya and Laby [37] suggested that this was due to two reasons:
one is that the material generally becomes weak under high
temperatures, and two, the structure of the nickel layer owing to
the electroplating process yielded layers where the nickel is not
properly stuck to the PCM. These suggestions warrant caution when
considering nickel as a shell material however it should not be
discounted purely on this finding. Maruoka et al. [38] investigated
the use of encapsulated PCMs as a storage medium to recover waste
heat from industrial processes. To achieve this they investigated
copper as the PCM encapsulated by a nickel shell, (see Fig. 4).
To test if this capsule would be thermally stable at the high
temperatures intended, thermal cycling tests were undertaken. The
capsule (diameter 3 mm) was heated from room temperature to
1100 1C, held at this temperature for 1 h and then allowed to cool
naturally to room temperature. This process was undertaken up to 50
times assuming there was no breakage observed in the shell. From
this test it was concluded that a nickel capsule was not suitable for
this application as it was unable to prevent breakage. However when
an inhibition layer was inserted (carbon or ruthenium) the nickel-
Fig. 5. SEM image of TiO2 mEPCM [39].
insert shell was stable over the 50 cycles. This has led to the
conclusion that if an insert is added to the nickel shell, it becomes a
provides a thermally tested method of encapsulation for high viable option for high temperature applications.
temperature TES, and should be considered as a reference point for
further commercial packed bed encapsulated PCM systems. Wei
et al. [35] studied the effect of geometry, capsule diameter, shell 2.2.2. Microencapsulation (mEPCM) materials
thickness and void fraction of a stainless steel capsule with a PCM Cao et al. [39] investigated the possibility of microencapsulating a
core. They determined that a smaller diameter, thin walled paraffin wax core with a titanium dioxide shell, (see Fig. 5). The
spherical capsule provided the highest energy density and thermal addition of the titanium dioxide shell was shown to prevent the
stability. They found the void fraction had no measurable effect on paraffin from degrading quickly, while maintaining the degradation
spherical capsules. High temperature testing was not conducted onset temperature (240 1C) and the peak weight loss temperature
on the samples but the high thermal stability of stainless steel (300 1C). The high melting point of pure titanium dioxide makes it a
warrants further investigation. Maruoka and Akiyama [36] tested feasible choice for high temperature TES applications.
the thermal stress of an encapsulated PCM of various sizes. They He et al. [40] investigated the use of sodium silicate as a shell
used lead as the PCM and a nickel film as the encapsulation material for a n-octadecane core, (see Fig. 6). It was found that the
material. The capsules were heated from room temperature to microcapsule successfully delayed the evaporation of n-octade-
673 K (400 1C) then allowed to cool back to room temperature. cane from the capsule suggesting the silica wall can prevent the
This was undertaken 50 times to gather results. Analysis of the encapsulated n-octadecane from evaporating at the normal boil
thermal stress indicates that a capsule of diameter 0.5 mm and point, thus improving the degradation temperature of the micro-
with a nickel layer 25 μm thick was stable for 50 cyclic tests. capsules. Thermal stability of the silica shells was also investigated
Capsules with a diameter of 1, 3 and 4 mm all with a nickel layer with stage II decomposition occurring at more than 375 1C for all
50 μm thick were also stable for 50 cyclic tests. These results samples. It is suggested that this is due to water evaporation which
suggest that nickel could theoretically be used as a shell material occurs when the silica wall undergoes condensation. This water
84 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87

