Review

Phase Change Material Evolution in Thermal Energy Storage

Systems for the Building Sector, with a Focus on
Ground-Coupled Heat Pumps
Silvia Barbi 1, Francesco Barbieri 1,*, Simona Marinelli 1, Bianca Rimini 1,2, Sebastiano Merchiori 3,
Michele Bottarelli 3,4 and Monia Montorsi 1,5

1 Department of Science and Methods for Engineering, University of Modena and Reggio Emilia, Via
Amendola 2, 42122 Reggio Emilia, Italy; [email protected] (S.B.); [email protected] (S.M.);
[email protected] (B.R.); [email protected] (M.M.)
2 Interdepartmental Research Center for Industrial Research and Technology Transfer in the Field of

Integrated Technologies for Sustainable Research, Efficient Energy Conversion, Energy Efficiency of
Buildings, Lighting and Home Automation, EN&TECH, University of Modena and Reggio Emilia,
Via Amendola 2, 42122 Reggio Emilia, Italy
3 TekneHub Laboratory, University of Ferrara, Via Saragat 13, 44122 Ferrara, Italy;

[email protected] (S.M.); [email protected] (M.B.)

4 Department of Architecture, University of Ferrara, Via Quartieri 8, 44121 Ferrara, Italy

5 Interdepartmental Center for Applied Research and Services in Advanced Mechanics and Motoring,

INTERMECH-Mo.Re., University of Modena and Reggio Emilia, Via P. Vivarelli 10/1, 41125 Modena, Italy
* Correspondence: [email protected]

Citation: Barbi, S.; Barbieri, F.; Abstract: The building sector is responsible for a third of the global energy consumption and a
Marinelli, S.; Rimini, B.; Merchiori, quarter of greenhouse gas emissions. Phase change materials (PCMs) have shown high potential for
S.; Bottarelli, M.; Montorsi, M. Phase latent thermal energy storage (LTES) through their integration in building materials, with the aim
Change Material Evolution in
of enhancing the efficient use of energy. Although research on PCMs began decades ago, this
Thermal Energy Storage Systems for
technology is still far from being widespread. This work analyses the main contributions to the
the Building Sector, with a Focus on
employment of PCMs in the building sector, to better understand the motivations behind the
Ground-Coupled Heat Pumps.
restricted employment of PCM-based LTES technologies. The main research and review studies are
Polymers 2022, 14, 620. https://
doi.org/10.3390/polym14030620
critically discussed, focusing on: strategies used to regulate indoor thermal conditions, the variation
of mechanical properties in PCMs-based mortars and cements, and applications with ground-
Academic Editors: Mariaenrica
coupled heat pumps. The employment of materials obtained from wastes and natural sources was
Frigione, Giovanni Dal Poggetto and
also taken in account as a possible key to developing composite materials with good performance
Cristina Leonelli
and sustainability at the same time. As a result, the integration of PCMs in LTES is still in its early
Received: 26 January 2022 stages, but reveals high potential for employment in the building sector, thanks to the continuous
Accepted: 3 February 2022 design improvement and optimization driven by high-performance materials and a new way of
Published: 5 February 2022 coupling with tailored envelopes.
Publisher’s Note: MDPI stays
neutral with regard to jurisdictional Keywords: phase change materials; latent thermal energy storage; sustainable buildings;
claims in published maps and ground-coupled heat pumps; energy reduction; materials design; eco-friendly materials;
institutional affiliations. sustainable materials; green economy

Copyright: © 2022 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
This article is an open access article Since the last decade of the twentieth century, the problem of fossil fuel consumption
distributed under the terms and
and the dependency on non-renewable energy sources emerged in the building sector. In
conditions of the Creative Commons
this field of application, human beings are facing different challenges: the reduction of
Attribution (CC BY) license
consumption, the rise of efficiency in energy production and use, and, lastly, the
(https://creativecommons.org/license
employment of sustainable resources. In fact, the building sector requires more than 33%
s/by/4.0/).
of the global energy demand and represents the source of approximately 25% of

Polymers 2022, 14, 620. https://doi.org/10.3390/polym14030620 www.mdpi.com/journal/polymers

Polymers 2022, 14, 620 2 of 33

greenhouse gas emissions [1]. Despite a flattening of CO2 emissions between 2013 and
2016, building-related emissions began to grow back in recent years, leading to a total
increase equal to 5% from 2010 to 2019. Fossil fuel use has also grown, at an average rate
of 0.7%/year, in the same period [2]. The reduction of greenhouse gas emissions and the
rational use of energy have become a global widespread endeavor, especially in the
European Union (EU), where a relevant need for energy saving in buildings has been
recognized and put into practice. In fact, the more recent EU environmental policies for
the building sector have promoted the spread of renewable energy technologies [3,4]. The
need to enhance sustainable energy employment in this field could be satisfied through
different approaches and technologies.
One of these technologies is thermal energy storage (TES), which allows the storage
of heat or cool energy in well-tailored materials during low demand periods to release
them when needed. The storage mechanism in TES architectures is usually carried out
using the sensible or latent heat of specific materials, taking advantage of the specific heat
and temperature change with the former, and of the phase-change latent heat performed
at a given temperature with the latter [5,6]. Sensible heat TES (SHTES) architectures
generally use cheap storage materials, such as water, bricks, or rocks, and for this reason,
they are established and widespread technologies. Latent heat TES (LHTES) systems, by
contrast, are based on phase change materials (PCMs) and offer the advantages of a fairly
constant working temperature and the enhanced energy density of their storage material,
which allows the storing of 5–14 times more energy than SHTES in the same volume,
therefore reducing the size of the storage system [7,8]. In fact, PCMs can be organic,
inorganic, and eutectic compounds characterized by high values of phase-change latent
heat. The main classes of PCM are shown in Figure 1.

Figure 1. Main classes of PCM [9].

The majority of organic PCMs are composed of paraffin waxes (CH3(CH2)nCH3), with
melting temperatures between 20 °C and 70 °C, thereby fulfilling the needs of LHTES
architectures in the buildings sector in a wide range of latitudes [6]. Fatty acids
(CH3(CH2)nCOOH) constitute the second main group of organic PCMs, with melting
temperatures between 17 °C and 64 °C. Other organic substances generally exploited as
PCMs are esters, alcohols, and glycols [6,10]. Among inorganic PCMs, hydrated salts are
the main category. With respect to organic compounds, they have a wider range of
Polymers 2022, 14, 620 3 of 33

melting points, reaching temperatures up to 140 °C [11,12]. Molten salts have also been
considered, but their high melting temperatures (>250 °C) make them unattractive for the
building sector [13]. Finally, eutectics can also be considered, as they are made of mixtures
of two or more pure PCMs, which can be organic–organic, inorganic–inorganic, or
inorganic–organic. They show well-defined melting points, but their properties and
performances must be further investigated as they are the result of very specific
formulations that could be difficult to control for industrial purposes and when handling
large volumes of material [9,14].
Every category of PCM, taking into account the solid-liquid latent heat, presents
several advantages but also drawbacks, as listed in Table 1, which limit their practical and
commercial applications in the building sector [15]. There are also some limitations
common to all categories, namely high costs, low thermal conductivity, and long-term
stability, which make SHTES even more widespread and profitable than LHTES [16].
Among phase changes, solid–liquid is the most employed in practice. In fact, even if the
latent heat of the liquid–gas transition is generally higher, the relevant associated volume
change must be considered, as it can lead to many severe critical issues in the design of
liquid–gas-based TES, such as partially flexible PCM containment or safety devices due
to slight temperature changes [6]. On the other hand, PCMs based on solid–solid
transition take advantage of the passage between a crystalline and an amorphous solid
phase. The lack of a liquid or gas phase prevents leakage problems, but this PCM category
shows a lower phase change energy compared to PCMs based on solid–liquid transition.
Moreover, their phase change temperatures are usually higher than those required for
building applications [9,17].

Table 1. Principal advantages and disadvantages of organic, inorganic, and eutectic PCMs [15].

Organics Inorganics Eutectics

Non-corrosive
Greater phase change enthalpy
Advantages Low or no undercooling Sharp melting point
Greater density
Chemical and thermal stability
Undercooling
Lower phase change enthalpy
Corrosion
Disadvantages Low thermal conductivity Lack of data
Phase separation
Flammability
Phase segregation, lack of thermal stability

Since the early studies from 1990 onwards, the use of LHTES technology was
considered in the building sector to enhance energy management and consumption,
dividing the final PCM applications (for heating or cooling purposes) into active and
passive [6]. The significant difference lies in the fact that in active applications, the thermal
energy is available only when necessary, using mainly on/off auxiliaries such as heating,
ventilation, and air conditioning systems (HVAC). Passive applications, instead, aim to
include PCMs directly into building elements, using only the surrounding environment
as their energy source, allowing automatic and continuous energy storage or release and
providing thermal comfort with minimum or no use of HVAC systems [18,19].
Active applications include the use of TES coupled with conventional HVAC systems
(e.g., floor or ceiling heating plants) or with heat pumps to optimize the electric energy
demand from high-peak to off-peak periods [20]. Other active applications consider solar
energy systems and solar air collectors integrated into building walls, as well as the use
of ventilation mechanisms with free cooling, that take advantage of low night
temperatures to store coldness in building materials and release it during the day.
Passive technologies include standard solar walls, so-called Trombe walls, and the
inclusion of PCMs in construction materials such as concrete, mortars, and insulation
materials, or in building elements, such as windows, shutters, wallboards, and bricks [20].
Polymers 2022, 14, 620 4 of 33

An important aspect in all the applications is that the employed PCM must be tai-
lored for a specific use, considering its nature (organic or inorganic), its percentage in the
formulation, and, especially, its precise melting temperature according to climatic condi-
tions, building design, and thermal comfort requirements. As PCMs can be fully inte-
grated with the TES architecture, the environmental sustainability of all the system must
also be taken into consideration. Several environmental analyses based on the life cycle
assessment (LCA) methodology have shown that the environmental impact resulting
from the production, installation, and disposal of PCMs is largely recovered from the en-
vironmental benefit obtained thanks to energy savings (from 15% to 35% of energy saved
based on climatic conditions) [21]. However, other studies have shown that the use of
PCMs as paraffins or salt hydrates, while reducing energy consumption, does not signifi-
cantly reduce the overall impact compared to the use of a conventional insulation mate-
rial, such as polyurethane, suggesting that the production and the disposal phases of PCM
life cycles need to be further investigated [22]. For example, paraffin production is mainly
based on fossil oils, although materials derived from renewable sources have also recently
been developed [23]. The production process is very similar for all fossil-based materials,
regardless of the length of the carbon chain that determines the melting point. The envi-
ronmental impact can therefore be considered identical for the individual materials [24].
Thereafter, more recent studies focus on more sustainable organic materials not based on
fossil fuels. For example, the biodegradability of a plant-based PCM was analyzed and
compared to paraffins and salt hydrates, demonstrating the total decomposition of the
plant-based material after 4 months [25].
Despite the considerable number of studies on PCM integration in LHTES systems,
elements, or materials, their application in the building sector is far from being wide-
spread. The aim of this work is to analyze the developments of PCM applications in the
building sector, since their early stages, through an analysis of research and review pa-
pers. In the first period (2000–2010), described in the Section 2, the main focus was on the
improvement of PCMs’ general properties. Next, a focus on the more recent and peculiar
applications in the building sector is presented, according to the materials’ evolution in
recent years. In fact, during 2010–2021, research in the building field was mainly driven
by PCM application, as very different effects can be exploited depending on the relative
placement of PCMs in a building or in specific climatic areas. Finally, research concerning
the coupling of PCMs to ground-coupled heat pump (GCHP) technology is discussed. In
fact, this technology, by employing the soil as a form of underground thermal energy stor-
age, is one of the most promising and innovative LHTES architectures, as it is not influ-
enced by seasonal effects.

