energies
Article
Innovative Development of Programmable Phase Change
Materials and Their Exemplary Application
Kristin Lengsfeld 1, *, Moritz Walter 2 , Martin Krus 1 , Sandra Pappert 2 and Christian Teicht 2






Citation: Lengsfeld, K.; Walter, M.;
Krus, M.; Pappert, S.; Teicht, C.
Innovative Development of
Programmable Phase Change
Materials and Their Exemplary
Application. Energies 2021, 14, 3440.
https://doi.org/10.3390/en14123440
Academic Editor: Francesco Nocera
Received: 12 May 2021
Accepted: 8 June 2021
Published: 10 June 2021
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Attribution (CC BY) license (https://
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4.0/).
Energies 2021, 14, 3440. https://doi.org/10.3390/en14123440
1 Department Hygrothermics, Fraunhofer Institute for Building Physics IBP, Fraunhoferstr. 10,
83626 Valley, Germany; martin.krus@ibp.fraunhofer.de
2 Department Energetic Systems, Fraunhofer Institute for Chemical Technology ICT, Joseph-von-Fraunhofer-Str.
7, 76327 Pfinztal, Germany; moritz.walter@ict.fraunhofer.de (M.W.); sandra.pappert@ict.fraunhofer.de (S.P.);
christian.teicht@ict.fraunhofer.de (C.T.)
* Correspondence: kristin.lengsfeld@ibp.fraunhofer.de
Abstract: The research project Fraunhofer Cluster of Excellence “Programmable Materials” aims to
develop new materials that can change their properties according to defined boundaries. This article
describes the development and use of a novel programmable phase change material (PCM) for latent
heat storage applications. At the moment, these PCMs have a programmable trigger mechanism
incorporated that activates the crystallization of the material as a reaction to a defined stimulus so
that the stored heat is released. In future development stages, programmability is to be integrated
on the material level. The latent heat storage that is based on PCMs can be recharged by using the
energy of the sun. As an example, for a possible application of such a material, the use of a novel
programmable PCM in greenhouses to support heating energy reduction or to reduce the risk of
frost is explained. Using the hygrothermal simulation tool WUFI® Plus, the effects in greenhouse
constructions without and with commercially available or novel programmable PCMs are calculated
and presented in the present article. The calculations are based on the material data of calcium
chloride hexahydrate (CaCl2 -6H2 O), as this material serves as a basic material for the development
of programmable PCM compositions. The results of the simulations show a positive impact on the
indoor temperatures in greenhouses in view of the risk of frost and the reduction of heating energy.
Thus, the vegetation period can be extended in combination with a lower energy load. By an eligible
actuation mechanism, an inherent material system for temperature control can be created.
Keywords: PCM; programmable and switchable material; hygrothermal building simulation WUFI® ;
thermal management; latent heat storage; energy efficiency
1. Introduction
Within the framework of the research project Fraunhofer Cluster of Excellence “Pro-
grammable Materials” (CPMs), novel materials and material systems are being developed,
which, due to their structure, can be used to specifically and reversibly change proper-
ties in building components or to realize adaptable systems without auxiliary equipment.
This opens up new areas of use and applications. One part of the cluster project deals
with the development of cycle-stable programmable phase change materials (PCMs) for
latent heat storage, which, due to their composition, are activated by means of a defined
programmable trigger impulse. This impulse might be induced as a reaction to, e.g., an ex-
ternal temperature change, irradiation, or an electric or magnetic field. In consequence
of the activation, the PCM releases the stored latent heat by exothermic crystallization.
This activation-based utilization of PCMs opens a wider range of possible use cases com-
pared to the classic application, e.g., as passive thermal mass in buildings [1,2].
The first development step deals with the cycle-stable basic material, the so-called
switchable PCM. This kind of PCM is characterized by the ability to store its latent phase
change enthalpy over a large number of cycles even below its crystallization temperature
https://www.mdpi.com/journal/energies
Energies 2021, 14, 3440 2 of 13

in a supercooled state. A switchable PCM has already been implemented in different

applications. The material is used in hand-warming pouches [3] or even in larger heat
storage modules for domestic heat supply, as described in [4–6]. The material is then com-
bined with a mechanical switch that is triggered manually or by a sensor-based electronic
control. Within the CPM project, a trigger mechanism made of programmable material
is developed that is able to maintain the triggering activity without auxiliary energy and
sensors. The aim of actual development efforts is to combine switchable PCMs with a
suitable programmable switch to create a programmable PCM system in the state of a
laboratory-confirmed system. The long-term goal within the cluster project is to incorporate
the programmable ability to trigger itself on the material level of the PCM and implement
it in a free-field test setting.
The amount of heat released from the storage material or the heat storage, respectively,
is not influenced by the small trigger mechanism incorporated in the storage volume.
In consequence, comparing a programmable PCM system to conventional PCMs might
serve as a valid benchmark for future programmable PCMs as well. The fact that these
newly developed materials and systems open up new application possibilities will be
demonstrated in this work. More precisely, the impact in terms of usability and energy sav-
ing will be compared by the results of simulations. The application will be calculated and
evaluated exemplarily for different variants using the hygrothermal building simulation
software WUFI® Plus(Version 3.2.1.0 with an in-house add-on module for PCM, Valley,
Bavaria, Germany).
Based on the simulation results, the effect of programmable PCMs in comparison to
commercially available PCMs is intended to be evaluated by the exemplary application
as thermal storage in greenhouse constructions. In this use case, the PCM serves as a
heat buffer to protect plants and their root systems, e.g., from frost damage, as described
in [7–9]. Therefore, the PCM is activated as soon as a critical temperature in the greenhouse
is reached. Solar energy might be used to recharge the heat storage system in a natural way.
This process can be repeated an infinite number of times, and the programmable PCM
system can thus be used as an additional support to the heating of the greenhouse.
In the following, the principles of the newly developed programmable PCM are
explained. Afterwards some background information about the chosen example of green-
houses for the simulations is listed, and proximate information about the input into the
simulation tool WUFI® Plus and results of the application of the newly developed pro-
grammable PCM are compared to other state-of-the-art systems.

