“Preparation and characterization of thermal storage aggregate based on

phase change material”

“Fabricación y caracterización de agregado almacenador de energía a base de material de cambio de
fase”

Abstract
In this study were fabricated a novel composite with potential application for thermal storage energy
materials, based on the Butyl Stearate (BS) phase change properties. The butyl stearate was impregnated on
crushed pumice as lightweight aggregated (LWA) carrier, making a form-stable phase change material
(FSPCM) for fabrication of a concrete/mortar aggregated, it is reached by mixing this impregnated carrier with
graphite powder and polymerizing by polyester resin. This form-stable phase change material was thermally
evaluated, founding the stored energy by latent heat in the phase change transition to solid-liquid process of the
butyl stearate on the composite, submitting the sample at differential scanning calorimetry analysis (DSC). Two
different samples were tested with different proportions on the PCM loads. The results have shown suitable
thermal energy storage in the melting process to a building materials.

Keywords: PCM, FSPCM, Butyl Stearat, Graphite Powder, Light Weight Aggregate, Thermal
characterization.

Resumen
En este trabajo se fabricó un nuevo composite con potencial como material alamacenador de energía, basado
en las propiedades de cambio de fase del Estearato de Butilo (BS). El estearato de butilo es impregnado en
pomacita triturada como agregado ligero (LWA), logrado un material de cambio de fase en forma estable
(FSPCM) para la fabricación de agregado para mortero o concreto, lo cual es logrado mezclando este agregado
ligero impregnado con polvo de grafito y polimerizando con resina poliester. Este material de cambio de fase
en forma estable fue evaluado térmicamente, encontrado la energía almacenada por calor latente en la transición
de fases solido-líquido del estearato de butilo, sometiendo la muestra a calorimetría diferencial de barrido
(DSC). Dos diferentes muestras fueron evaluadas a diferentes proporciones de PCM. Los resultados muestran
energía una apta energía almacenada en el proceso de fusión para materiales de construcción.
Palabras Clave: PCM, FSPCM, Estearato de butilo, Agregado Ligero, Polvo de grafito, Caracterización
térmica.