2. PCMs’ Evolution in the Building Sector

2.1. The Early Stages: 2000–2010
At the very beginning of this period, the topics covered by the most significant re-
search concerned PCMs’ basic properties, thereby almost neglecting the implications of
outer factors for their efficient use as building material. In particular, these topics were
heat transfer modeling [26,27], the conservation of temperature-sensitive materials, and
thermal storage enhancement [14,28,29], as well as their first possible building applica-
tions, such a through impregnated wallboards [9,30]. Concerning basic properties, the ma-
terials were classified as PCMs considering mainly their significant liquid–solid phase
change latent heat (at least 100 kJ/kg), and this led to a list over 150 organic and inorganic
materials, both commercial and non-commercial. At this stage, the highest latent heats
recorded were: 816 kJ/kg, attributed to a LiF–CaF2 (80.5:19.5) eutectic mixture among in-
organic compounds; and 250 kJ/kg, related to paraffin wax, among organics. It is also wor-
thy of note that Rubitherm (www.rubitherm.de , accessed date 04/02/2022) and EPS Ltd.
(Sonning, UK, epsltd.co.uk , accessed date 04/02/2022) were evaluated, during 2010, as the
most relevant commercial PCM manufacturers in the world, with the highest number of
Polymers 2022, 14, 620 5 of 33

available products (29 and 61, respectively). Nevertheless, several critical points common
to the majority of PCMs arise, such as long-term stability, low thermal conductivity, den-
sity variation over the transition phase, corrosion, and subcooling or phase segregation.
These drawbacks are particularly relevant for inorganic PCMs, including eutectic mix-
tures, such as LiF–CaF2, and limit their employment despite the higher value of their latent
heat. In particular, LiF–CaF2 eutectic mixtures have shown a linear coefficient of expan-
sion near to 30 × 10−6 K−1 and relevant changes over time (after 9 months) in density (−2%)
and porosity (+2.1%) [31]. In addition, the numerical simulation and modeling of the heat
transfer during the phase change, called the moving boundary problem, was also consid-
ered as a critical point to study, over several work cycles, to validate numerical simula-
tion, due to a lack of experimental studies [14,26,32].
As a possible strategy to overcome PCMs’ intrinsic low thermal conductivity, highly
tailored encapsulation methods were investigated, as a promising way to increase PCMs’
heat transfer while avoiding large phase separations [28]. In particular, macro-encapsula-
tion was analyzed as a viable and economical way of making PCM employment more
efficient, giving them a self-supporting structure designed for their intended application.
Examples of macro-encapsulation strategies are shown in Figure 2. They include metal
tubes (Figure 2a), metal spheres (Figure 2b) that could be arranged to form a packed bed,
PCM spheres (Figure 2c), aluminum pouches (Figure 2e), and rectangular flat panels in
polyvinyl chloride (PVC) or aluminum (Figure 2d,f).

(a) (b) (c)

(d) (e) (f)

Figure 2. Examples of different container shapes used for PCM encapsulation: (a) tubes, (b) metal
spheres, (c) PCM spheres, (d) rectangular PVC panels, (e) aluminum pouches, (f) flat panel [33].

These different tested geometries show different peculiarities. With flat panels and
pouches, it is possible to achieve more surface area per unit of storage volume, having less
weight and volume with respect to bulk PCMs. Subsequently, the solidification time re-
sults reduced to 4 h and the melting time reduced to 6 h, making it acceptable for free
cooling by employing a low PCM thickness [34,35]. Nevertheless, the panel geometry was
Polymers 2022, 14, 620 6 of 33

found to be superior to pouches as, under the same environmental conditions and by em-
ploying a commercial organic PCM, the first showed higher cooling power (+12.5%) and
shorter melting times (−45%) [36]. Cylindrical PCM pipes are easier to fabricate, having
the same heat transfer characteristics with respect to flat panels and a lower heat loss rate
[33,37,38]. In fact, in this geometry, heat transfer takes place in the axial and radial direc-
tions, with an increased area of convective heat transfer. Concerning spherical geometry,
PCMs or metals balls have larger surface areas per unit of volume compared to cylindrical
geometry and heat transfer can be tailored by selecting the ball’s diameter. For example,
balls up to 3 mm in diameter were tested, demonstrating that the solidification time is
about 1.5 h, which is suitable for free-cooling applications [36]. In particular, a LHTES
configuration based on PCM spherical geometry encapsulation (Figure 3) has been inves-
tigated as a possible solution to increase the heat transfer rate between the PCM and the
heat transfer fluid (HTF) while avoiding direct contact between them[28]. However, the
main problem of the packed-bed configuration concerns the complex modeling of both
the heat transfer process between PCM and HTF considering the container and the PCM
phase change inside the container itself [28].

Figure 3. Packed-bed LHTES system diagrams with spherical macro-capsules [28].

When sphere geometry concerns restrained diameters (<5 μm), the micro-encapsula-
tion definition is employed. Micro-encapsulation architecture, thanks to the larger heat
transfer area between micro-encapsulated particles, ensures an even greater thermal con-
ductivity with respect to sphere geometry encapsulation (or macro-encapsulation). How-
ever, a further encapsulation was needed, in these years, to collect all the micro-spheres,
consequently reducing the micro-encapsulation’s beneficial effects on the final thermal
conductivity dramatically [28]. In fact, further collection of the micro-capsules forces the
majority of the heat transfer to occur through conduction, significantly limiting the overall
heat transfer rate. In this context, for macro-encapsulated PCMs, the PCM-HTF heat trans-
fer process modeling, as well uncertain long-term stability, requires more investigation
due to micro-encapsulation architecture [39]. In addition, cost must also be considered,
and at the early stage of the research this was among the most expensive storage methods
for PCMs [28].
To overcome micro-encapsulation issues, more complex geometries, such as the use
of fins or extended surfaces in the PCM, to provide additional heat transfer surface, were
studied in order to enhance thermal conductivity [29]. Nevertheless, it has been demon-
strated that their employment must be finely tuned with respect to their final application,
as the beneficial effect of fins decreases with increases in the heat transfer coefficient. For
Polymers 2022, 14, 620 7 of 33

this reason, in most cases, fins must be included at the side of the PCM container and their
use must be regulated if melting or solidification phases are to be enhanced [29]. In addi-
tion, fins can vary widely in material, number, and thickness, as these parameters are cru-
cial to promote both conduction and convection processes during PCM phase change.
From several studies, it was demonstrated that heat transfer during PCM melting is
mainly ruled by natural convection, therefore, in this case, fins could be helpful to further
promote the natural convection process [29]. In fact, generally, the same material as the
PCM’s envelope is employed. Rectangular fins are the most frequently used due to their
very simple geometry and low-cost manufacturing, but ring-shaped fins were also em-
ployed in configurations in which the PCM is placed around HTF tubes, as shown in Fig-
ure 4. Numerical models that compared the latter solution with a system without fins,
demonstrated that the great majority of heat was conducted through the fins along the
radial direction. For different ranges of mass flow rate and inlet temperature, a consider-
able amount of increase in the energy stored was observed due to the presence of fins,
increasing with the fins’ number, up to + 63% with 19 fins [29,40].

Figure 4. Ring-shaped fins added to a shell-and-tube LHTES unit [29].

The impregnation of porous structures with PCMs was investigated as another viable
way to increase their thermal conductivity. However, the final result depends not only on
the materials’ thermal conductivity itself, but also on their mean pore size [29]. In fact,
several numerical studies demonstrated a substantial decrease in the response time of the
porous metal matrix-PCM system; consequently, a high porosity (up to 85%), for the ob-
tainment of the highest possible performance, must be promoted. However, this solution
raise concerns related to the final disposal of the porous structure, as the PCMs’ presence
inside the porosity must be considered and evaluated at the end-of-life when recycling or
landfill disposal are needed. The most commonly investigated materials were metals, e.g.,
aluminum or copper, and carbon-based materials, such as graphite, which presents a nat-
ural porous structure, or expanded graphite (EG) [29,41].
Metals can also be added to the PCM in the form of high-conductivity particles, or as
metal structures (e.g., metal rings or screens). However, particle mass fraction must be
carefully designed to enhance thermal conductivity, without lowering the thermal storage
capacity of the PCM. In fact, metal structures usually occupy much more volume (20%) in
the PCM with respect to other technologies, such as fins (7%). Copper, aluminum, and
silver are the most studied metals for applications with particles, due to their high cost
and enhanced thermal conductivity, while steel is preferred for metal structures or ex-
tended geometries. With metals, only paraffin-based PCMs can be used, because of the
corrosion phenomenon due to salt hydrates [26,29]. Among carbon-based materials, char-
acterized by high thermal conductivity and low density, carbon fibers have been consid-
ered, as they can be added in the PCM in form of fibers, brushes, or cloths. This material
allows a good enhancement of thermal conductivity with a volume fraction of approxi-
mately around 1% and a reduction in solidification time of around 23%, but also presents
high costs due to the need for a very uniform distribution of fibers in the PCM [29].
Polymers 2022, 14, 620 8 of 33