2. Materials and Methods

2.1. Switchable Phase Change Materials and Programmable Phase Change Materials
Phase change materials have a high melting enthalpy ∆Hm , i.e., a lot of energy is
required to transform the materials from the solid to the liquid state. During this process,
the temperature in the material ideally remains constant. This material property thus
enables a large amount of (latent) heat to be stored in connection with a small temperature
change around the melting temperature Tm . Conversely, the same applies to the extraction
of energy (heat of solidification) from the material. In contrast, energy absorption and
release in the case of sensitive heat storage in water or bulk storage systems are achieved
by changing the temperature of the storage material over a large range. The correlation
between the amount of supplied and dissipated heat and temperature is shown in Figure 1
for the latent heat storage. Salt hydrates can be classified as inorganic phase change
materials. A characteristic feature of this class of substances is the occurring crystallization
delay, in this context also called “supercooling.” Instead of crystallizing, the material
changes into the metastable state of a supersaturated melt during cooling without a phase
change. Crystallization only starts with a delay at the crystallization temperature Tc < Tm .
This supercooling is represented symbolically in Figure 1 as ∆Tsup .
 Energies 2021,14,
Energies 14, 3440 PEER REVIEW 3 of 13
Energies2021,
2021, 14,xxFOR
FOR PEER REVIEW 33of
of1313

Figure
Figure
Figure1.1.1.
Exemplary
Exemplary
Exemplarydepiction
depictionofofof
depiction the
the supplied
thesuppliedheat
suppliedheatabove
heatabovethe
abovethematerial
thematerialtemperature
materialtemperature
temperaturewith
with
with aarepresen-
arepresen-
represen-
tation of the melting enthalpy ΔH m and supercooling during the cooling process ΔTsup.
tation
tationof
ofthe themelting
meltingenthalpy
enthalpyΔH∆Hmmand andsupercooling
supercoolingduring
duringthe
thecooling
coolingprocess ∆Tsup
processΔT .
sup .

According
Accordingtoto
According tothetheclassical
the classicalcrystallization
classical crystallizationtheory
crystallization theory[10],
theory [10],the
[10], thecause
the causefor
cause forthe
for thecrystallization
the crystallization
crystallization
delay is to
delayisisto
delay be
tobe found
befound
foundin in the
inthe process
theprocess
processofof formation
offormation
formationand and growth
andgrowth
growthof of the
ofthe seed
theseed crystals
crystalsand
seedcrystals andmore
and more
more
precisely
precisely in
precisely in theinthe
the contribution
contribution ofofthe
the surface
surface energy
energy required
required for
for the
the formation
formation
of the surface energy required for the formation of seed crys- of
of seed
seed crys-
crystals
tals
talstotothe
to the thetotal
total total crystallization
crystallization
crystallization enthalpy
enthalpy ∆Gc ΔG
enthalpy . ΔG
Thisc. This
enthalpy
c. This
enthalpyhas ahas
enthalpy aamaximum
maximum
has maximum∆GcritΔG crit, which
, which
ΔG must
crit, which
must be
be overcome
must overcome
be overcome for
for crystal crystal
growth.
for crystal ∆Gc results
growth.
growth. ΔG c results
ΔGc results from
from from the
the lower lower dependency
dependency
the lower dependency of the
there-
of theofrequired re-
quired
quired surface
surfacesurface
energyenergy∆Gs (~r
energy ΔG 2s (~r2) compared to the volume energy released by crystal growth
ΔG)s compared
(~r2) comparedto thetovolumethe volume energy released
energy by crystal
released growth
by crystal ∆Gv
growth
ΔG v 3
(~r).3∆G
(~r ).ΔG isalso
also dependent on the temperature
temperatureofofthe themelt
meltTTTand andthethedegree
degreeofof ofthe
3
(~r
ΔG v ). v vis
ΔG v is also dependent
dependenton onthethetemperature the melt and the degree the
the
supercooling
supercooling ΔT ∆T .
supsup The
. corresponding
The corresponding courses
courses of the
of free
the
supercooling ΔTsup. The corresponding courses of the free enthalpies of crystal growth in enthalpies
free enthalpiesof crystal
of growth
crystal in
growth
relation
relation totoaato
in relation crystallization
a crystallization
crystallization nucleus
nucleus are
areshown
nucleus are shown
shown schematically
schematically
schematically ininFigure 2.2.The
in Figure
Figure The2.extent
The extent
extent and
and
stability
and of
stabilitythe supercooling
of the mainly
supercooling depend
mainly on
depend the material
on the or
material
stability of the supercooling mainly depend on the material or on the material-specific criti- on the
or material-specific
on the material-specificcriti-
cal
calcrystallization
critical
crystallization enthalpy
crystallization enthalpy ΔG
enthalpy ∆Gin
ΔGc.c.This
This turn
. This
c in turnin can turn
can bebeinfluenced,
can among
amongother
be influenced,
influenced, otherthings,
among otherby
things, the
things,
by the
(local)
by the
(local) manipulation
(local) manipulation
manipulation ofofthe
theparameters rrand
andΔT
of the parameters
parameters ΔTsup . . ∆Tsup .
rsupand

Figure
Figure2.2.2.Representation
Representation ofofthe
of critical
thethe enthalpy
critical difference
enthalpy ΔG
difference withwith
ΔGc∆G maximum
maximumΔG ∆Gand
ΔGcritcrit its
itsde-
Figure Representation critical enthalpy difference c with
c maximum crit and
and its
de-
pendence
pendence on the
on theamount of supercooling ΔT sup, as well as on the radius r of the idealized crystalli-
ΔTsup,∆T
dependence on amount of supercooling
the amount of supercooling as sup
well as well
, as on the
asradius
on ther radius
of the idealized crystalli-
r of the idealized
zation
zationnuclei
nuclei[10].
[10].
crystallization nuclei [10].

