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Solar Energy 94 (2013) 344–351

www.elsevier.com/locate/solener

Effect of D-mannitol polymorphism in its thermal energy

storage capacity when it is used as PCM
Camila Barreneche a,b,1, Antoni Gil a, Falguni Sheth a, A. Inés Fernández b,1,
Luisa F. Cabeza a,⇑
a
GREA Innovació Concurrent, Universitat de Lleida, Edifici CREA, Pere de Cabrera s/n, 25001 Lleida, Spain
b
Department of Materials Science & Metallurgical Engineering, Universitat de Barcelona, Martı́ i Franqués 1-11, 08028 Barcelona, Spain

Received 11 February 2013; received in revised form 3 May 2013; accepted 26 May 2013
Available online 19 June 2013

Communicated by: Associate Editor Halime Paksoy

Abstract

The main objective of this paper is to study the possible use of D-mannitol as phase change material (PCM) for thermal energy stor-
age. PCM are materials that have high phase change enthalpy and this thermophysical property gives them the ability to store energy as
latent heat. D-mannitol is a material which has different morphological phases (polymorphism); here were studied b-form and d-form.
Different polymorphic forms produce changes on melting point of D-mannitol. For this reason it is necessary to establish a suitable work-
ing temperature range for the use of D-mannitol as phase change material. The thermal characterization was performed with DSC anal-
ysis using 0.5 K min1 slow-dynamic method. Polymorphism analysis of D-mannitol was analyzed to associate the thermal behavior
obtained by DSC with a specific polymorphic phase. D-mannitol presented three different thermal behaviors: the first one had a melting
peak at 167 °C, the second was a double melting peak at 155 °C and 166 °C, and the third a single peak at 155 °C. Due to irregular
results, two working range were studied and through the thermal characterization, it was possible to define a working range where D-
mannitol could be used as PCM for energy storage: this range is between 135 and 175 °C. Furthermore, it was possible to differentiate
two crystalline phases of D-mannitol applying FT-IR analysis and to link them with thermal behavior observed in DSC. The percentage
of times each thermal behavior is observed in DSC analysis was calculated. d-form is obtained 15.8% of analyzed cycles, the b-form
appears 44.7% of times, and an intermediate transition between the two phases is found 39.5% of cycles.
Ó 2013 Elsevier Ltd. All rights reserved.

Keywords: Phase change materials; Thermal energy storage; D-Mannitol; Polymorphism; Thermophysical characterization; Differential scanning
calorimetry

1. Introduction tial scanning calorimetry (DSC) Günther et al., 2006;

Thermal analysis of materials used for energy storage is
a prerequisite of its application. One of the most widely
used equipment for thermophysical analysis at is differen-
⇑ Corresponding author. Tel.: +34 973 00 35 77.
E-mail address: lcabeza@diei.udl.cat (L.F. Cabeza).
1
Tel.: +34 93 402 12 98.
Mehling and Cabeza, 2008.
Thermal energy storage (TES) propose phase change
material (PCM) as materials which are able to store high
amount of energy as latent heat during the phase change
(Farid et al., 2004; Zalba et al., 2003). Furthermore, melt-
ing point of PCM must be closed to selected work temper-
ature range and it must own high specific heat in order to
provide sensible heat to the system, and high thermal con-
ductivity (solid and liquid state) to support charging and