In these years, to overcome these challenges in PCM design and optimization, the
mathematical and numerical modeling of phase change and heat transfer phenomena that
take place in LHTES systems were approached first. Two main models and related cate-
gories were developed during the 2000–2010 period: those based on the first law of ther-
modynamics, which aimed to quantify the amount of stored energy; and those based on
the second law, which aimed to quantify the usefulness of stored energy. Consequently,
the two models were concern with energy and exergy analysis, respectively. Most of the
studies in this period focus only on energy analysis, while exergy-based evaluation is less
frequently considered, despite its value and complementarity with the first. This trend is
due to the fact that most energy-based models are validated through experimental set-
ups, while the acceptability of exergy-based models suffers from a lack of evidence against
experimental data [27,41]. Historically, simplified analytical approaches were proposed
with the so-called Stefan problem and Neumann method, as clearly reported by GSH Lock
[42]. However, to comprehend the behavior of these phenomena, numerical codes are
needed, as they formally implement and solve energy and heat transfer equations, based
on different finite or volume element numerical approximations.
The research on PCM applications in the building sector was at its very early stage
during the period of 2000–2010. Trombe wall and building block applications were inves-
tigated with both organic PCMs, such as paraffin wax and stearic acid, and inorganic salt
hydrates. In this context, several studies demonstrated that for a given amount of heat
storage, the addition of PCM (~20% of the weight being paraffin) requires less Trombe
wall volume (−20%) and weight. At the same time, concrete and wallboard functionaliza-
tion (direct mixture), mainly with mainly organic PCMs, such as paraffin waxes or fatty
acids, were considered [6,30]. Despite the promising results of these studies in terms of
good heat transfers, some critical issues must be highlighted. The most important of all
was the small number of suitable commercial materials, which must have both a transition
temperature falling in the human comfort range (20–32 °C) and a reasonable cost of em-
ployment in amounts high enough to be mixed with concrete [6,9]. In addition, to enhance
the free cooling phenomenon, the combination of at least two PCMs was suggested to
allow year-round thermal management [33]. In fact, free cooling takes advantage of low
night temperatures to store coldness in building materials enriched with PCMs, or in
LHTES units, and release it for indoor cooling during the daytime and, for this reason, is
strongly influenced by seasonal variation. Thereafter, it is almost impossible to choose
only one PCM as it would melt/solidify only for a part of the year.

2.2. Further Material Evolution from 2011 to 2015

In this period, in contrast with the previous decade, discussed in 2.1, more efforts
were dedicated to the specific application of PCM technology in the building sector, by
further considering the main issue related to a specific technology (e.g., micro-encapsula-
tion) or applications in different building elements (e.g., walls, mortars, glazing units).
According to Cabeza et al. [43], and as shown in Table 2, at the beginning of this period
(2010), many substances were investigated as PCMs for specific applications and temper-
ature ranges in the building sector. Subsequently, in this period, PCM classification also
started to take into account applications in the building sector. As shown in Table 2, most
of these substances are constituted by organic materials, mainly paraffins and fatty acids,
due to their high performance/cost ratio compared with the other PCM categories.
Polymers 2022, 14, 620 9 of 33

Table 2. PCM classification according to different application types and temperature range in the
building sector up to 2010, according to Cabeza et al. [43].

Hot-Water High-Temperature
Cooling Comfort Applications
Applications Applications
Temperature range −30/+21 °C +22/+28 °C +29/+60 °C +61/+120 °C
Total PCM number 45 34 103 62
Organic (paraffins, fatty acids,
23 (51.1%) 22 (64.7%) 50 (48.5%) 28 (45.2%)
organic mixtures) (%)
Inorganic (salt, salt hydrates,
6 (13.3%) 7 (20.6%) 45 (43.7%) 19 (30.6%)
metals, inorganic mixtures) (%)
Eutectics (%) 14 (31.1%) 5 (14.7%) 8 (7.8%) 15 (24.2%)

As shown in Table 3, the number of commercial PCMs available in 2010 was limited
to 88 products, which is quite low if compared with the 244 total PCMs in Table 2, as
confirmed by Zhou et al. [44]. In addition, it can be noted that at this stage, no commercial
PCM had been developed for hot-water applications; nevertheless, the great majority of
the total number of PCMs were devoted to this application (Table 2). A possible reason
for this trend is that commercial products had been developed for more recent and ad-
vanced applications at that time, while hot-water applications were the most consolidated.
Later studies reported a strong acceleration of the development of new PCMs dedicated
to the building sector. A comparison between commercial products is represented in Fig-
ure 5, which shows that in the same temperature range (15–33 °C), the number of com-
mercial PCMs grew from 20 to 90 in 4 years, from 2011 to 2015. The growth concerns all
PCM categories, but organic substances show the highest increase during these years with
great variability in the technology used, e.g., tubes or mats filled with PCMs, gypsum
boards, floor tiles, windows, heat exchangers, or ventilation systems with PCMs [43,45].

Table 3. Classification of commercial PCMs according to different application types and tempera-
ture ranges in the building sector up to 2010, according to Cabeza et al. [43].

Higher-Temperature
Cooling Comfort Applications
Applications
Temperature range −33/+21 °C +22/+28 °C ≥29 °C
Total PCM number 24 13 51
Organic (paraffins)
2 (8.3%) 5 (38.5%) 29 (56.9%)
(%)
Inorganic (salt
solutions, salt 22 (91.7%) 8 (61.5%) 20 (39.2%)
hydrates) (%)
Unclassified (%) 0 (0.0%) 0 (0.0%) 2 (3.9%)
Polymers 2022, 14, 620 10 of 33

Figure 5. Comparison between 2011 and 2015 of commercial PCMs useful for building applications,
in the 15–33 °C range [43,45].

Some of the first studies in this period (2011–2012) still focused more on the issues
concerning PCMs’ intrinsic properties than on the problems facing their application in
building materials [43,44]. The main critical points that arose in this period were: the need
to further enhance the heat transfer due to PCMs’ low thermal conductivity (from 0.2
W/m⋅K for paraffins to 0.5 W/m⋅K for hydrated salts); the long-term stability of PCMs with
an increasing number of thermal cycles; the compatibility between the PCM and its con-
tainer, such as corrosion between salt hydrates and metal and the dimensional stability of
plastics containing organic PCMs; and the phase segregation or subcooling of salt hy-
drates [43,44]. In fact, in this period, investigations tried to exploit salt hydrates’ peculiar-
ities due to their intrinsic higher phase change enthalpy, by reducing their possible draw-
backs. Later studies in this period show that these problems were not completely solved
for specific categories of PCM, even in the following years.
In fact, the long-term stability of paraffins was assessed, as all the materials tested
showed almost no changes in their properties after a number of thermal cycles, between
300 and 5000 [46]. Different studies demonstrated that the stability of fatty acids depends
instead on their purity degree, as compounds with a purity degree between 90% and 95%
(e.g., stearic acid, palmitic acid, myristic acid, or lauric acid), showed a latent heat drop
after 900–1200 thermal cycles [46]. Phase separation and the supercooling of salt hydrates
were improved, respectively, by employing thickening agents (e.g., attapulgite clay, pol-
yvinyl alcohol, silica gel) and nucleating agents (e.g., Borax, sodium pyrophosphate dec-
ahydrate), subsequently leading to improved long-term stability (e.g., CaCl2 6H2O can
reach 1000 working cycles without phase separation by addition of NaCl and H2O) but
with a more complex PCM formulation to keep under control during their fabrication
[45,46].
With respect to the previous period (2000–2010), in these years (2011–2015), more
specific ways were found to incorporate PCMs into building elements. According to Zhou
et al. [44], five main methods can be defined, as follows:
- Direct incorporation: the PCM and the building material are physically mixed at the
solid state.
- Immersion: a building element, e.g., bricks or concrete, is dipped into a liquid PCM,
which enters into the open pores thanks to capillary forces.
- Macro-encapsulation: the PCM is encapsulated inside a container with a variable
shape.
Polymers 2022, 14, 620 11 of 33

- Micro-encapsulation: the PCM is encapsulated through a thin film of a polymeric

material to form particles with low dimensions, with a diameter lower than 5 μm.
- Shape stabilization: the formation of a composite material (SSPCM, shape-stabilized
phase change material), where the PCM is the matrix, while another material acts as
the reinforcement (e.g., HDPE).
Among the listed methods, micro-encapsulation was particularly investigated, as
new improvements in this field are related to innovative and more specific manufacturing
technologies. In fact, compared with macro-encapsulation, the safety of PCM handling,
due to the reduced dimension, must be carefully taken into account; the development of
new, environmentally safe materials became a significant trend during this period, as well
as the improvement of the stability of the microencapsulated PCM by up to 100 cycles
[44]. In addition, since the overall thermal conductivity can also be potentially lowered by
the material used for the shell due to the restrained PCM mass fraction, thinner encapsu-
lations were investigated in these years through the employment of high-molecular-
weight polymeric film [28]. For this reason, the main categories of PCM considered for
micro-encapsulation are paraffins (e.g., heptadecane or octadecane) and fatty acids (e.g.,
eicosanoic or stearic acids) that have intrinsically higher thermal conductivity with respect
to salt hydrates [47,48].
Taking into account the specific application of PCMs in the building sector, although
the sector involves different building elements, wallboards, concrete, floor and ceiling sys-
tems, windows, and shading elements were investigated, as these construction elements
offer large areas for heat transfer within building enclosures. Nevertheless, between 2011
and 2015, the number of empirical studies on these applications was quite limited, partic-
ularly for windows and shading units as they are a weak link between internal and exter-
nal conditions in buildings, and they are quite challenging to simulate or replicate in la-
boratory conditions [44,49,50]. A greater number of studies also concerned the numerical
simulation of the inclusion of PCMs in building elements, particularly walls. These studies
mainly aimed to evaluate the optimal phase change temperature needed, or the energy
consumption and thermal performance related to the PCM inclusion in the building, de-
pending on seasonal variation and geographic location [44]. The results demonstrate that,
at this stage of the research, numerical approaches driven by specific index estimation,
such as thermal resistance, heat storage coefficient, and index of thermal inertia, are able
to estimate temperature variation with good approximation (~2 °C) [44].
Wallboards and gypsum plasterboards functionalized with PCMs have been investi-
gated as cheap lightweight materials capable of enhancing the thermal comfort and man-
agement of buildings through the reduction of internal temperature fluctuations [44,51].
Many studies consider only organic PCMs with a phase change temperature between 18
°C and 30 °C, such as PEG 600, butyl stearate, micro-encapsulate paraffin, or capric acid
and lauric acid mixtures. The matrix or supporting material of the panel is usually made
of gypsum, polycarbonate, or high-density polyethylene (HDPE). Empirical studies
demonstrated that during winter, these wallboards are capable of reducing the indoor
wall temperature fluctuation by 1.15 °C and reducing the heat dispersion towards the
outside environment [51]. Wallboards used for cooling purposes allow a decrease in the
indoor temperature during the summer peak of up to 4 °C, but this is possible only if the
PCM’s solidification (up to 60 wt% of micro-encapsulated paraffin) is reached during the
night; consequently, at sufficiently low temperatures, this application is strongly depend-
ent on seasonal variation and temperature fluctuation [44,48,50]. In addition, it has been
demonstrated that PCMs’ integration in wallboards is strongly affected by the efficiency
of the manufacturing technique, and on the PCM/matrix ratio, as very different particle
size distributions can be achieved, leading to different heat transfer efficiencies. In fact, a
very restrained diameter of 0.16 μm can be achieved through the chemical route, such as
emulsion polymerization, whereas greater diameters, up to a few millimeters, can be
achieved with physical methods, such as spray drying [48]. The choice of the shell material
Polymers 2022, 14, 620 12 of 33