AAAswitchable
switchablephase
switchable phasechange
changematerial
change materialis
material isisdefined
defined
defined asas
a aphase
as aphase
phase change
change
change materialthatthat
material
material that re-
re-
releases
leases
leases the phase
the phase
the phase transformation
transformation
transformation energy
energy
energy stored
storedstored in
in its in its supercooled
its supercooled
supercooled melt
melt meltonly
only only in interaction
in interaction
in interaction with
with
with aacontrollable
a controllable
controllable trigger.
trigger.
trigger.Therefore,
Therefore,
Therefore, some
somesome necessary
necessary
necessary requirements
requirements
requirements have
have toto
have tobe
be satisfied
satisfied
be by
satisfied
by
by the
thethe PCM.
PCM.
PCM. Besides
Besides
Besides an
ananextensive
extensive and
and
extensive and reliable
reliable
reliable inclination
inclination
inclination for
forforsupercooling
supercooling
supercooling of
ofof at
at atleast
least 20
least 20K,
20
 switching mechanism might respond to various types of external stimuli as, e.g., magnetic
or electric fields, temperature, irradiation, pressure, or humidity. One functional design is
described in the following section, and Figure 3 shows an exemplary sketch of the pro-
grammable PCM–gel actuator.
Energies 2021, 14, 3440 Classical crystallization theory indicates that a suitable crystallization surface might 4 of 13
be used as a physical trigger for activating the exothermic crystallization of the PCM. This
surface might be exposed by a seed crystal of the PCM itself or by a suitable nucleating
agent. Both approaches have been verified in numerous in-house experiments. With re-
the material
gard has toagents,
to nucleating be cycleit stable, which
has been meansthat
observed thathomogeneous
there is no noteworthy
dispersionloss
of in
thephase
nu-
change enthalpy over a large number of cycles.
cleating agent is crucial for a reliable initiation of the crystallization. Local fixation of nu-
cleatingA programmable
agents, e.g., onphase
the PCM change material is wall,
encapsulation definedhadasnoa PCM that is modified
reproducible effect ontothere-
spond to a chosen external stimulus in the way that it releases the stored
crystallization. The actual switching mechanism, therefore, uses both nucleating agents phase change
enthalpy
and by exothermic
the crystalized crystallization
PCM itself. A nucleatingand agent
without an additional
is dispersed macroscopic
in a small portion switch-
of the
ing mechanism.
PCM As mentioned
(1). Within this small portionbefore, currentPCM,”
of “seeding programmable
the rangePCM systems consist
of supercooling of a
is elimi-
switchable PCM where a programmable triggering mechanism is incorporated.
nated or at least reduced to a minimum. To prevent the migration of nucleating agents The pro-
grammable trigger mechanism is the second main emphasis of research efforts. It consists
and resulting contamination of the whole PCM, this small portion is surrounded by an
of a physical trigger and a programmable switching mechanism. The programmable
immobilized PCM layer (2) and an encapsulation layer (3) with a single small opening (4).
switching mechanism might respond to various types of external stimuli as, e.g., mag-
This opening is sealed by the switching mechanism (5). To maintain the programmable
netic or electric fields, temperature, irradiation, pressure, or humidity. One functional
character of this switching mechanism, it can be realized of various responsive materials,
design is described in the following section, and Figure 3 shows an exemplary sketch of
as, e.g., shape memory polymer, which is also investigated by a section of the CPM project.
the programmable PCM–gel actuator.

Figure
Figure3.3.Exemplary
Exemplarysketch
sketchofofthe
theswitching
switchingmechanism
mechanismwithwithnucleating
nucleatingagent
agentdispersed
dispersedininaasmall
small
portion of the PCM (1), immobilized PCM layer (2), encapsulation layer (3) with a small opening
portion of the PCM (1), immobilized PCM layer (2), encapsulation layer (3) with a small opening (4),
(4), and sealing mechanism (5).
and sealing mechanism (5).

2.2. Application of Programmabletheory

Classical crystallization Phase indicates
Change Materials—Greenhouse Constructions
that a suitable crystallization surface might
be used
In agriculture, vegetable and ornamental plants are bred worldwide andofcultivated
as a physical trigger for activating the exothermic crystallization the PCM.
in greenhouses. Various statistical analyses in [11,12] show that the cultivation areas nu-
This surface might be exposed by a seed crystal of the PCM itself or by a suitable in
cleating agent.
greenhouses Both approaches
are increasing haveespecially
every year, been verified in numerous
in vegetable in-house
cultivation. Theexperiments.
two graphs
inWith regard
Figure to nucleating
4 show agents, itofhas
the development been observed
cultivated areas ofthat homogeneous
greenhouse crops dispersion
in Germany of
the the
and nucleating agent for
Netherlands is crucial
severalforyears.
a reliable
Bothinitiation
graphs showof thethat
crystallization. Local fixation
there is a continuous in-
of nucleating
crease. agents,and
In the flower e.g.,ornamental
on the PCM encapsulation
plant wall, had
cultivation sector, no 25%
about reproducible effect
of the area is
on the crystallization. The actual switching mechanism, therefore, uses both
cultivated under glass, which, according to [13], corresponds to an area of about 1629 hec- nucleating
agents and the crystalized PCM itself. A nucleating agent is dispersed in a small portion
tares.
of the PCM (1). Within this small portion of “seeding PCM,” the range of supercooling
is eliminated or at least reduced to a minimum. To prevent the migration of nucleating
agents and resulting contamination of the whole PCM, this small portion is surrounded by
an immobilized PCM layer (2) and an encapsulation layer (3) with a single small opening
(4). This opening is sealed by the switching mechanism (5). To maintain the programmable
character of this switching mechanism, it can be realized of various responsive materials,
as, e.g., shape memory polymer, which is also investigated by a section of the CPM project.