equates to a 5 wt% loss. The high thermal stability and low cost of successfully microencapsulated n-octadecane using p(butyl
sodium silicate as a shell material warrants further investigation at methacrylate) (PBMA) and p(butyl acrylate) (PBA) as the shell
higher temperatures. material. Qiu et al. [48] used divinylbenzene (DVB) and pentaer-
Khakzad et al. [41] investigated the possibility of using mela- ythritol triacrylate (PETA) as crosslinking agents. TGA analysis of
mine–formaldehyde (M–F) resin as a shell material. On this the samples tested show stage I decomposition occurring between
occasion hexadecane (HD) was used as the core material. Samples 221 1C and 248 1C, (stage I decomposition is usually associated
were made using different surfactant amounts and various stirring with the weight loss from the loss of the PCM through the porous
rates. It is suggested from the results that a higher surfactant wt% shell). Stage II decomposition for all samples occurred between
results in better M–F settling on HD droplet. This leads to a more 349 1C and 380 1C (stage II decomposition is associated with the
compact shell formation and higher thermal stability. The effect of thermal decomposition of the shell material). From the results it
the homogenized stirring speed was also investigated. It was was concluded that although successful encapsulation was
found that a speed of 6000 rpm leads to the highest degradation achieved, the low thermal decomposition temperature of even
temperature (388 1C) of all speeds investigated. The results of this the most thermally stable sample (BMA–PETA) is not enough to
research mirror the previous results by [42]. Li et al. [43] recently suggest its use in most high temperature applications. Ma et al.
investigated the possibility of microencapsulating n-octadecane [49] investigated the use of temperature adjustable encapsulated
using a hybrid shell of MPS (3-(trimethoxysilyl) propyl methacry- PCMs by using a binary mixture of butyl stearate and paraffin as
late) and VTMS (vinyltrimethoxysilane). Thermal testing was the core material and a poly(methyl methacrylate-co-divinylben-
undertaken using DSC and TGA. The results from this investigation zene) (P(MMA-co-DVB)) copolymer as a shell material. They
suggested that a micropolymer of pure VTMS is thermally achieved this by regulating the weight ratio of butyl stearate to
stable (2 wt% loss) to 318.2 1C. However when the core material paraffin. A TGA analysis was undertaken to investigate the thermal
of n-octadecane was added to the pure VTMS, polymer leakage stability of the mEPCM on the 11 samples prepared. Results from
occurred due to poor encapsulation. It can be concluded from this this analysis showed two weight loss peaks. The first weight loss
test that VTMS as an encapsulation material for n-octadecane is peak occurring between 200 1C and 290 1C for all samples was
unfeasible. Also due to the starting degradation temperature of the attributed to the decomposition of the core materials, while the
test samples being all below 287 1C, it is suggested that the hybrid second weight loss peak occurring between 375 1C and 420 1C for
shells start to degrade before n-octadecane diffuses out comple- all samples was attributed to the decomposition of the co-polymer
tely. This renders VTMS as a shell material as a poor choice for high shell. Results from the thermal stability tests suggest that the
temperature TES applications, regardless of the PCM encapsulated. onset temperature of the first and second decomposition steps of
Li et al. [44] investigated the effect of carbon nanotubes (CNT) on the microcapsules increases with the increasing weight ratio of
the thermal and mechanical properties of microcapsules. The butyl stearate. All samples decomposed completely above 450 1C.
prepared microcapsules used urea-formaldehyde resin (UFR) as Qiu et al. [50] investigated the use of copolymer encapsulation shells
the shell material for a stearyl alcohol core. Degradation of the UFR for a core of n-octadecane. Results from testing suggested that n-
shell was shown to occur between 250 1C and 350 1C for both the octadecane content as high as 77.3% could be achieved. It was also
microcapsule and the carbon nanotube microcapsule. It was reported that crosslinking of the polymers greatly increased thermal
shown that the addition of the carbon nanotubes increased the stability. Of the investigated encapsulations, the MMA–BMA copoly-
thermal stability of the microcapsules by 38 1C prior to 100 mer had the highest degradation temperature. The stage II peak of
thermal cycles and 37 1C after thermal cycling. This result was weight loss on the TGA curves suggests that the copolymer breaks
attributed to the high thermal conductivity of CNTs and strong down at 385 1C. These results suggest that the copolymer is best
interaction between the CNTs and UFR. This interaction is said to suited to medium temperature applications (E300 1C) rather than
restrict the mobility of the polymer chains [45]. In addition it was high temperature applications, regardless of the PCM used as a core
found that the CNTs can hinder the permeation and transfer of gas. material. Salüan et al. [51] successfully used poly(urea–urethane) as a
Interestingly the results from this paper also show that the shell material for a xylitol core. Salüan et al. [51] discovered the
addition of carbon nanotubes has a significant impact on the thermal degradation of the poly(urea–urethane) microparticles occur
average particle size and distribution. The average particle size of in two consecutive steps. It was concluded that the weight loss at the
the standard microcapsules was 6.54 μm; however microcapsules temperatures between 200 1C and 400 1C may be attributed to the
with carbon nanotubes added had an average particle size of decomposition of poly(urea–urethane) network. Then from 220 1C,
0.1 μm. The particle size distribution of the carbon nanotube the degradation and the depolymerization of polyurethane polymer
mEPCM was also found to be much more concentrated. These
results seem to confirm earlier predictions by Xu et al. [46] on the
effect of carbon nanotubes on particle size and distribution.
The low degradation onset temperature and small particle size
suggests that a UFR shell with CNTs is not suitable for high
temperature applications. However the successful addition and
increased performance of CNTs suggests further investigation is
required with other PCMs and shell materials. Yu et al. [47]
investigated the possibility of using calcium carbonate as a shell
material for a n-octadecane core, (see Fig. 7).
The results from testing suggest that microencapsulation of
n-octadecane by calcium carbonate increases the thermal stability
of the PCM from 195.8 1C to 215.3 1C. At this point it was found
that the PCM had evaporated and escaped through the calcium
carbonate pores. It is therefore suggested that a PCM with a higher
melting point could theoretically be much more stable at higher
temperatures than those achievable by n-octadecane. The high
melting point of pure calcium carbonate also makes it a feasible
choice for high temperature TES applications. Qiu et al. [48] Fig. 7. SEM micrographs a (30/70) n-octadecane–CaCl2 mEPCM [47].
 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87 85