also plays a very important role, driving microencapsulated PCMs’ morphologies, shell
mechanical strength, heat capacities and thermal stabilities. Among the organic materials
that are easiest to manipulate for microencapsulation fabrication, the most frequently em-
ployed are: polystyrene, polyurea, polymethyl methacrylate, arabic gum, amino resin,
urea formaldehyde resin, melamine, and formaldehyde resin. Nevertheless, their employ-
ment should be restricted due to their flammability, toxicity, and low heat conductivity.
By contrast, the inorganic materials employed are mainly silica-based due to their desira-
ble properties, such as their chemical and thermal stability, flame retardancy, high storage
capacity and good compatibility with building materials [48]. Due to this complexity in
the period investigated, a new category of PCMs arose, named composite PCMs. Moreo-
ver, direct solar gain and the ventilation rate should be considered together as environ-
mental temperature fluctuation, as they can affect the effective temperature measured on
the wallboard, leading to over or underestimation of the PCMs’ performance. Finally, it
must be noted that, in several studies, the amount of the building element (e.g., a wall)
covered with PCM, or with PCM added to it, is not always specified, and this leads to an
increased difficulty in quantifying the real performance of the PCM, which also makes it
more challenging to compare between different studies [10,44,48,49,51,52].
The integration of PCMs into floors and ceilings is usually intended to charge the
materials with heat or coolness during the night and release them during the day, shifting
the peak of electricity consumption to the off-peak period and allowing the use of cheaper
energy. Wallboards have also been used in ceilings, coupled with active systems to en-
hance indoor thermal regulation. Metal containers (typically iron or steel) filled with salt
hydrates or micro-encapsulated paraffin mixed with gypsum or rock wool were placed
on the ceiling and coupled with active systems, as a ventilation system or a capillary sys-
tem of water tubes. The results demonstrated that these systems are able to store coolness
during the night and release it during the day, reducing the maximum peak temperature
by up to 2 °C [48]. A similar principle is used in underfloor heating or cooling systems,
which could be coupled with PCM plates to store heat or coolness [10,44,48].
Different studies investigated the addition of PCMs into concrete matrices, as they
are characterized by a high thermal mass, which allows the storage of thermal energy.
Furthermore, for this application, usually, only organic PCMs are considered, e.g., paraf-
fin, butyl stearate, dodecanol, and tetradecanol [53]. One of the main critical points inves-
tigated, in greater depth than in previous years, was how to promote the addition of PCMs
into the concrete matrix, avoiding an excessively strong decrease in mechanical proper-
ties. In fact, although the addition of micro-encapsulated PCMs seems to consistently re-
sult in the worsening of mechanical properties, the final product is still appropriate for
several building purposes. It has been demonstrated that a compressive strength of over
25 MPa and a tensile splitting strength of over 6 MPa, without any variation after 6
months, can be reached by adding a 5 wt% of commercial PCM called Micronal from BASF
[44,53]. On the other hand, other studies report a 13% decrease in compressive strength
for each 1% of micro-encapsulated paraffin added to the matrix, or a decrease equal to
32% for a 5% addition of micro-encapsulated PCM [48,53]. The difference among these
results must be founded in the fact that, during these years, specifically tailored commer-
cial materials have been developed in order to limit the concrete’s property loss. The loss
of workability and the higher costs connected to the addition of PCM to concrete are ad-
ditional problems, and the limited percentage of material that could be added could result
in a low increase in the total heat storage capacity for concrete [49]. Furthermore, micro-
encapsulated PCM addition between 1% and 5% grants an increase in concrete-specific
heat capacity; it is also the cause of lower thermal conductivity. Experiments performed
on concrete cubicles (Figure 6) with 5% paraffin-based commercial PCM demonstrated
that summer peak temperatures could be lowered by up to 3 °C with PCM addition when
compared with concrete only [51,53]. On the other hand, it is not clear whether this lower
peak was due to the higher thermal capacity or to the lower thermal conductivity of the
material, although this performance can be repeated every day only if the PCM is allowed
Polymers 2022, 14, 620 13 of 33

to completely solidify during the night [44,48,49,51,53]. In this context, PCM leakage out
of micro-capsules must also be considered as a potentially critical issue, not only for over-
all technical performance but also for environmental safety [51].

Figure 6. Test of concrete cubicles enhanced with PCM [51].

In these years, as previously suggested, a limited number of studies also investigated

more sophisticated ways of introducing PCMs into building elements, such as windows
or shutters. Window improvement could be a viable way of reducing heat loss during
winter, while shutters integrated with PCMs could reduce the amount of heat that enters
buildings during summer, as they are the main paths in charge of heating loss or absorp-
tion, through solar radiation, of the overall building structure. For these reasons, some
studies focus on the addition of PCMs to glazing and shading elements. The use of salt
hydrates (with a melting interval of 24–29 °C) with conventional glass for windows is
reported, as they are both inorganic materials and are, therefore, more chemically com-
patible [45,49]. The two materials showed good compatibility and a reduction in heat
losses equal to 30% compared with conventional glass, even though leakage problems are
reported [49]. Other studies reported that the use of salt hydrates in windows during sum-
mer could reduce the gained energy amount by up to 50% [45,49]. Nevertheless, one gen-
eral issue is the transmittance of salt hydrates with respect to visible wavelength, a prop-
erty that greatly depends on the physical state of salt hydrates. In fact, even in the most
optimized systems, salt hydrate-enhanced windows cannot guarantee a clear view of the
environment beyond them. The use of salt hydrates (with a melting interval of 26–30 °C)
is also reported for vertical slats employed as shading units. Their use in summer granted
lower indoor temperatures (between 1 °C and 2 °C), even though the salt hydrate phase
change during the night was prevented by the outside temperature, without the use of a
mechanical ventilation system [45,48,49].
During the same years (2011–2015) there was a growing but limited interest related
to the environmental sustainability of PCMs to determine the global benefits of such so-
lutions, as also demonstrated by an increasing interest in more advanced microencapsu-
lation techniques and materials. Consequently, the contribution of the relevant life cycle
phases was included in some studies, and the possible burdens of shifting from one life
cycle phase to another was taken into account due to the use of these emerging technolo-
gies within the construction systems. A life cycle assessment study of an alveolar brick
construction system, incorporating salt hydrates SP-25 A8 encapsulated in CSM (compact
storage module) panels, demonstrated that a reduction in the environmental impact was
produced due to the energy savings achieved during the operational phase, compensating
for the increase in the environmental impact due to the use of PCM [54]. Furthermore, the
environmental impact due to the inclusion of ester as PCM in building envelopes was
studied and compared to other PCMs (paraffin and salt hydrates). The results demon-
strated that the impact of ester used as PCM slightly improves the effect obtained in the
case of using salt hydrates during the manufacturing impact. On the other hand, the use
Polymers 2022, 14, 620 14 of 33

of salt hydrates or ester as PCM led to impact reductions of 9% and 10.5% respectively,
compared to the case of using paraffin [55].

2.3. The More Recent Evolution from 2016 to 2021

In these years, studies were mainly focused on the different applications of PCMs in
the building sector by exploiting their peculiarities in specific technologies, as macro- and
micro-encapsulation, or on specific building elements, as mortars.

Table 4. PCMs studied for building applications in the period 2016–2021, according to Akeiber et
al. [19], Liu et al. [56], Singh Rathore et al. [57], and Da Cunha and De Aguiar [58].

Melting Point
Category Encapsulation Type Shell Material Reference
(°C)
RT 18 Organic 18 Macro Steel [56]
Capric acid and lauric
Fatty acids 20 Macro Stainless steel [56,58]
acid
EPDM and furnace
RT 21 Paraffin 21 Macro [19]
dust
SP 22 Inorganic 21 Macro / [19]
Hexadecane Paraffin 22 Macro Copper [56]
Micronal DS-5008X Organic 23 Micro Acrylate polymer [19,57,58]
Inertek Organic 23+27 Micro Polymer [58]
PEG 600 Polymer 21–25 Macro PVC [56–58]
Micronal DS 5001 X Organic 23–26 Micro Acrylate polymer [57,58]
Capric acid and 1- Fatty acid and
26 Macro Aluminum [19,56]
dodecanol fatty alcohol
Dodecanol Fatty alcohol 26 Micro / [57]
Capric acid and
Fatty acids 26 Micro Polystyrene [57]
myristic acid
Capric acid and
Fatty acids 26 Macro Gypsum wallboard [19,56]
palmitic acid
SP 25 Salt hydrate 26 Macro Aluminum [56,58]
Calcium chloride
Salt hydrate 25–27 Macro PVC [19,56]
hexahydrate
Macro Aluminum
RT 27 Organic 28 [56–58]
Micro /
RT 28 Organic 28 Micro / [57]
RT 28HC Organic 27–29 Macro Aluminum [19,56,58]
MG29 Paraffin 27–29 Macro Glass [19]
Micro CaCl2
Octadecane Paraffin 28–29 [57]
Micro PMMA/tio2
Micro Brookite (TiO2)
Eicosane Paraffin 30 [57,58]
Macro Galvanized steel
Capric Acid Fatty acid 30 Macro Aluminum [19,56]
Salt hydrate Salt hydrate 31 Macro Polymer [56]
RT 35 Organic 28–35 Macro Aluminum [19,56]
Tetradecanol and Fatty alcohol and
29–32 Macro PE-RT [56]
myristic acid fatty acid
MPCM37-D Paraffin 37 Micro Polymer [57]
RT 42 Organic 38–43 Macro Stainless steel [56]
Polymers 2022, 14, 620 15 of 33