2.2. Application of Programmable Phase Change Materials—Greenhouse Constructions

In agriculture, vegetable and ornamental plants are bred worldwide and cultivated
in greenhouses. Various statistical analyses in [11,12] show that the cultivation areas in
greenhouses are increasing every year, especially in vegetable cultivation. The two graphs
in Figure 4 show the development of cultivated areas of greenhouse crops in Germany and
the Netherlands for several years. Both graphs show that there is a continuous increase.
In the flower and ornamental plant cultivation sector, about 25% of the area is cultivated
under glass, which, according to [13], corresponds to an area of about 1629 hectares.
Greenhouses are often single glazed and are, therefore, highly energy intensive to be
operated. However, they also offer optimum conditions, as they provide the highest light
transmission. Despite the possibility of saving energy, double or triple glazing is not yet
widely used in this area because of the associated costs and reduced light transmission,
Energies 2021, 14, 3440 5 of 13

which is crucial for plant growth. Yet, it is also possible that, especially at low outside
temperatures, the light transmission of thermal insulating glazing may be higher at times,
as there is no condensation on the inside. The development of low-energy greenhouses5has
Energies 2021, 14, x FOR PEER REVIEW of 13
already been investigated by [14]. In this context, different approaches to energy saving
were analyzed from both an energy and lighting point of view.

(a)

(b)
Figure4.4.Statistical
Figure Statisticalanalyses
analysesofofthe
thegreenhouse
greenhousecultivation
cultivationareas:
areas:(a)(a)development
developmentofof vegetable
vegetable cul-
culti-
tivation
vation under
under glass
glass in Germany
in Germany in years
in the the years 2016–2018
2016–2018 Reproduced
Reproduced fromPublisher:
from [11], [11], Publisher: Statis-
Statistisches
tisches Bundesamt; (b) development of vegetable cultivation under glass in the Netherlands in
Bundesamt; (b) development of vegetable cultivation under glass in the Netherlands in 2015–2016
2015–2016 Reproduced from [12], Publisher: Statista Research Department.
Reproduced from [12], Publisher: Statista Research Department.

Greenhouses
The are often
energy required single glazed
to operate and are,generally
greenhouses therefore, highly energy
depends intensive
on the plant to be
cultures
operated.
and However,
the outdoor theyconditions.
climate also offer optimum
The use of conditions, as they
greenhouses hasprovide the highest
the advantage that light
the
transmission. Despite the possibility of saving energy, double or triple
vegetation phase/development of the plants can be optimized on the one hand, and, glazing is not yet
widely used in this area because of the associated costs and reduced light
on the other hand, the period for the cultivation of the plants can be extended compared transmission,
which
to is crucial
open-field for plant According
cultivation. growth. Yet, to itthe
is type
also possible
of plant,that,
it is especially
important at tolow
haveoutside
very
temperatures, the light transmission of thermal insulating glazing may
uniform temperatures in greenhouses, as plants such as gerberas, for example, are be higher at times,
very
as there to
sensitive is no condensation
temperature on the inside.
fluctuations The development
and require of low-energy
a certain temperature withingreenhouses
a narrow
has already been investigated by [14]. In this context, different approaches to energy sav-
ing were analyzed from both an energy and lighting point of view.
The energy required to operate greenhouses generally depends on the plant cultures
and the outdoor climate conditions. The use of greenhouses has the advantage that the
Energies 2021, 14, 3440 6 of 13

range throughout the year [15]. Depending on the plant species, the greenhouse must be
heated at night even during the summer months to allow the plants to grow. It may also
be necessary to heat the greenhouse during the transitional periods of spring and fall to
prevent frost damage or a drop in temperatures to critical levels for the plants.
The use of phase change materials (PCMs) is intended to create a way of reducing
temperature fluctuations and avoiding the risk of frost damage to plants in the greenhouse.
By releasing the energy stored in the PCM, the required heating output could be reduced
during the transitional months, and the utilization phase of the greenhouses could be
extended. The application of a conventional PCM in greenhouses is summarized, e.g.,
in [7–9]. One of the advantages of programmable PCMs over a conventional PCM is that
the time of activation of the exothermic process can be explicitly controlled according to
the requirements. By using the solar energy entering the greenhouse through the glazing,
the PCM storages can be recharged naturally and without additional energy input after
activation to be ready for use again at the next critical temperature range.
Based on this knowledge, the use of commercially available and programmable PCMs
is further investigated by means of simulation calculations for a greenhouse. The temper-
ature range in which the PCM storage units are supposed to work strongly depends on
the use and requirements of the plant cultivations in the greenhouse. In the following,
a distinction is made between two applications: the first application is to prevent frost
damage caused by temperatures below freezing point, and the second application is to en-
sure that the temperature in the greenhouse does not drop below 12 ◦ C to protect sensitive
plant cultures.

2.3. Programmable Phase Change Materials for Greenhouse Applications

The usable heat of heat storage based on programmable PCMs depends on the selection
of the PCM, the amount of PCM, and the prevailing supercooling of the melt. These param-
eters also represent necessary input values for the hygrothermal building simulation.
At the moment, a suitable programmable PCM system is not available for greenhouse
application. A corresponding material might be synthesized as eutectic mixtures of calcium
chloride hexahydrate (CaCl2 -6H2 O) and other additives [16]. The suitability, e.g., the stable
supercooling range of such materials, is the subject of current in-house investigations.
For this reason, and as the goal of this simulation study is the determination of the
general potential of a programmable PCM in greenhouse applications, the simulation is
firstly carried out on the basis of the material data of calcium chloride hexahydrate. The re-
sults can then be evaluated as a qualitative assessment of the potential of implementing
programmable phase change materials in greenhouse operation.
As a raw material, CaCl2 -6H2 O is a very promising candidate for programmable PCM
systems, which binds 6 molecules of water per salt molecule in its crystal structure. At a
temperature of 29–30 ◦ C, the salt hydrate melts, and the salt dissolves in its crystal water.
The mass-related enthalpy of fusion is about 190 J/g [17] (confirmed by our measurements).
As a result of our measurements, the material reliably remains in a supercooled state
down to a temperature of 7 ◦ C without crystallizing. The stable supercooling interval thus
amounts to approximately 22 ◦ C.
The material data for the programmable PCM in the hygrothermal simulation are
summarized in Table 1.