1. Introducción

The thermal energy storage by latent heat defines how much heat can absorb or release when a phase transition
occurs. It means, in a continuous heat flow system, there is an isothermal process while the molecular chemical
bonds breaks, making the transition between the solid and liquid stages. This property is searched for
construction materials in order to stabilize the temperature of the interior spaces, which means an increment of
the thermal inertia. In other words, as much thermal energy can storage a material by latent heat, it should be
less sensitive to the environment temperature fluctuations. One particular way to attach this property to a
material, especially a composite, is adding phase change materials (PCM). Several authors explains the potential
of PCM in the saving energy, (Anisur et al., 2013) make a compilation of the quantitative data on the potential
saving energy, showing a lot of positive information, specifically for the building and housing sector. There is
an effort by the scientific community to develop passive systems of thermal energy storage by common
construction materials as cementitious materials, bricks, laminated gypsum boards, and all those materials that
normally are included in buildings or residential house.
(Kuznik et al., 2011) Set 4 mainly ways to include PCM in building materials: (1) Direct impregnation, refers
to a direct immersion in liquid PCM a prefabricated building element. (2) Microencapsulation which are micro
spheres that can add directly on cementitious mixtures. (3) Shape stabilized PCM, this refers to mix the PCM
with other materials, in such way that the liquid PCM does not leak from the composite when the temperatures
are higher than the melting point. (4) Others, which can manipulate the PCM into the sealed capsules like
pouches or metal squares to build composed walls (Silva et al., 2012; Lai and Hokoi, 2014; Vicente and Silva,
2014; Lee et al., 2015). (Salunkhe and Shembekar, 2012) on the other hand describes 3 types of encapsulated
according to the capsule size: nanoencapsulation (0-1000nm), microencapsulation (0-1000m) and
macroencapsulation (above 1mm). These classifications match at some point, the microencapsulation are one
of the most investigated forms of a PCM even more in the cementitious/gypsum mixtures, as shown by several
authors (Medrano et al., 2007; De Gracia and Cabeza, 2015; Lecompte et al., 2015). Nevertheless other forms
have an important field of investigations in order to develop thermal storage aggregates for building materials,
several works lead to an easy way to fabricate this aggregates with most common materials and methods than
the microencapsulations. For example, the form-stable phase change materials (FSPCM) brings an alternative
way of fabrication a material with thermal storage properties, making a PCM composites with materials as
polymers, or in general any material with the melting point above the working temperature. In the construction
field, the principal application for this materials are develop a mortar/concrete mixtures, acting in endothermic
stage, like a heat collector and storing a portion of this heat by latent heat, and in the exothermic stage, like a
heat supplier, releasing the stored heat in the endothermic stage.
One popular FSPCM is the macrocapsules, which fabrication has been by several methods and materials, (Alam
et al., 2015) enclosure PCM compressed powder in spherical forms on polymer coating and then a metal layer,
(Cui et al., 2017) enclose an organic paraffin into a hollow steel balls, and then fabricate mortar panels.
Many works employs porous materials as PCM carrier, like Light Weight Aggregate (LWA), (Kastiukas et al.,
2016) impregnate technical grade paraffin on expanded clay, and cover this PCM-LWA with different coating
materials, then incorporate this composites into squares panels made from a geopolymeric binder to stablish
their thermal performance. (Memon et al., 2015) make macrocapsules by impregnation of paraffin on expanded
clay and added to a cementitious mixture making a thermal energy storage mortar, testing its mechanical
properties. (Sakulich and Bentz, 2012) impregnate four different PCM (Paraffin wax, vegetable oil, PEG 400 y
PEG 600) on expanded clay and naturally porous pumice, (Wen et al., 2017) prepare an eutectic PCM by capric
and lauric acid, via vacuum impregnation on expanded perlite and expanded vermiculite, reaching a composite
PCM in stable form.
In order to reach suitable aggregates to building materials with thermal storage properties, several phase change
composites in stable form (FSPCM) has been fabricated and characterized, and there is a great opportunity area
developing new FPCM´s and improving those in the literature.
Many of this FSPCM’s has been reported low thermal conductivity, which leads to an inefficient heat absortivity
from the heat flow in the system especially in organic PCM. In order to attend this issue, (Calvet et al., 2013)
found a significant reduction in thermal energy storage/discharge time, increasing the thermal conductivity by
adding graphite particles to the PCM, and many researchers have developed different PCM composites
including a graphite particles in different structures as a thermal conductivity promoter, (Meng and Wang, 2013;
Lv et al., 2016) makes an FSPCM with expanded graphite as k riser agent, (Tang et al., 2016) employs graphene
particles to improve the thermal conductivity, (Jeong et al., 2013) improves this thermal conductivity with
exfoliated graphite expanded nanoparticles. All these studies report a wide range of thermal conductivities in
their respective FSPCM’s. (Cheng et al., 2010) make a direct comparison between the thermal conductivity of
FSPCM’s with two of those graphite-based materials: the expanded graphite (EG) and graphite powder (GP),
resulting widely larger the FSPCM with EG.
Many of the works cited previously reports latent heats over the 100 J/s, which can consider as good PCM as
far as thermal energy storage material by PCM is concerned. But a complete characterization implies several
tests, including TGA, DSC, Hot Plate test (Thermal tests), SEM (Morphological tests), even on the PCM
mortars/concrete mechanical tests are necessary.
This paper discuss the process and proportions to fabricate a form-stable phase change material (FSPCM) from
the Butyl Stearate (BS), because of its suitable properties as organic PCM (Ling and Poon, 2013), crushed
pumice as a carrier material, polyester resin as agglutinate and graphite powder as thermal exchange process
accelerator. Also, the thermal characterization of this composite has been carried out by DSC and comparing
the melting latent heat of composites with different loads of PCM.