According to Table 4, which reports a summary of the most studied materials accord-
ing to Akeiber et al. [19], Liu et al. [56], Singh Rathore et al. [57], and Da Cunha and De
Aguiar [58], the majority of experimental studies still consider organic PCMs. Paraffins
(e.g., hexadecane, octadecane, and eicosane) are the most investigated, followed by fatty
acids (e.g., capric acid, lauric acid, and palmitic acid). The phase change temperature of
PCMs usually varies between 18 °C and 30 °C, but there are some applications with higher
temperatures, between 37 °C and 43 °C, according to climate changes and particular
needs. The same trend was also confirmed by Song et al. [59], who list the applications of
PCMs in different parts of the building envelope, namely walls, ceilings, and floors. How-
ever, the distribution of studies between different building elements is not equal. Accord-
ing to Zhu et al. [60] and Da Cunha and De Aguiar [58], the majority of studies concern
wall applications (approximately 60% of studies), followed by ceiling and floor applica-
tions, which mainly include the introduction of PCMs into concrete, gypsum boards or
panels. Considering Table 4, macro-encapsulation techniques were still favorable with re-
spect to microencapsulation, due to the still-high cost of the latter.
An additional focus on the experimental studies performed on PCM applications be-
tween 2019 and the first half of 2021 is presented in Table 5 (passive applications) and
Table 6 (active applications). The trend presented by the studies in Table 4 is mainly con-
firmed, as paraffins were the most studied PCMs during these years, with some excep-
tions, such as tetradecanol and hexadecanol or coconut oil. All the materials studied are
organic, with a small number of exceptions that consider two salt hydrates, namely CaCl2
∗ 6H2O and MgCl ∗ 6H2O. Nearly half of the studies still consider macro-encapsulated
PCMs, while micro- or nano-encapsulated PCMs are a minority, as shape-stabilized
PCMs. The phase change temperatures range from 17 °C to 44 °C, and walls are again the
most studied building elements; however, the inclusion of PCMs in the ceiling and floor
is also studied. Most of these studies investigate the performance of building elements in
passive conditions in field tests, attempting to understand whether the inclusion of PCMs
alone could prevent or minimize the use of active systems to regulate indoor thermal con-
ditions in different climates, as well as avoiding energy consumption.

Table 5. Main experimental studies on passive applications performed on building elements con-
taining PCMs between 2019 and 2021.
Building Position in
Reference Test Scale PCM PCM Form Tmelt (°C) Remarks and Results
Material Building
The PCM decreased the cooling load, peak,
aluminum
[61] field test RT28HC macro 28 wall and average temperature in the room by
panel
0.8 °C when coupled with the radiative panel.
The PCM blind was used to reduce the
blind in a
aluminum overheating problem typical of double skin
[62] field test PX 35 micro 35 double-skin
panel facades in summer, stabilizing the internal air
façade
temperature between the two glass layers.
The PCM roof allowed a reduction of indoor
air temperature fluctuations from 7% to 15%.
SSPCM Combined with a high-reflectivity roof, it
[63] field test paraffin (paraffin + 25.5 concrete panel roof reduced the indoor air temperature
graphite) fluctuation from 8.5% to 17.0%, while the
inner surface temperature of the roof was
reduced by 2.2 °C.
The integration of PCMs reduced both indoor
and materials’ temperature. Cool roof
polyurethane materials benefit from lower phase change
[64] lab test paraffins SSPCM 25, 31 and 44 roof
membrane temperatures (25–35 °C), while common dark
membranes show a better performance with
higher temperatures (31–45 °C).
macro PCM reduced the indoor average
[65] lab test CaCl2 ∗ 6H2O (Polyvinyl 26 wallboard Wall temperature and its fluctuations, but this was
chloride) highly dependent on climate conditions.
Polymers 2022, 14, 620 16 of 33

Tensile strength of the wood fiber composite

was reduced up to 58%, and flexural strength
wood fiber-
lab and field up to 68% with 40 wt% of PCM. Use of PCM
[66] paraffin nano 27.4 polymer floor
test coupled with natural night ventilation help to
composite
reduce the overheating period (temperatures
above 23 °C) to about 50%.
The PCM in south-facing walls and window
allowed a higher reduction of indoor
[67] field test coconut oil macro 22.6 pouches walls, windows temperatures (up to 7.2 °C) If the PCM is
applied only on the wall, the reduction is
equal to 5.2 °C.
The PCM (30 wt%) helped to stabilize the
indoor temperature but not enough to reach
plaster
[68] field test n-octadecane nano 23.3 walls, ceiling the comfort range (18–23 °C), so natural
wallboard
night-time ventilation is required during
summer.
The PCM enhanced the heat balance of the
integration of
window by 10% during the heating season
[69] field test RT28 macro 27.5 separate TES window
but suffered from overheating during
in the window
summer.
The PCM integration in the wood walls
CaCl2 ∗ 6H2O showed a reduction in overall temperature
polyethylene
[70] field test and MgCl ∗ macro 21 wall fluctuations equal to 57%, while the
containers
6H2O mixture day/night fluctuations were reduced by 62%
with respect to the reference room.
Tetradecanol attenuated better than
hexadecanol heat waves at the west wall.
33.8 However, the reference board performed
SSPCM
1-tetradecanol (tetradecanol) plaster better on both PCM-enhanced boards when
[71] field test (PCM + wall
1-hexadecanol 41.8 wallboard placed on the east wall. This suggests that the
diatomite)
(hexadecanol) suitable phase change temperature depends
also on the orientation of the elements of the
building.
Depending on the encapsulating material and
on the orientation of capsules
copper or
(vertical/horizontal), the PCM (12–15%)
PVC tubes
n-octadecane reduced the peak heat flux in the wall
[72] lab test macro 32.2 embebbed in wall
(RT26) between 12% and 33% with respect to a
insulated
reference insulation panel. Copper was
panels
shown to be more efficient than PVC as
encapsulating material.
The internal temperature of the window
decreased by 7.6 °C when filled with PCM
[73] field test RT28HC macro 28 glass window instead of air, and the CFD model suggested
that PCM thickness should not exceed 30
mm.

Table 6. Main experimental studies on active applications performed on building elements contain-
ing PCMs between 2019 and 2021.
Building Position in
Reference Test Scale PCM PCM Form Tmelt (°C) Remarks and Results
Material Building
BioPCM was not efficient for cooling during
wallboard
paraffin (DuPont SSPCM summer, but it was found to be effective in
laminated with
Energain). Soy (DuPont 21.6 winter, to increase the thermal inertia of
aluminum
[74] field test and palm oil Energain) (Energain) 25 walls, ceiling buildings.
(Energain)
(BioPCM Q25 macro (BioPCM) Energain reduced the peak temperature by
pouches
M51) (BioPCM) 3–4 °C and the daily temperature
(BioPCM)
fluctuations to 1–2 °C.
The PCM increased maximum floor
[75] lab test paraffin SSPCM 17.2 resin sheet floor temperatures during heating and cooling
respectively by 5.04 °C and 1.08 °C. The
Polymers 2022, 14, 620 17 of 33

cooling delay time of the floor was increased

up to 3.6 h.
Macroencapsulated PCM showed higher
cooling power with respect to the one with
microencapsulated PCM but lower respect
[76] lab test paraffin macro 24 Panel steel ceiling
to the one without PCM. This panel also
showed greater flexibility in shifting the
cooling load to off-peak hours.
The inclusion of PCM was useful to shift the
floor, wall, heating load to low-peak periods. Inclusion
[77] field test coconut oil macro 25 steel
ceiling of PCM in the ceiling was less efficient than
inclusion in floor and walls.
The PCM increased the thermal storage
capacity of the floor by 77.36% and
stabilized indoor thermal stability. The heat
[78] field test not specified micro 27.8 steel floor gained from solar radiation and stored in the
PCM floor can increase indoor air
temperature by 3 °C if coupled with the
ventilation system.

As previously suggested, in this period, one of the principal innovations was due to
the introduction of PCMs to mortars. The introduction of PCMs into concrete and mortars
was reviewed by Rao et al. [79] and Berardi and Gallardo [80]. Different kinds of mortar
were considered, but cement mortar was the most studied, as shown in Figure 7, com-
pared to other types, such as lime mortar, aerial lime, and gypsum, or geopolymer mortar.

Figure 7. Number of different combinations of PCMs and mortars investigated in the period 2016–
2021 [79].

From the analysis of these studies, paraffins were the most frequently studied of the
PCM categories with the potential to be incorporated into mortars, as they do not disturb
the hydration reactions. On the other hand, common direct incorporation methods, in-
cluding the wet mixing or immersion technique, usually imply a high risk of leakage of
the PCM in its liquid phase, or an interaction with the matrix during its lifetime, and this
problem is quite critical for organic PCM employment [58,80]. Other direct incorporation
methods tested require a supporting material, which is often cheaper than those used for
macro or micro-encapsulation, to avoid PCM leakage [79,80]. Silica fume and expanded
graphite were studied as supporting materials, as they also enhance the thermal conduc-
tivity of the PCMs. Other materials studied were expanded perlite or vermiculite,
Polymers 2022, 14, 620 18 of 33

lightweight aggregates (LWA), or rice husk aggregates, as they are chemically compatible
with mortars [79,80]. The use of paraffin and expanded graphite showed good chemical
compatibility with lime mortar, but involved too high a cost due to the micro-encapsula-
tion process [79]. LWAs (based on clay, pumice, diatomite, and expanded vermiculite or
perlite) were enriched with PCMs through the vacuum impregnation technique, which
enables the absorption of PCM up to 73 wt%, and then coated with epoxy or polyester
resin, or limestone powder, to avoid leakage [80]. However, it was demonstrated that the
use of these coatings reduced the thermal conductivity of the whole material, while the
addition of LWAs enriched with PCMs is reported to reduce the compressive strength of
mortars from 10% to 72%, depending on the LWA material and the PCM percentage
added [80]. Nevertheless, the use of expanded perlite (30 wt%) was successfully tested to
control the leakage of paraffin [80].
The use of micro- and macro-encapsulation was also studied to add PCMs into mor-
tars. For the first, commercial polymeric microencapsulated PCMs were employed, often
as a replacement of a part of fine aggregates used in concrete or mortars, such as sand.
The results showed that the amount of micro-encapsulated PCMs should not exceed 6
wt% of concrete (which corresponds to 10–12% of volume) to limit the reduction in the
workability and compressive strength of the whole material, which is usually around 40%
for the compressive strength when the PCM weight percentage is higher than 3% [80]. The
use of micro-encapsulated PCMs also reduces the thermal conductivity of the material
with respect to the concrete without any PCM. In fact, despite the higher specific surface
of micro-capsules with respect to macro-capsules, they have lower thermal conductivity
than common sand. Moreover, their addition increases porosities of the concretes, which
are filled with low-conductive air. This effect causes a drop from 25% to 50% in the ther-
mal conductivity of concrete when a 5% mass of PCM is added [58,80]. Macro-encapsu-
lated PCMs employ stainless steel to encapsulate the PCM, leading to many advantages,
such as lower leakage compared to micro-encapsulated PCMs, and the unmodified com-
pressive strength of the mortar [79]. The use of other materials, such as PVC or other pol-
ymers, should allow the use of inorganic PCMs not compatible with metals, such as salt
hydrates. However, there are almost no studies on them, probably due to several critical
issues such as phase separation, supercooling, and the lack of long-term stability
[58,59,79,80].
Table 7 lists other experimental studies focused on the inclusion of PCMs in concrete
and mortars between 2019 and 2021. With respect to the studies presented in Tables 5 and
6, no salt hydrates are considered, but a greater variety among organic PCMs can be ap-
preciated. In fact, a consistent number of them belongs to alcohols or fatty acids, as well
as paraffins. The majority of PCMs were included in mortars in a shape-stabilized form,
mainly obtained through the impregnation of natural porous materials (e.g., perlite, pum-
ice, diatomite, vermiculite). Other studies evaluated the inclusion of PCMs in microencap-
sulated form, and only a few works investigated the direct inclusion in the mortar [81–
83]. Portland cement is the most studied binder, but alkali-activated cements and geopol-
ymers also seem to be considered as viable alternatives. No problems due to chemical or
physical interactions between PCM and mortar/concrete emerged; nevertheless, the per-
centage of PCM must be limited (up to 20 wt% in the mortars), mainly to control the de-
crease in mechanical properties, such as compressive strength and flexural strength
[82,84–87]. Instead, the decrease in the workability of fresh mortar/concrete is usually
solved by adding more water in the initial mixing of the materials or by using a super-
plasticizer [81,84,88,89].
Polymers 2022, 14, 620 19 of 33