2.4. Procedure of Hygrothermal Building Simulations

Based on the information specified above and the investigation report [18], a 3D
simulation model of a Venlo greenhouse is developed for the hygrothermal building simu-
lations. For the investigations, the hygrothermal building simulation tool WUFI® Plus is
used. Its capabilities and verifications are described in [19,20]. The simulations performed
are intended to show how the use of commercially available PCMs and optimized, pro-
grammable phase change materials can minimize the risk of frost in the transition period
 lation.

melting Temperature (range) 18 °C–20 °C

enthalpy of fusion 190 J g−1
Energies 2021, 14, 3440 minimum supercooling temperature 7 °C 7 of 13
effective crystallization temperature (set by trigger mechanism) 15 °C

2.4. Procedure of Hygrothermal Building Simulations

on the one hand, and, on the other, reduce the heating energy demand. The calculated
resultsBased on the
are then information
graphically specifiedand
evaluated above and the investigation report [18], a 3D sim-
assessed.
ulation model of a Venlo greenhouse is developed for the hygrothermal building simula-
tions.
Table 1.For the investigations,
Essential thematerial
input of estimated hygrothermal building simulation
data of programmable tool WUFIsimulation.
PCM for hygrothermal
® Plus is

used. Its capabilities and verifications are described in [19,20]. The simulations performed
melting
are Temperature
intended to show(range)
how the use of commercially available PCMs and 18 ◦ C–20 ◦C
optimized, pro-
enthalpy of fusion 190 J g −1
grammable phase change materials can minimize the risk of frost in the transition period
◦C
onminimum
the one supercooling
hand, and, temperature
on the other, reduce the heating energy demand.7 The calculated
effective crystallization temperature (set by trigger mechanism) 15 ◦ C
results are then graphically evaluated and assessed.
The calculations are carried out according to the flow chart shown in Figure 5. In
The to
addition calculations are carried
the materials used forout according
the individual to the flow chart
building shown inthe
components, Figure 5. In ad-
calculations
dition to the materials used for the individual building components, the
also consider boundary conditions such as air change, moisture production, the capacity calculations also
consider
of boundary
the heating conditions
system, such as air
and, if necessary, change,
other moisture
technical production,
equipment theaircapacity
for the of the
conditioning
heating
in system, and,
the examined room,if necessary, other
as well as the technical
quantity andequipment
switchingfor the of
point airthe
conditioning
PCM used.inThis the
examined room, as well as the quantity and switching point of the PCM
requires suitable hygrothermal material characteristics for the used building materials used. This requires
suitable
and hygrothermal
the applied material
phase change characteristics
material. for information
As a result, the used building materials
about the situation andat the
the
applied phase change material. As a result, information about the situation
enclosure surfaces, the indoor air, and the energy demand at real transient boundary con- at the enclosure
surfaces,
ditions the indoor air, and the energy demand at real transient boundary conditions
is obtained.
is obtained.

Figure
Figure 5.
5. Flowchart
Flowchart for
for carrying
carrying out
out aa hygrothermal
hygrothermal building simulation using PCMs.

As aabasis
As basisforforthe
thecalculations,
calculations, a three-aisled
a three-aisled glasshouse
glasshouse in Venlo
in Venlo construction
construction is
is im-
implemented 2
plemented (see(see Figure
Figure 6). 6).
TheThe greenhouse
greenhouse hashas a floor
a floor area
area of of
144144m2m andand a net
a net volume
volume of
of approximately 3 It is assumed that 80% of the area is equipped with planting
approximately 650650
m3. mIt is. assumed that 80% of the area is equipped with planting tables
tables
in in which
which the PCM the can
PCMbecan be integrated.
integrated. A sunAprotection
sun protection
system system
is notis considered
not considered in
in the
the simulations at this stage, but its implementation is planned for further
simulations at this stage, but its implementation is planned for further calculations. The calculations.
The Friedrichshafen
Friedrichshafen regionregion
is used is used
for theforoutdoor
the outdoor
climate,climate,
as theasregion
the region
around around Lake
Lake Con-
Constance
stance is of
is one one ofmain
the the main
fruitfruit
and and vegetable
vegetable growing
growing areasareas in Germany.
in Germany.
In addition to the scenarios with different PCMs, it is being investigated what advan-
tage can be expected of using thermal insulation glazing (WSG) (U-value = 1.1 W m−2 K−1 )
compared to single glazing (ESG) (U-value = 6 W m−2 K−1 ) in terms of minimum tem-
perature and hours with temperatures below the freezing point. A constant infiltration
of 0.15 h−1 is assumed for the ventilation of the greenhouse. The mechanical ventilation
is controlled in dependence on the temperature. At indoor air temperatures up to 34 ◦ C,
the air exchange rate is 0.8 h−1 and increases to 10 h−1 above 34 ◦ C in order to prevent
overheating in the greenhouse. Heating is not applied when comparing single-pane and
thermal insulation glazing. Based on these standard variants, the use of a newly developed,
programmable phase change material is further investigated with regard to the risk of
Energies 2021, 14, 3440 8 of 13

Energies 2021, 14, x FOR PEER REVIEW

frost in the greenhouse. For this purpose, a programmable PCM is implemented in8 the
of 13
◦
simulations, which is activated at an outdoor air temperature of 0 C.

Figure6.6.Venlo
Figure Venlogreenhouse
greenhousedesigned
designedwith
withthe
thesimulation
simulationsoftware.
software.