0038-092X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2013.05.023
 C. Barreneche et al. / Solar Energy 94 (2013) 344–351
discharging processes in storage system used (Tyagi and
Buddhi, 2007; Sharma et al., 2009). Additionally, PCM
must not change volume during phase change transforma-
tion and it must not emit vapors allowing conventional
containers (Sharma and Sagara, 2005; Khudhair and
Farid, 2004). Thermophysical properties of D-mannitol
found in the literature are: melting point (Tm) is 166–
167 °C, and melting enthalpy (Hm) is 316 kJ kg1 Zalba
et al., 2003; Sharma and Sagara, 2005. These noble thermal
properties allow D-mannitol to be used as phase change
material (PCM). Materials with similar thermophysical
properties (heat storage capacity, melting point, thermal
conductivity, etc.) have been widely studied to apply them
as PCM (Günther et al., 2006).
D-mannitol is a natural carbohydrate and this com-
pound has functional groups which define it as a polyol.
The chemical structure of this substance can be seen in
Fig. 1 (de Oliveira Pedro et al., 2009). This carbohydrate
is used in different fields of science: due to its sweet flavor,
D-mannitol is used as a food additive; as a medicine addi-
tive (Martı́nez et al., 2004), in organic synthesis (de Oliveira
Pedro et al., 2009); in medicine, etc.
This substance presents different polymorphic phases.
Several compounds crystallize in different crystalline forms
while retaining the same chemical composition producing
changes in the melting point of D-mannitol (Mullin, 2001).
Polymorphism of D-mannitol has been widely studied
previously. Pitkanen et al. (1993) studied several polymor-
phic phases of D-mannitol obtaining seven forms: a, b, c, d,
j and j0 . These D-mannitol phases were characterized ther-
mally and its polymorphic phases were characterized with
X-ray diffraction analysis and crystal data of polymorphic
behavior was listed. Furthermore, Burger et al. (2000)
obtained three different phases of D-mannitol and they were
characterized with DSC, FTIR, FT-Raman, and produced
an energy-temperature diagram of the different phases
studied; Cornel et al. (2010) studied the kinetics and ther-
modynamics of these phase changes of the D-mannitol;
and finally Barone et al. (1990) studied enthalpies and
entropies of three physical transformation process of D-
mannitol: vaporization, sublimation, and fusion.
The most stable phase of D-mannitol is the b-form at
ambient temperature (Pitkanen et al., 1993). The metasta-
ble phase (d) is achieved when this material is heated up
and it is cooled with fast cooling. The melting temperature
of both structures, Tm, is 167 °C and 155 °C, respectively,
and their enthalpies of fusion, Hm, are 287 kJ kg1 and
288 kJ kg1, respectively (Burger et al., 2000; O’Sullivan
et al., 2003).
Fig. 1. D-mannitol chemical structure (E., 2006).
345
The main objective of this paper is to study the possible
use of D-mannitol as phase change material (PCM) for
thermal energy storage. The thermal properties of this sub-
stance promote its application, for example, in solar cool-
ing where heat from the sun can be stored at around
160–180 °C to improve the performance of the absorption
chiller (Chidambarama et al., 2011). Therefore, D-mannitol
is characterized thermally by DSC and the results are cor-
related with its polymorphic phases by FTIR spectroscopy.
2. Materials and methodology
2.1. Materials
D-mannitol characterized in this paper is commercialized
by QUIMIVITA. The pure D-mannitol has the stable phase
of its phases: b-form.
During the thermal characterization, each sample ana-
lyzed is a pure new sample of D-mannitol. Furthermore,
a new sample is used to the polymorphic characterization
(b-form), and the obtained results are compared with a
sample cycled 5 times by DSC which melting temperature
is 155 °C (d-form).
2.2. Thermal characterization
Thermophysical characterization was performed with
DSC analysis. This is a powerful technique where the sam-
ple and one reference (sapphire) are subjected to a certain
heating rate between one established temperature range.
Sapphire is a material completely inert within huge temper-
ature range. The heat difference between both signals (sam-
ple and reference), is due to the enthalpy absorbed by the
sample (Hhne et al., 2003). The equipment used to per-
formed thermophysical characterization was a DSC-822e
commercialized by Mettler Toledo, and 15 mg samples
were analyzed in an aluminum crucible of 40 ll under a
N2 flow of 80 mlmin1.
The analysis method used for D-mannitol thermal char-
acterization was slow-dynamic method applying 0.5 Kmin
1
heating rate between 25 °C up to 200 °C (Mehling and
Cabeza, 2008). Slow heating rate (0.5 K min1) is the most
common operating mode used when analyzing PCM with
DSC and it was wholly described previously (Günther
et al., 2009; Barreneche et al., 2013).
A total of 14 samples were analyzed, three were cycled
once, three were cycled twice, five were cycled three times,
and three samples were cycled five times applying DSC
analysis.
2.3. Polymorphic characterization
Polymorphism analysis of D-mannitol was performed in
order to associate the thermal behavior obtained by DSC
analysis with a specific crystalline phase.
The analysis was performed by FT-IR. The equipment
used is a Thermo IZ10 and it was used coupled to an
346 C. Barreneche et al. / Solar Energy 94 (2013) 344–351