Table 7. Experimental studies on the inclusion of PCMs in concrete and mortars between 2019 and
2021.
PCM Latent
Incorporation in
PCM PCM Tmelt Supporting Building Heat
Reference PCM the Results
Form (°C) Material Material Capacity
Concrete/Mortar
(kJ/kg)
The PCM prevented a concrete
temperature rise, improved its
[81] Butyl stearate bulk 23.4 none concrete direct 134.2 workability, and reduced the
corrosive damages on steel
embedded in concrete.
The PCM lowered both the phase
change temperatures (from 37–40 °C
to 13–17 °C) and the phase change
Hydraulic
enthalpy (from 129 kJ/kg to 7–9
lime, gypsum, impregnated
[84] PEG 1000 SSPCM 37–40 Lecce stone 129 kJ/kg). Both flexural and
cement aggregates
compressive strength showed a
mortars
considerable decrease for all the
binders with a water increment of
15%.
Microencapsulated PCM (up to 20%)
Alkali- enhanced the heat storage capacity
Micronal 5008 acrylic
[85] micro 23 activated microcapsules 100 of the cement but decreased its
(Octadecane) polymer
cements compressive strength from 43% to
50%.
The addition of composite PCM to
the cement led to a significant
Capric acid and decrease in its compressive strength
myristyl alcohol expanded impregnated (from 54% to 82% decrease for 10
[90] SSPCM 17–32 cement 167.2
(weight ratio = perlite aggregates wt% to 30 wt% of composite
9:1) addition). Indoor temperature
fluctuations were reduced, and no
leakage was shown.
The use of steel balls (30%)
prevented leakage problems but
reduced the concrete’s compressive
strength by 18%. A total of 5% of the
blending of cement mass was replaced with slag
[88] Butyl stearate macro 19 steel balls concrete macrocapsules 107.3 and fly ash to solve this problem.
and concrete Coarse aggregates substitution (10%
in volume) with steel balls greatly
enhanced the heat transfer efficiency
without lowering too much the
mechanical properties.
PCM addition to concrete reduced
compressive strength from 18.5 MPa
(0% PCM) to 14.9 MPa (20% PCM).
The addition of PCM up to 10% does
not cause significant changes in
[82] paraffin bulk 20–23 none concrete direct 107.3
flexural and compressive strength.
The direct incorporation of PCM
increased the liquid/binder ratio and
decreased the water absorption of
concrete.
The addition of PCM from 0% to
Alkali- blending of 30% caused a serious reduction in
[91] BSF26 micro 26 not specified activated microcapsules 110 mechanical properties (compressive
cements and cement and flexural strength). No more than
20% of PCM should be added.
The mortar was enriched with 6 wt%
Portland of PCM, enhanced with copper oxide
[83] 1-dodecanol bulk 22 none direct 195
cement and titania, generating a 10%
decrease in the compressive strength
Polymers 2022, 14, 620 20 of 33

SSPCM (Pumice + 34 wt% of PCM)

showed good compatibility, no
octadecane
leakage, and good thermal stability.
(75%) and impregnated
[92] SSPCM 20.4 pumice cement plaster 232.7 Cement mortar was formed with 30
eicosane (25%) aggregates
wt% of the SSPCM achieving
eutectic mixture
sufficient thermal regulation
properties.
The SSPCMs (62 wt% of capric acid
capric acid 31.3
190.2 (Capric and 56 wt% of PEG) showed good
and (Capric Portland impregnated
[93] SSPCM pumice acid) thermal stability. Plaster enriched
polyethylene acid) cement aggregates
148.5 (PEG) with SSPCM (20 wt%) for thermal
glycol (PEG 600) 9.9 (PEG)
regulation in buildings.
A plaster with 6 wt% PCM was
expanded
hydraulic lime tested, showing no leakage problems
perlite, impregnated
[94] PureTemp 23 23 and Portland 227 and compressive strength, similar to
hydrated materials
cement plaster a commercial plaster taken as
lime
reference.
No leakage was detected and the
time delay in temperature rising was
Portland
expanded impregnated verified with respect to concrete
[95] n-nonacosane SSPCM 64 cement 195
perlite aggregates without PCM. Compressive strength
concrete
decreased by 40% (from 37.5 MPa to
22.5 MPa).
The addition of 20 wt% of SSPCM
Lauric acid (66
(37% of PCM) to the cement mortar
wt%) and
Portland impregnated fly reduced the compressive strength by
[86] myristic acid (34 SSPCM 32.2 fly ash 177
cement mortar ash 54% (from 45.12 MPa to 20.21 MPa)
wt%) eutectic
and flexural strength by 67% (from
mixture
5.25 MPa to 1.74 MPa).
The addition of 20% of SSPCM (27%
Capric acid (82 of PCM) to the mortar showed good
wt%) and temperature regulation properties.
Portland impregnated
[87] stearic acid (18 SSPCM 24.7 silica fume 178 Its compressive and flexural strength
cement mortar silica fume
wt%) eutectic were respectively decreased by 37%
mixture and 36.57% compared with the
reference mortar.
Up to 20 wt% of PCM was added to
polymer the mortar. The compressive
mechanical
[96] Nextek 37D micro 37 not specified modified 190 strength decreased from 64 MPa to
blending
cement mortar 14 MPa, while the flexural strength
decreased from 8.6 MPa to 4.8 MPa.
The addition of 15 wt% and 30 wt%
of SSPCM decreased the
compressive strength of the
geopolymer
geopolymer concrete, respectively,
expanded concrete, impregnated
[97] RT27 (paraffin) SSPCM 26.5 189 by 35% and 64%. However, the
perlite geopolymer materials
addition of 30 wt% SSPCM to the
foam concrete
geopolymer foam concrete enhanced
its compressive strength by 87% and
its thermal storage capacity by 181%.
Up to 6 wt% of PCM was added to
the concrete. The compressive
clasting light Portland
impregnated strength decreased by 76.5%
[98] paraffin SSPCM 58.1 shale cement 178.3
aggregates compared with the reference
ceramsite concrete
concrete, while specific heat capacity
increased by 41.2%.
The use of diatomite increased the
thermal storage capacity of the
expanded
SSPCM (52 wt% of PCM) by 15.6%
vermiculite Portland impregnated
[89] paraffin SSPCM 25.2 175.6 and enhanced both its strength and
and cement aggregates
long-term stability. The mortar with
diatomite
diatomite-based SSPCM had a
compressive strength 25% higher
Polymers 2022, 14, 620 21 of 33

with respect to the mortar enriched

only with vermiculite-based PCM
(45 wt%).

In this period (2016–2021), particular attention was put on applications related to spe-
cific seasonal temperatures and variations, leading to a very peculiar situation that re-
quired the use of multiple PCMs (with different phase change temperatures), or well-tai-
lored PCMs, as previously detailed for microencapsulated PCMs. In addition, following
both the climate change issues all over the world and the acceleration of the building sec-
tor in countries (e.g., India and Saudi Arabia) with extremely hot climates (up to 45 °C),
PCM investigation specifically tailored for particular climates is a practical and actual
need [8,19,57,99,100].
In this context, a direct contribution is also given to the environmental aspects,
through a more focused investigation concerning the life cycle assessment analysis per-
formed on PCM applications in constructions. Nevertheless, the environmental impact of
PCMs’ use in the building sector is still an aspect that needs to be studied and that could
have important outcomes on the choice of materials and technologies [101]. For instance,
one of the advantages of macro-encapsulation over micro-encapsulation is the easier sep-
aration between the PCM and the shell material, which simplifies their recovery at the end
of life [56]. This perspective was investigated by Kylili and Fokaides [102], which studied
the impact on the environment through a literature review on the life cycle assessment
(LCA) studies performed on PCM applications in buildings. For the most part, these stud-
ies used the EI99 Environmental Impact Assessment methodology and focused only on
some of the life cycle stages of the investigated materials, particularly the manufacturing,
operational, and disposal stages. Compared to organics (such as paraffins, fatty acids, pol-
yethylene glycol), inorganic PCMs (such as salts hydrates) are less dangerous as they are
chemically stable and can be recycled (Table 8). Other variables were the seasonal condi-
tions, as some studies considered only the summer or the winter season, and the systems’
lifetime, which varied between 50 and 100 years. The results demonstrated that PCMs
incorporated in building materials have a lower impact on the environment compared to
reference cases, without any addition of PCMs. However, these LCA findings are highly
dependent on the scopes and considered phases. The majority of studies did not consider
the lifetime duration of PCM-enriched building materials. Between the manufacture, op-
erational, and disposal stages of these materials, usually only one or two are analyzed.
The results showed that the use of PCMs in building materials is not always environmen-
tally friendly and is highly dependent on life stages. For instance, one of the studies high-
lighted that the addition of PCMs in a ventilated double-skin façade is environmentally
efficient only if the operational period of the façade lasts at least 31 years. Below this value,
the environmental impacts due to manufacturing and the disposal of the façade would
overcome the benefits provided by the addition of PCM [102].

Table 8. Environmental impact of PCMs for building applications. Adaptation from Kylili and
Fokaides [18,101,102].