InInaaddition
further step, to the
thescenarios
effect of the with different
newly PCMs,programmable
developed, it is being investigated
latent heat what
material ad-
isvantage can befor
investigated expected
a variant ofwith
using thermal insulation
integrated heating and glazing
a minimum(WSG)temperature
(U-value = 1.1 W ◦m
of 12 C.−2
In −1 ) compared
K this variant, to thesingle
PCMglazing
switches (ESG) (U-valueto
in response = 6theW outdoor
m K ) in
−2 −1 airterms of minimum
temperature ◦
at 15tem- C
toperature
release and hours
energy. Thewith temperatures
material itself has below the freezing
a melting point. A 18
range between constant ◦ C and can
and 20infiltration of
be0.15 h−1 is at
melted assumed for the ventilation
these temperatures duringofwarmerthe greenhouse.
periods, e.g., The during
mechanical ventilation
the day. For theis
calculation
controlled in variant with a minimum
dependence indoor air At
on the temperature. temperature
indoor air of 12 ◦ C, a commercial
temperatures up to 34 °C,PCM the
with a melting/solidification range of 18 and ◦
19h C,aboverespectively,
air exchange rate is 0.8 h and−1 increases to 10 −1 34 °C inisorder used for comparison.
to prevent over-
The simulations
heating are evaluated
in the greenhouse. in terms
Heating is notof applied
the frequency with whichsingle-pane
when comparing the temperatureand ther-in
the
malgreenhouse
insulation falls
glazing.below the set
Based on lower temperature
these standard limit ofthe
variants, 0 ◦use
C, andof awith
newly regard to the
developed,
heating energy required to guarantee ◦ C. The results are
programmable phase change materiala is minimum temperaturewith
further investigated of 12regard to the risk of
shown in the following graphs and tables.
frost in the greenhouse. For this purpose, a programmable PCM is implemented in the
simulations, which is activated at an outdoor air temperature of 0 °C.
3. ResultsIn a further step, the effect of the newly developed, programmable latent heat mate-
The
rial is following evaluations
investigated for a variantregarding the effect
with integrated of theand
heating applied programmable
a minimum temperaturephaseof
change material are based on the temperature curves in a
12 °C. In this variant, the PCM switches in response to the outdoor air temperature at 15 greenhouse without heating.
Figure 7 shows
°C to release the two
energy. Thetemperature
material itself curves
has aover onerange
melting year for a greenhouse
between 18 and 20with single
°C and can
glazing (red line) compared to thermal insulation glazing (blue
be melted at these temperatures during warmer periods, e.g., during the day. For the cal- line). Due to the glazing
type,
culationthe greenhouse
variant withwith single glazing
a minimum indoor cools down considerably
air temperature of 12 °C, more at night. During
a commercial PCM withthe
day, thermal insulation glazing leads to higher temperatures
a melting/solidification range of 18 and 19 °C, respectively, is used for comparison. The and increased ventilation
requirements
simulations are compared
evaluated to single
in terms glazing.
of theTable 2 presents
frequency withthe minimum
which temperatures
the temperature of
in the
the outdoor air and the results of the different simulation
greenhouse falls below the set lower temperature limit of 0 °C, and with variants. The number of hours
regard to the
(based onenergy
one year) duringto which the interior temperature drops below ◦ C is summarized.
heating required guarantee a minimum temperature of 120 °C. The results are
For
shownthe two
in thevariants
following withgraphs
a programmable
and tables.PCM, the latent heat storage system is activated
in the simulation as soon as the outdoor air temperature falls below 0 ◦ C. The released heat
indicates
3. Results that the risk of frost in the greenhouse can be reduced by approximately 20% in
a construction with tempered glass. In a greenhouse equipped with thermal insulation
glazing, Thethis
following
can evenevaluations
be reducedregarding the effect85%
by approximately of the
to aapplied
few hours programmable
per year. phase
change material and
In vegetable are based on the temperature
plant cultivation, there arecurves in a greenhouse
many varieties that require without
higherheating.
min-
Figure 7 shows the two temperature curves over one
imum temperatures. The use of programmable PCMs for this purpose is being further year for a greenhouse with single
glazing (red in
investigated line) compared to
a greenhouse with thermal
heating insulation
and thermal glazing (blue line).
insulation Due For
glazing. to the
theglazing
simu-
type, the greenhouse with single glazing cools down
lation, a heating system with a 16 kW output is used, which is controlled such that considerably more at night. During
the
the day, thermal
temperature in theinsulation
greenhouse glazing
does leadsnot dropto higher
belowtemperatures
12 ◦ C, if possible. and increased
In the variantventilation
using
requirements
the newly developed compared PCM,to single glazing.
the control Table 2 presents
parameter is basedthe on minimum
the PCM being temperatures
activatedof
the outdoor air and the results of the◦ different simulation
at an outdoor air temperature of 15 C and recharged between 18 and 20 C. In contrast, variants. The number
◦ of hours
(based on one year) during which the interior temperature
the commercially available PCM has a melting and solidification temperature of 18/19 drops below 0 °C is summa- ◦ C.

Figure 8 shows an example of the time curve of indoor temperatures over a period ofis
rized. For the two variants with a programmable PCM, the latent heat storage system
14activated in the simulation
days in March. as soon as
Here, the different the outdoor
effects air temperature
of commercial and programmablefalls below 0 °C.heat
latent The
released heat indicates that the risk of frost in the greenhouse can be reduced by approx-
imately 20% in a construction with tempered glass. In a greenhouse equipped with ther-
mal insulation glazing, this can even be reduced by approximately 85% to a few hours per
year.
Energies 2021, 14, 3440 9 of 13

storages become apparent. In Figure 8, the blue line shows the temperature curve of the
indoor air temperature for the greenhouse variant with thermal insulation glazing and a
heating control for temperatures above 12 ◦ C and a higher air change rate of 10 h−1 over
34 ◦ C. Depending on the influence and operation of the heating system or rather high
Energies 2021, 14, x FOR PEER REVIEW 9 ofair
13
change rate the minimal and maximal temperature range in the greenhouse can be adhered
to without PCM.

Figure 7.
Figure 7. Comparison
Comparison of
ofthe
thetime
timedependence
dependenceofofindoor
indoorairair temperatures
temperatures forfor single
single (red)
(red) andand ther-
thermal
mal insulation glazing (blue).
insulation glazing (blue).

Table 2. Table 2. Minimum

Minimum temperatures
temperatures and of
and number number
hours of
below 0 ◦below
hours 0 °Cthe
C during during
year. the year.