and oligomers were observed. Most of the reactions implied in the polystyrene shell. However thermal stability tests show a slight
degradation mechanism lead to the formation of crosslinked com- decrease in thermal stability (325 1C for St–MMA capsule). The
pounds with urea groups. This step was followed by a recombination degradation temperature for a pure St–MMA polymer was found to
in urea oligomers, which were degraded at higher temperature, be 320 1C. These results indicate that although a polystyrene shell
between 280 1C and 350 1C. There was no observed change in onset provides a slightly higher thermal stability, the St–MMA shell
temperature of degradation (E225 1C) of various samples. provides a much higher energy density and would be better suited
From the results it is suggested that as the poly(urea–urethane) for TES applications. Zhang et al. [55] encapsulated n-octadecane with
decomposes at 400 1C, regardless of the PCM used, it is best suited silica using a sol–gel method. Results from the thermal analysis (TGA
to medium temperature applications and not the high tempera- and DTG) suggest that the most thermally stable form of silica shell
ture applications suggested. Fang et al. [52] successfully encapsu- (60/40 wt/wt n-octadecane/TEOS @ pH 2.45) has a stage II decom-
lated paraffin wax with a silicon dioxide (SiO2) shell, (see Fig. 8). position temperature of 325 1C. Zhang et al. [55] concluded that the
Thermal stability testing suggests two weight loss peaks. The first weight loss of about 7 wt% between 280 1C and 350 1C is due to the
step occurs between 20 1C and 80 1C. This was concluded to be from elimination of the water produced by further condensation of the
the release of water molecules from the SiO2 shell. The second rapid silica at high temperatures, which is attributed to the incomplete
weight loss that occurs from 200 1C to 350 1C is attributed to the condensation reaction of silanols under low temperatures in the sol–
thermal degradation of the paraffin wax molecular chains. This value gel process. These results were further verified by Zhang et al. [56]
seems to coincide with previous thermal stability testing on paraffin when a silica shell was used to encapsulate n-octadecane through an
wax [53]. Results from this research suggest that SiO2 would be a interfacial polycondensation method. Again the results show a second
suitable candidate for high temperature applications. Sánchez-Silva rapid weight loss around 325 1C. The weight loss is attributed to the
et al. [54] successfully microencapsulated paraffin wax using styrene complete dehydration of the silica shell material by further condensa-
(St) and methyl methacrylate (MMA) as the shell material. The results tion at high temperatures. Yu et al. [42] investigated the use of M–F as
show an increase in capsule diameter (380 μm for St–MMA), an a shell material. Thermal stability tests suggest that a pure M–F
increase in encapsulation (43.17% for St–MMA) and an increase in polymer has a significant weight loss at 404 1C which is attributed to
average melting heat (87.5 J/g compared to 41.65 J/g) over a the decomposition of the M–F resin. Moreover thermal stability tests
of the microencapsulated n-dodecanol with a M–F shell shows
significant weight losses at 177 1C and 371 1C. The lower weight loss
is attributed to the evaporation of the core material n-dodecanol and
some reagents. This indicates that the shell of microPCMs is broken
and the core material n-dodecanol starts to be evaporated. The
second weight loss step is attributed to the decomposition of the
M–F shell. This result suggests that the microPCM has a lower thermal
shell stability than the pure M–F resin. Sánchez et al. [57] initially
experimented with microencapsulating paraffin wax with a polystyr-
ene shell. The results of this study show successful encapsulation of
the wax with an average diameter of 238 μm and a PCM encapsula-
tion of 20.56%. The thermal stability of this process was also
investigated. Three weight loss peaks were discovered upon TGA
analysis. The TGA plot of the microcapsules showed a loss of 23 wt%
below 100 1C. This was attributed to the elimination of methanol and
water (drying of surface wetting agents). Between 120 1C and 250 1C,
Fig. 8. SEM image of MEPCM2 [52]. another weight loss (21 wt%) was observed. This was attributed to the

Table 3
Potential of shell materials in various situations.

Group Potential materials Advantages Disadvantages Potential applications

Metallic Steel (stainless and carbon), nickel– – High mechanical strength – High potential – For use in high temperature situations where
chromium/carbon/ruthenium – Can form an encapsulation for corrosion ceramic shells are inappropriate e.g. liquid metal as the
using a variety of methods – Expensive heat transfer fluid
(electroplating,
preformed, etc.)
– High thermal stability
(generally around 1000 1C)

Inorganic Silicon dioxide, titanium dioxide, sodium – High thermal stability – Porous shell – For use in high temperature situations e.g. power
silicate, calcium carbonate, silica (generally around 1000 1C) can lead to leakage generation, high temperature industrial processes
– High mechanical strength (cement and metal manufacturing)
– Less expensive than
metallic shells

Plastic M–F, VTMS, UFR, BA–DVB, P(MMA-co- – Can form an encapsulation – Relatively low – For use with expected temperatures between
DVB), BMA–MMA copolymer, poly using a variety of methods thermal 300 1C and 400 1C, e.g. building cooling, various
(urethane–urea), St–MMA, polystyrene (chemical and physical stability industrial processes (food and paper manufacturing)
methods) (400 1C max)
– Less expensive than – Low thermal
metallic shells conductivity
86 R. Jacob, F. Bruno / Renewable and Sustainable Energy Reviews 48 (2015) 79–87

paraffin wax. The last peak at 340 1C with an additional weight loss of [12] Tay NHS, Belusko M, Castell A, Cabeza LF, Bruno F. An effectiveness-NTU
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