PCM Name in the EI99 Impact kg/Material [EI99 Pt]

Paraffin Paraffin, at plant, RER 0.208
Calcium chloride, CaCl2, at
Salts hydrates 0.058
regional storage, CH
Disposal, paraffin (assumption) 0.015
Disposal, salts hydrates (assumption) 0.008

Another way to reduce the environmental impact of PCMs is to consider biodegrada-

ble substances or materials derived from wastes. Some studies, such as those reported in
Table 9, consider natural substances as PCMs, e.g., coconut oil or beeswax [103,104]. Other
Polymers 2022, 14, 620 22 of 33

studies, such as those listed in Table 9, try to use natural materials (e.g., wood) or wastes
(e.g., fly ashes, glass scraps) as supporting materials to produce SSPCMs.

Table 9. Experimental studies on the use of natural substances or wastes as PCMs or supporting
materials.
Composite Latent
PCM Tmelt Supporting Type of
Reference PCM Heat Capacity Remarks and Results
(°C) Material Incorporation
(kJ/kg)
capric acid, vacuum
[105] 25.5 fly ash 45.38 Fly ash was obtained from a power plant.
lauric acid adsorption
transparent The composite material showed good transmittance up to
(delignified) 84% by decreasing thickness (up to 0.5 mm) of the
vacuum
[106] PEG 1000 38 wood and 76 composite material. No changes in elastic modulus were
impregnation
polymethyl observed, except a reduction in flexural strength (70.5 MPa
methacrylate instead of 129.6 MPa) due to the inclusion of PCM.
Heptadecane 62 wt% was found to be the optimum
n- activated carbon one-step
[107] 25.1 138.2 content, to avoid leakage and enhance thermal
heptadecane from pine cones impregnation
conductivity.
mechanical A paraffin/rice husk ratio equal to 50% prevented leakage
[108] paraffin 52.1 rice husk ash mixing and 68.1 problems. PCM and rice husk ash showed good
impregnation compatibility and thermal stability.
The composite showed good chemical and thermal
capric acid
performance stability after 600 phase change cycles. The
(83 wt%)
presence of PCMs decreased the water absorption from
and stearic
Scots pine vacuum 80% to 20%, enhancing wood’s hydrophobicity and anti-
[109] acid (17 24.7 94
sapwood impregnation swelling efficiency. The mechanical properties of wood
wt%)
were also enhanced: modulus of rupture (+22.3%),
eutectic
modulus of elasticity (25.3%), and compression strength
mixture
parallel to grain (24.5%).
NaHPO4 ∗
12H2O (58
wt%) and The composite material, with 40% of diatomite, was coated
diatomite, impregnation,
Na2CO3 ∗ with a polymer to avoid leakage problems. Supercooling
[110] 25 polyurethane coating, UV 102.6
10H2O (42 was almost eliminated (0.5 °C) performance stability
acrylate curing
wt%) confirmed up to 300 phase change cycles.
eutectic
mixture
A microencapsulated PCM was integrated (up to 20 wt%)
Nextek 24D
in a soil and reed fiber mixture. The thermal conductivity
(paraffin
silty-clay soil and mechanical decreased by up to 14%. Water vapor permeability’s
[111] and 22.4 Not specified
reed fiber mixing decrease was 20%. The compressive strength was not
polymeric
affected by the addition of PCM; however, the soil-fiber
shell)
mixture itself showed low values of compressive strength.
PCM and supporting materials are both biodegradable and
obtained from renewable sources. Good chemical
PureTemp cuttlebone one-step 145 for both
[112] 23 compatibility and limited leakage was demonstrated with a
23 pomelo peel impregnation composites
thermal storage efficiency equal to 70% of the pure PCM.
The performance stability was confirmed up to 100 cycles.
The PCM impregnation efficiency in the glass-ceramic
porcelain
vacuum foam was between 24% and 39%. Thermal properties still
[113] organic 29.9 stoneware and Not specified
impregnation need to be measured and leakage problems need to be
soda-lime glass
addressed.
expanded The addition of expanded graphite up to 7% led to a
ultrasonication
OM37 graphite and decrease in latent heat storage capacity, while thermal
[114] 39.1 and vacuum 99.3
(inorganic) expanded conductivity increased by 114% and no leakage was
impregnation
vermiculite detected.
expanded glass
PureTemp vacuum Glass aggregates absorbed up to 80% of PCM and, when
[115] 201 aggregates and 92.7
23 impregnation coated with fly ash, showed no leakage problems.
fly ash (coating)
Polymers 2022, 14, 620 23 of 33

In addition, to make PCM-enhanced building materials more attractive for the mar-
ket, in this last period the need arose to perform comprehensive cost analyses and eco-
nomic evaluations on the applications of these materials in the building sector, as high-
lighted by different authors [8,19,57,79]. Furthermore, to achieve this scope, the adoption
of common and standardized procedures should be considered. Firstly, they should con-
cern all the procedures used to design and produce PCMs-enriched materials for the
building sector, such as mortars. Secondly, the methods used to measure the thermal
properties of PCM-based materials should also be standardized. For example, one of the
most common methods currently used to evaluate the melting temperature and phase
change latent heat is differential scanning calorimetry (DSC), which analyses samples
with a mass in the order of a few milligrams. This amount is not enough to give a good
measure of heterogeneous materials, such as a mixture of cement mortar and micro-en-
capsulated PCM leading to a mismatch between measured and real values of the investi-
gated thermal property [57,79,80]. To enhance the measurements’ standardization, other
methods could be used, such as the T-history method or the use of a heat flow meter ap-
paratus, which is suggested both by the Quality Assurance RAL-GZ 896 [116] and the
Active Standard ASTM C1784 [117] documents.

3. Future Challenges: PCM–GHE Coupling

Among renewable energy technologies, air-source heat pumps (ASHPs) and ground-
coupled heat pumps (GCHPs) have been regarded, in recent years, as reliable and efficient
solutions for residential air conditioning applications; their use has also been driven by
their use of renewable-source electricity, which avoids the use of primary energy [118].
GCHP technology uses the soil as underground thermal energy storage and represents a
viable alternative to common ASHPs. In fact, GCHPs do not suffer from seasonal effects,
which lower both the efficiency and heating/cooling capacity of ASHPs. In fact, ASHPs
have a low initial installation cost and are easily applicable; however, they can suffer due
to low ambient temperature in winter, frosting on the outdoor evaporator, and hot am-
bient temperatures in summer. When ASHPs encounter these extreme conditions, their
overall efficiency and heating/cooling capacity is reduced, and defrosting can waste more
than 12% of the full seasonal heating load [119]. By contrast, GCHPs can achieve higher
efficiency than ASHPs by employing underground thermal energy storage (UTES) to pro-
vide more moderate operating temperatures for the heat pump. GCHPs can be installed
at any location where drilling or earth trenching is feasible. Besides their higher efficiency,
their cost-effectiveness is mainly penalized by their ground heat exchangers (GHEs), since
the very low soil thermal diffusivity requires larger sizes, which leads to higher initial
costs [120].
Ground heat exchangers usually consist of a buried piping loop, which can be in-
stalled in vertical boreholes or shallow horizontal trenches (also referred to as VGHEs and
HGHEs, respectively). The use of VGHEs can benefit from the relatively stable tempera-
ture in the deep ground, beyond 20 m. However, a substantial thermal imbalance between
seasonal heating and cooling loads can result in a larger temperature rise or fall in the
ground over the year. The common solution to mitigate this problem is the significant
oversizing of the VGHE, which ultimately reduces the economic feasibility of the project.
Otherwise, a supplemental thermal source (air or solar) may be integrated into the ground
loop to smooth the imbalance as well [121]. By contrast, an HGHE is generally installed in
shallow ground up to 2 m deep. Therefore, it is more subject to variation in the environ-
mental conditions; however, this can actually mitigate the above-mentioned issue of ther-
mal imbalance in mild climate [122]. A prominent advantage is that the installation of
HGHEs only needs a fairly simple trench excavation, and the removed soil can be directly
re-employed for backfilling. Additionally, installation at shallow depths allows consider-
able freedom in the design of the GHE geometry, and the geologic characterization is not
as essential as it is for HGHEs [123]. Further, HGHEs may allow the easy mixing of the
backfilling material with PCMs for higher performance. In view of these distinctive
Polymers 2022, 14, 620 24 of 33

advantages, the research interest in the development of advanced HGHEs for building
applications has grown in recent years.
The GCHP technology is not new, as its first applications are reported in the first
decade of the twentieth century; nevertheless, the problems exposed previously concern-
ing installation and functioning strongly hindered its wide spreading. For this reason, the
integration of PCMs in vertical and horizontal GHEs is still a recent field of research and
there are few studies concerning this technology, most of which are numerical studies.
Table 10 shows the different studies that analyzed PCMs’ integration in different parts of
a GCHP. Between 2012 and 2015, there were only works dedicated to a numerical analysis
of PCM integration in the GHE backfilling material, while from 2016 to now only a few
studies performed empirical investigations. Several studies aimed to assess which were
the advantages and issues related to PCMs’ addition in the backfilling material.
Dehdezi et al. [124] analyzed the thermal properties of a microencapsulated paraffin
wax-soil mixture and simulated numerically the effects of the PCM addition on the soil
temperature around a shallow-ground GCHP. The addition of microencapsulated paraf-
fin wax caused a reduction in soil thermal conductivity and diffusivity, with a 3 °C lower
temperature variation in the soil and a higher (17%) coefficient of performance (COP) of
the GCHP. Similar findings were highlighted by Bottarelli et al. [125], who studied the
coupling of a novel shallow GHE, a so-called flat-panel, with microencapsulated paraffin
mixed directly with the backfill soil. The presence of microencapsulated paraffin
smoothed the ground temperature variations due to seasonality and GCHP action, also
ensuring a higher COP for the GCHP itself. To mitigate the problem concerning low ther-
mal conductivity, Wang et al. [126] compared, through a numerical simulation, the sepa-
rated use of soil, a mixture of n-decanoic acid and lauric acid (7:3 v:v) as pure PCM, and
PCM with the addition of metal particles, as grout in a vertical GCHP. The results demon-
strated that the replacement of common soil with the n-decanoic acid/lauric acid mixture
could reduce the amount of land area needed to install the GCHP by 18%, while the use
of enhanced PCM led to a reduction of land area of 29%. The importance of thermal con-
ductivity enhancement for the PCM grout was also confirmed by Chen et al. [127], who
investigated paraffin as a PCM. However, thermal conductivity also depends on soil char-
acteristics, such as groundwater presence, which increases it. Qi et al. [128] investigated
the influence of different PCMs (RT27, a commercial paraffin from Rubytherm and a mix-
ture of capric acid and lauric acid (66:34)), with and without the addition of metal parti-
cles, on the backfilling grout of a vertical GCHP, finding that the thermal radius effect was
smaller using PCMs independently of the metal particles’ addition. Zhang et al. [129] com-
pared the performance of a common vertical GCHP with a shallow-ground GCHP sur-
rounded by a cylindrical underground thermal battery (UTB) filled with water and a com-
mercial mixture of salt hydrates as the PCM. The results demonstrated that the UTB guar-
antees more stable temperatures of heat transfer fluid with a ten times shorter borehole
compared to a conventional vertical GCHP. Bonamente and Aquino [130] carried out a
performance analysis, through numerical simulation, and a life cycle assessment study of
a vertical GCHP coupled with an upstream LHTES for space conditioning. The analysis
was based on a prototype and considered the impacts of the system from the production
of input materials to the end-of-life of the GCHP. The LCA analysis highlighted the high
relative impact of the LHTES but also the capacity to lower the whole plant energy con-
sumption and environmental impact.
Since 2016, only a small number of studies have experimentally verified the effect of
PCMs in the backfilling material of a GCHP. Li et al. [131] simulated the use of crushed
stone and shape-stabilized PCM (a mixture of decanoic acid and lauric acid (3:2 v:v)) con-
crete enhanced with silica and graphite as grout for a U-tube vertical GHE. The model’s
effectiveness was proven through an experimental measurement of the backfilling mate-
rial at a laboratory scale. The simulation proved that PCMs increase the heat storage ca-
pacity of the borehole and lower its influence radius on the temperature of surrounding
soil, while graphite and silica enhance the heat exchange. Yang et al. [132] performed an
Polymers 2022, 14, 620 25 of 33