Variants Minimum Temperature (◦ C) Minimum

Number of HoursNumber
< 0 ◦ C (haof −1 )
Variants Temperature Hours <0 °C
outdoor air −11.8 1082
tempered glass without PCM −9.1 (°C) 599 (ha−1)
tempered glass with programmableoutdoor
PCMair −8.9 −11.8 482 1082
thermal insulation glazing without PCM glass without PCM
tempered −4.2 −9.1 165 599
thermal insulation glazing with programmable PCM −1.8 25
tempered glass with programmable PCM −8.9 482
thermal insulation glazing without PCM −4.2 165
When using commercially available PCMs, the stored energy is released as soon as the
thermal insulation glazing with programmable PCM −1.8 25
temperature in the latent heat storage reaches the melting point of 18 ◦ C. The introduced
latent heat is reflected in the temperature curve by a brief slowing down of the cooling in
In vegetable and plant cultivation, there are many varieties that require higher min-
the room. Nevertheless, an additional heating system is still required in the period shown
imum temperatures. The use of programmable PCMs for this purpose is being further
to maintain the minimum temperature of 12 ◦ C, as some of the heat is released too early,
investigated in a greenhouse with heating and thermal insulation glazing. For the simu-
and, thus, the temperature in the greenhouse is kept at a higher level than necessary. Due to
lation, a heating system with a 16 kW output is used, which is controlled such that the
the larger temperature difference to the ambient air, larger heat losses occur, and the stored
temperature in the greenhouse does not drop below 12 °C, if possible. In the variant using
heat is not sufficient to maintain the temperature in the greenhouse above 12 ◦ C. The green
the newly developed PCM, the control parameter is based on the PCM being activated at
line shows the effect of a programmable PCM on the curve of the interior temperature in the
an outdoor air temperature of 15 °C and recharged between 18 and 20 °C. In contrast, the
greenhouse. Being able to define the switching parameter for the release of the latent heat
commercially
allows available
for a more PCM
targeted has
heat a melting
release. andapplication,
In this solidification
thetemperature
switching pointof 18/19
of the°C.PCM
Fig-
ure
is set8 to
shows an example
an outside of the time
temperature of 15curve of effect
◦ C. The indooroftemperatures over a is
the released energy period
shown ofwith
14 days
the
in March. Here, the different effects of commercial and programmable latent
curve of the indoor air temperature (green line). It becomes evident that in the represented heat storages
become
time apparent.
period, In Figure
the indoor 8, the blue line
air temperature shows above
is always the temperature
12 ◦ C due curve
to the of the indoor
release of latentair
temperature for the greenhouse variant with thermal insulation glazing
heat, and, therefore, no additional heating energy needs to be introduced. Furthermore, and a heating
control
the for temperatures
temperature above 12
curve in Figure °C and
8 shows a higher
that the roomair temperatures
change rate of of10
thehvariants
−1 over 34 °C.
with
Depending
PCM on the
rise with influence
a slight and operation
time delay, as the PCM of the heating
storage hassystem orthermal
to store rather high
energy air change
for the
rate the
next cycleminimal andactivated
after being maximalattemperature
night. The dailyrange in the greenhouse
maximum temperatures canarebethus
adhered
reached to
without PCM.
less frequently compared to the standard design, implying that the increased air exchange
When 34
rate above using commercially
◦ C needs available
to be ensured lessPCMs, the stored
frequently energy isThe
by ventilation. released
extentastosoonwhich as
the temperature in the latent heat storage reaches the melting point of 18 °C. The intro-
duced latent heat is reflected in the temperature curve by a brief slowing down of the
cooling in the room. Nevertheless, an additional heating system is still required in the
period shown to maintain the minimum temperature of 12 °C, as some of the heat is re-
 released energy is shown with the curve of the indoor air temperature (green line). It be-
comes evident that in the represented time period, the indoor air temperature is always
above 12 °C due to the release of latent heat, and, therefore, no additional heating energy
needs to be introduced. Furthermore, the temperature curve in Figure 8 shows that the
Energies 2021, 14, 3440 room temperatures of the variants with PCM rise with a slight time delay, as the 10 PCM
of 13
storage has to store thermal energy for the next cycle after being activated at night. The
daily maximum temperatures are thus reached less frequently compared to the standard
design, implying that the increased air exchange rate above 34 °C needs to be ensured less
the heatingbyenergy
frequently requirement
ventilation. is influenced
The extent to which by thethe use ofenergy
heating commercially available
requirement and
is influ-
programmable PCM can be seen in the comparison of the calculated
enced by the use of commercially available and programmable PCM can be seen in the consumption values in
Table 3. Related to a whole year, the heating requirement can be reduced
comparison of the calculated consumption values in Table 3. Related to a whole year, the by approximately
20% when
heating using a programmable
requirement can be reducedPCM. The largest positive
by approximately 20% when effect
using onathe reduction of
programmable
PCM. The largest positive effect on the reduction of the heating requirement storage
the heating requirement due to the additional heat energy of the latent heat can
due to the
be identified
additional heatinenergy
spring of
and theautumn. Thisstorage
latent heat can becanseenbeinidentified
the comparison
in spring of and
the curves
autumn. of
the calculated thermal energy demand values in Figure 9 for the whole
This can be seen in the comparison of the curves of the calculated thermal energy demand year and even
more detailed
values in Figurein9Figure
for the10 for spring.
whole Figure
year and even10 shows
more that, starting
detailed in Figure from approximately
10 for spring. Fig-
mid-February, the use of the programmable latent heat storage leads
ure 10 shows that, starting from approximately mid-February, the use of the programma- considerably to a
reduction of the required heating energy.
ble latent heat storage leads considerably to a reduction of the required heating energy.

Comparisonof
Figure8.8.Comparison
Figure ofthe
thetime
timedependence
dependenceof ofthe
theindoor
indoorair air temperatures
temperatureswhen
when using
using thermal
thermal
insulationglazing
insulation glazingwithout
withoutaaPCMPCM(blue),
(blue),with
withaa commercially
commerciallyavailable
availablePCM
PCM (gray),
(gray), and
and with
with aa
Energies 2021, 14, x FOR PEER REVIEW 11 of 13
newlydeveloped,
newly developed,programmable
programmablePCM PCM(green),
(green), which
which is is activated
activated at at
anan outdoor
outdoor air air temperature
temperature of
15 15 ◦ C.
of°C.