2. Experimental investigation.
2.1 – Materials.
The form-stable phase change materials (FSPCM) means the solid form of a composite with the PCM in its
structure, it should be capable of make the phase transition without modifications on its form. The FSPCM
developed in this work is made up of three principal components: The LWA carrier (crushed Pumice), the phase
change material (Butyl Stearate), and an agglutinate (Polyester resin). Also, in order to have a FSPCM with
high thermal conductivity, graphite powder was aggregated. The specified materials used in this work as a
carrier was triturated pumice obtained from a stone mine in the community of San Clemente belonging to a
Pedro Escobedo City, Queretaro, Mexico. The particle size used was 0.074 -0.114 mm, achieved by sieving the
material and picking the held by No. 200 mesh. This particle size was selected after several impregnation tests
with different sizes, identifying the one with good and stable impregnation weight percentage. The phase change
material was butyl stearate which has a melting temperature around 16 °C and a heat capacity of 168.98°C
(Hawes et al., 1990; Ling and Poon, 2013). The agglutinate was polyester resin pre-accelerated wit an
endothermic catalyst (Benzoil peroxide), provides by Mexochem Corporativo S.A de C. V. Depending on the
environment conditions which the material works, exist the possibility of insufficient thermal energy storage to
reach a complete phase change on the PCM available, an approach to solving this issue is increasing the thermal
energy exchange effectiveness, thus, in this investigation graphite powder was added to the composite as a k
riser agent.
2.2 – Preparation of FSPCM
For this study an FSPCM was prepared by two main steps: the vacuum impregnation and polymerization, Figure
1 shows the schematic process followed. The impregnation process aim is to extract the air trapped in the
crushed pumice particles and fill with the butyl stearate, the pumice sample was put into the vacuum
environment while the butyl stearate was leaked, the process was reached in a low vacuum pump at 10 in Hg
of vacuum pressure during approximately 30 min for every sample. Figure 2 shows the vacuum impregnation
set up. The second step was the mixing and polymerization process, wich was made via polyester resin
polymerization of the mixed components, Error! Reference source not found. shows the proportions of the
tested samples. The PCM and agglutinate proportions was selected experimentally, in order to get loads with
good manageability FSPCM. On other hand, the graphite powder proportion was 10 wt %, in order to match
up with the loads in different works with similar materials (Cheng et al., 2010; Jeong et al., 2013; Meng and
Wang, 2013; Johansen et al., 2015; Lv et al., 2016; Tang et al., 2016).

PCM CARRIER
Vacuum
(Butyl (Crushed
impregnation.
Stearate) pumice)

AGLUTINATE
Mixing and
(Polyester FSPCM
polimerization.
resin)

K RISER
(Graphite
powder)

Figure 1 - FSPCM Fabrication process

Table 1 - Material mixing proportions.

Sample PCM LWA Agglutinate K riser
(Butyl stearat) (Crushed pumice) (Poliester resin) (Graphite powder)
FSPCM-1 30 9 9 3
FSPCM-2 30 12 9 3
 Butyl Liquids
stearat
trap

a)
b)

Vacuum
pump
Lightweight
aggregate
Figure 2 – a) Vacuum impregnation Setup b) FSPCM

2.3 – Thermal characterization.

In this work, the characterization aim is to find the FSPCM thermal energy storage when the phase transition
occurs, to quantify this property a DSC apparatus was utilized, evaluating the endothermic peaks founded
in the butyl stearate melting temperature, wich, from the data sheet and previous test was around the 16°C.
The DSC analysis was performed on a thermal analysis apparatus (Q2000 TA instrument. Querétaro,
Mexico). About 3-8 mg of every sample was placed in the aluminum pan and the measurements were taken
in a temperature range of 0-60 °C. The analysis was carried out with a temperature ramp of 10°C/min, under
a constant stream of neutral gas Every sample were analyzed 3 times and the phase change temperature was
reported as the average values.

Table 2 - Fusion latent heat and phase change temperature.

Peak Temp ΔH
(°C) (J/g)
FSPCM-1 22.32 27.16
FSPCM-2 21.22 32.95

3. Results and discutions.

The Figure 3 shown the endothermic peaks of the samples analyzed, the thermal energy storage was found
by integrating in time the thermogram obtained by the DSC analysis, the peak temperatures were 22.32 °C for
the FSPCM – 1 and 21.22°C for the FSPCM-2. This means the phase change temperature was modified in
reference with the pure butyl stearate, in the sample with most percentages of PCM was observed a slight
decrease phase change temperature. In reference with the phase change enthalpy, it was observed an increment
according to the PCM load was major, which was an expected behavior. The Table 2 sown the latent heat and
the phase change temperature of the FSPCM.
a) b)

c)

Figure 3 - FSPCM Fabrication process.

4. Conclutions
In this work, the process followed for the fabrication of the FSPCM were based on several works in the
literature, nevertheless, the development of thermal energy storage composites, leads to find the combination
of many materials and find FSPCs with good thermal characteristics, many others characteristics that should be
investigated once this FSPCM is mixed with cementitious materials, which is one of the principal aims of the
phase change materials. This work provides information that supports the thermal energy storage in the melting
process, specifically for the proportions employing for fabricating the samples analyzed, are suitable for
construction targets, but many others tests should be carried out in order to verify the compatibility and behavior
with building materials.
Thanks
The authors thank CONACYT for the support during all this investigation. Thanks to Mexochem
Corporativo S.A de C. V. For providing the catalyst for the polyester resin.
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