experimental thermal performance analysis of a borehole GHE on a laboratory scale to

validate the numerical simulation of a vertical GCHP with PCMs (a mixture of decyl acid
and lauric acid (66:34 v:v), and oleic acid) in the borehole backfill. The results confirmed
that PCM employment enhances the GCHP performance and lowers soil temperature var-
iations. Finally, Barbi et al. [133] studied experimentally the effect of PCMs’ addition in
the backfilling material, common silica sand, of a shallow-ground GCHP. The results of
tests on a laboratory scale demonstrated that the presence of sand promotes heat transfer.
The sand showed a change in some physical properties, such as lower grain size, after
some thermal cycles. However, the thermal performances of the mixtures remained con-
stant through cycles.
Other studies investigated the integration of PCMs with GCHP elements other than
the backfilling material. Zhu et al. [134] analyzed the energy and economic performances
of a hydrate sodium sulfate as PCM cooling tank coupled with a vertical GCHP for the
conditioning of an office building. This work demonstrated that the use of PCM storage
is useful, as it guarantees lower energy consumption and operational costs for the GCHP.
However, it also requires a careful design based on the building type, location, and system
utilization criteria. Pu et al. [135] compared numerically the performances of pure water
and water enriched with micro-encapsulated n-Octadecane as the PCM, and as the HTF
in a horizontal three-shaped and straight tube GCHP. The results demonstrated that the
use of micro-encapsulated PCM enhances water performance, but this depends on the
GCHP’s design. Other few works studied the implementation of micro-encapsulated n-
Octadecane slurries in the HTF of GCHPs to enhance its thermal properties. Kong et al.
[136] performed a field test with micro-encapsulated methyl stearate. To avoid the risk of
clogging in the GCHP system, the ground loop used only water as HTF, while the PCM
circulated in a separate loop, placed between the GHEs and the heat pump. Despite its
low latent heat, the PCM showed high durability and better performance as an HTF than
pure water, but its direct use in the ground loop is yet to be verified due to clogging issues.

Table 10. Studies on the integration of PCMs in different parts of GCHPs. Num = numerical study,
exp = experimental study, H = horizontal GHE, V = vertical GHE.
Melting Latent Heat
Reference Study Type GHE PCM PCM Employment
Point (°C) (kJ/kg)
one-dimensional finite difference micro-encapsulated
[124] num H 26 160 backfilling soil
transient heat transport model paraffin
decanoic acid and GHE’s borehole as
[126] num three-dimensional V 25 /
lauric acid mixture. grout.
water, micro-
[125] num two-dimensional H 0, 26 / backfilling soil
encapsulated paraffin
hydrate sodium sulfate
[134] num modified composite model V 8.3 95.4 GCHP
(type 47)
computational fluid dynamics RT6 8.0–8.5 140
[137] num V GCHP
simulations RT27 25.0–25.5 146
three-dimensional unsteady decanoic acid and backfill material in
[131] num V 20.15 128
model lauric acid mixture a GCHP
paraffin RT27.
three-dimensional finite element decanoic acid and 28–30 179 GHE’s borehole
[128] num V
model lauric acid mixture 20.4 138.8 grout.
(66:34)
micro-encapsulated
[136] exp / V 39.5 9.0–20.9 HTF in a GCHP
methyl stearate
[138] num finite element model V paraffin / 190 GCHP borehole
micro-encapsulated
paraffin.
three-dimensional unsteady 23–27 150
[139] num V Shape-stabilized grout with a GCHP
model 19.9 109.2
decanoic and lauric
acid mixture
Polymers 2022, 14, 620 26 of 33

decyl acid and lauric

exp & three-dimensional computational 20.55 133.65 backfilling material
[132] H acid (66:34)
num fluid dynamics 8.11 94.51 of a GHE
oleic acid
three-dimensional computational salt hydrate (Infinite R,
[129] num H 23 200 UTB with GCHP
fluid dynamics Insolcorp)
micro-encapsulated n-
[135] num Eulerian–Eulerian approach H 28–30 167 HTF in a GCHP
octadecane
exp & RT6 8.0–8.5 140 integrated with a
[130] computational fluid dynamics V
num RT27 25.0–25.5 146 GCHP
n-octadecane 28 241 backfilling material
[133] exp / H
paraffin A28 28 265 of a GCHP

From these results, it is clear that very different ways of enhancing GCHPs’ perfor-
mances and issues through PCMs have been tested, but current studies suffer from a lack
of experimental data and validation, as almost all of them present only numerical anal-
yses. Another important aspect is the system’s end-of-life, as PCM recovery and disposal
would be easier for horizontal GCHPs compared to vertical GCHPs.
Another possible use of PCMs concerns energy piles technology, where a closed loop
consisting of a GHE integrated into the concrete of foundation piles of structures can be
exploited [140]. Although several studies have already analyzed this technology, energy
piles still face different critical challenges, such as the effect of temperature variations, due
to the GCHP, on the internal stress distribution of the concrete pile or its bearing capacity
[141].
In addition, the integration of PCMs into concrete would enhance the GCHP’s effi-
ciency. However, there are many challenges linked to interactions between concrete, GHE
pipes, and PCMs, while the number of related studies is still very limited [142,143]. The
integration between PCMs and backfilling materials, or concrete in energy piles, could
also take advantage of previous studies performed in the building sector. For instance,
studies on the integration of PCMs in envelope materials as mortars or concrete (Table 7)
may be a good starting point to create backfilling grouts with known thermal and me-
chanical properties. However, GHE backfilling contributes to the building’s footprint.
Therefore, its enhancement should be considered as a further strategic opportunity for the
integration of larger thermal energy storage, which can better mitigate the synchrony loss
between supply and demand in using renewable energies.
Furthermore, the integration of PCMs with GHE backfilling materials does not affect
the building volume, (as occurs with HVAC), and the lower digging cost compensates for
its installation. Recently, to further reduce the GCHPs’ installation costs by shortening the
GHEs’ length, multi-source heat pump systems have been studied and designed on a res-
idential scale and for small building volumes [144,145]. The focus is on the exploitation of
the most advantageous energy source (air, ground, solar), which is selected according to
evolved temperatures. However, the ground is the sole source able to carry out thermal
storage and can therefore play a pivot role, which may be improved by PCMs.

4. Conclusions
This work analyzed the main review and experimental studies concerning the inte-
gration of phase change materials into building applications during the last twenty years.
The evolution of the research in this field was divided into three main stages (2000–2010,
2011–2015, and 2016–2021), and the evolution concerning phase change materials and
their application was discussed, with a focus on the studies performed between 2019 and
2021. Some conclusions can be drawn:
- among different classes of PCM, paraffins are generally preferred for integration in
building materials, due to their high performance/cost ratio, but more recent studies
(2019–2021) also consider other organic PCMs, namely alcohols and fatty acids, as
more specific applications need tailored materials.
Polymers 2022, 14, 620 27 of 33

- microencapsulation and shape stabilization represent the main technologies actually

used to incorporate PCMs into building materials, namely wallboards, mortars, and
concrete, as they ensure better thermal properties, while macro-encapsulation is pre-
ferred for glazing elements, due to their higher chemical stability.
- Field- and laboratory-scale tests designed to evaluate the influence of PCMs on in-
door thermal conditions are mainly focused on passive conditions and on avoiding
active HVAC plants. Nevertheless, the generally inconstant performance of PCMs
due to climate or seasonal conditions was determined. The use of active heating/cool-
ing systems, based on PCM employment, is highly recommended, ensuring a con-
stant performance of building elements during the same season or the whole year.
Finally, an overview of the integration of PCMs with ground-coupled heat pump
(GCHP) technology was carried out. The integration between PCM and ground-coupled
heat pump technologies is still at an early stage, as almost all the relevant studies are per-
formed only at the numerical level. The use of PCMs seems to be very promising for hor-
izontal GCHPs, as it allows the stabilization of soil temperature fluctuations and, conse-
quently, the whole performance, without high installation costs.
However, future research related to this new technology could greatly benefit from
the outcomes of previous studies about the integration of PCMs in building materials. The
integration of PCMs in the backfilling material could take advantage of the studies on the
integration of PCM in mortars and concrete. These materials are useful as backfilling for
GCHPs, as there are no requirements connected to their high mechanical properties. The
use of natural materials, such as expanded perlite or vermiculite, and their integration
with paraffins or biodegradable PCMs (such as PureTemp 23 or coconut oil) could also
help the development of this technology in a more environmentally friendly way, avoid-
ing potential environmental problems such as the leakage of melted PCMs into the
ground.

Author Contributions: Conceptualization, M.M. and M.B.; investigation, S.B., F.B. and S.M.; writ-
ing—original draft preparation, S.B., F.B. and S.M. (Simona Marinelli).; writing—review and edit-
ing, S.B., F.B. and S.M. (Sebastiano Merchiori); supervision, B.R. and M.M.; project administration,
M.B.; funding acquisition, M.B. All authors have read and agreed to the published version of the
manuscript.
Funding: This work was supported by the Emilia Romagna region in the framework of the project
“CLIWAX” co-financed by 2014–2020 POR FESR Emilia-Romagna Region Italy DGR 774/2015—
CUP F71F18000160009.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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