Table 3. Required heating energy to achieve a minimum temperature of 12 °C in the greenhouse.

Annual Heating Energy Heating Energy in the Period 15.02–01.11.

Variants
(kWh m−2 a−1) (kWh m−2)
without PCM 86 13
commercially available PCM 77 9
programmable PCM 70 4

Figure 9. Comparison of the required heating energy during a year when using thermal insula-
Figure 9. Comparison of the required heating energy during a year when using thermal insulation
tion glazing
glazing without
without a PCMa PCM
(blue),(blue),
with awith a commercially
commercially available
available PCM (gray),
PCM (gray), and
and with with a devel-
a newly newly
developed,
oped, programmable
programmable PCM (green).
PCM (green).
Energies 2021, 14, 3440 11 of 13

Table 3. Required heating energy to achieve a minimum temperature of 12 ◦ C in the greenhouse.

Annual Heating Energy Heating Energy in the Period

Variants
(kWh m−2 a−1 ) 15.02–01.11. (kWh m−2 )
without PCM 86 13
Figure 9. Comparison of the required heating energy during a year when using thermal insulation
commercially available PCM 77 9
programmable PCM glazing without a PCM (blue), with
70 a commercially available PCM (gray), and
4 with a newly devel-
oped, programmable PCM (green).

Figure 10. Comparison

Figure Comparison ofofthe
therequired
requiredheating energy
heating forfor
energy the the
period fromfrom
period 1 January to 21 to
1 January April
21 when
April
when
using using thermal
thermal insulation
insulation glazingglazing without
without a PCMa(blue),
PCM (blue),
with a with a commercially
commercially available
available PCM
PCM (gray),
(gray),
and withand with a developed,
a newly newly developed, programmable
programmable PCM (green).
PCM (green).

4.
4. Summary
Summary
Within
Within the framework
framework of of the
the research
research project
project Fraunhofer
Fraunhofer Cluster
Cluster ofof Excellence
Excellence “Pro-
“Pro-
grammable Materials,”programmable
grammable Materials,” programmable phasephase
changechange materials
materials aredeveloped,
are being being developed,
which of-
which
fer newoffer new possibilities
possibilities for energyforsaving
energyand saving and temperature
temperature control
control due due to
to their their com-
composition
and, in particular,
position the possibility
and, in particular, of externalof(largely
the possibility externaltemperature-independent)
(largely temperature-independent)activation
of the phase
activation of change
the phaseandchange
the associated
and theenergy release.
associated A possible
energy release.application
A possiblescenario was
application
developed and presentedand by means of hygrothermal ® Plus),
scenario was developed presented by means of building simulations
hygrothermal building (WUFI
simulations
based ®onPlus),
(WUFI the example
based on of the
greenhouses.
example ofBy integrating aByprogrammable
greenhouses. integrating a PCM, which is
programmable
adapted
PCM, to the
which application
is adapted scenario,
to the application on the one hand,
scenario, theone
on the riskhand,
of frost
thein theofgreenhouse
risk frost in the
can be reduced
greenhouse can bybe activating
reduced by the heat output,
activating and, output,
the heat on the other
and, hand,
on theaother
significant
hand, reduc-
a sig-
tion of the heating energy required to maintain a minimum temperature
nificant reduction of the heating energy required to maintain a minimum temperature can be achieved.
can
Theachieved.
be main advantage
The main ofadvantage
these heat of storage
these systems in thesystems
heat storage considered application
in the consideredisapplica-
that the
storage
tion tanks
is that the are recharged
storage naturally
tanks are recharged by solar energy.
naturally Thus,energy.
by solar the utilization
Thus, theand vegeta-
utilization
tion vegetation
and phase can be effectively
phase can be optimized
effectivelyand extended
optimized without
and extendedanywithout
additionalanyheat source.
additional
In comparison to greenhouses with single glazing and thermal insulation
heat source. In comparison to greenhouses with single glazing and thermal insulation glazing without
heat storage,
glazing withoutthe calculation
heat storage, results show that the
the calculation use ofshow
results phase change
that materials
the use canchange
of phase reduce
the number of hours in which frost can occur in the greenhouse by up
materials can reduce the number of hours in which frost can occur in the greenhouse by to 85%. Furthermore,
theto
up use of an
85%. optimized and
Furthermore, theprogrammable
use of an optimized PCM can andreduce the heating
programmable requirement
PCM can reduce by the
ap-
proximately
heating 20% if theby
requirement minimum temperature
approximately 20% in the greenhouse
if the does not dropinbelow
minimum temperature 12 ◦ C.
the green-
Due todoes
house the variety
not drop of below
material12 design
°C. Due options, further of
to the variety savings potential
material designcan be tapped
options, furtherin
the future. One of the next steps is to implement the newly developed
savings potential can be tapped in the future. One of the next steps is to implement the programmable PCM
in a free-field test setting to investigate and monitor their behavior under real conditions.
In this article, the potential of programmable phase change materials is demonstrated
by the example of vegetable and ornamental plant cultivation in greenhouses. However, the
development of programmable materials still contains a wide range of new and completely
different applications and uses, not only for agriculture, e.g., for air-conditioning systems.
In particular, there is the possibility to integrate the switching criteria and hence the
control technology of the system directly into the material by means of suitable actuation
Energies 2021, 14, 3440 12 of 13

mechanisms. Thus, a material-inherent system for temperature control can be created,

which, ideally, requires no further electronic control technology.

Author Contributions: Conceptualization, K.L. and M.W.; methodology, K.L., M.K., M.W., S.P. and
C.T.; software, K.L. and M.K.; investigation, K.L. and M.W.; writing—original draft preparation, K.L.
and M.W.; writing—review and editing, K.L., M.K., M.W., S.P. and C.T.; visualization, K.L. and M.W.;
supervision, M.K. and C.T.; project administration, M.K. and C.T. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by Fraunhofer Cluster of Excellence “Programmable Materials”.
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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