(a) Sample1 β phase: 246 J·g-1 (167 ºC)

(b) Sample2 transition δ and β phases:

238 J·g-1 (157 ºCand 167 ºC)

(c) Sample3 δ phase: 243 J·g -1 (157 ºC)

Fig. 2. Three different thermal behaviors obtained with DSC analysis of D-mannitol during melting process.
 C. Barreneche et al. / Solar Energy 94 (2013) 344–351
attenuated total reflection accessory (ATR) of diamond.
The equipment has available DTGS detectors, KBr beam
splitter and source Glowbar. The spectral range measured
was between 4000 and 500 cm1 and the resolution used
was 4 cm1.
To discern between the two possible D-mannitol crystal-
line phases, the bands obtained were compared between
2000 and 500 cm1 with those obtained by Burger et al.
(2000), to be able to characterize any possible polymorphic
transformation.
3. Results and discussion
3.1. Results of thermal characterization
The results obtained by DSC have three different ther-
mal behaviors, as shown in Fig. 2.
The first sample (sample 1) shows a single peak at
167 °C corresponding to 247 kJkg1 (Fig. 2a), the second
thermal behavior (Fig. 2b) has double peak at 156 °C
and 167 °C related with 238 kJ kg1 (see Fig. 3), respec-
tively (sample 2), and the third thermal behavior (Fig. 2c)
is a single peak at 157 °C linked with 234 kJ kg1 (sample
3). All curves represented in Fig. 2 were the result of the
third thermal cycle on DSC experimentation. DSC 822e
from Mettler Toledo has ±0.1 °C and ±3 kJ kg1 of
inaccuracy.
On the other side, sample 2 shows a double peak. The
global heat of fusion is 238 J g1 as Fig. 3 shows, then, this
exothermic peak will not affect neither contribute in total
heat accumulated by this material when it is used as
PCM. Furthermore, another key point is that total heat
of fusion of mixtures is slightly smaller than those of pure
phases (Pitkanen et al., 1993) and this fact justify the smal-
ler melting enthalpy found for sample 2.
Polymorphic transformations presented by D-mannitol
change the melting point of the substance while enthalpy
is almost constant after 5 cycles. In most of the cases,
PCM application depends on phase change temperature
and it is a parameter to take into account during the mate-
rial selection step.
Furthermore, the thermal behavior of D-mannitol dur-
ing the cooling process was also studied and it is regular
(Fig. 4). However, during the solidification process there
is subcooling/supercooling behavior because the phase
change temperature for all three samples representing each
thermal behavior is 119 ± 1 °C. This subcooling/supercool-
ing effect is also observed by Pitkanen et al. (1993). The
DSC curves of the third cycle from these three samples
are represented in Fig. 3.
To perform these DSC analyses of D-mannitol, the same
heating rate and the same amount of sample were used.
However, d-phase or b-phase formation it is not completely
controlled within the studied conditions. The polymorphic
phase formation depends on cooling conditions but not
only on the temperature range used to analyze the sample
and heating rate applied during the experiments.
347
3.2. Results of morphological characterization
First of all, it was observed that D-mannitol is a com-
pound with a thermal behavior difficult to predict due to
polymorphism.
Results of the morphological characterization of D-man-
nitol are shown in Fig. 5, representing the characterization
through FTIR of the two samples analyzed (pure D-manni-
tol without DSC cycling and D-mannitol cycled five times
by DSC). b and d phases vibrate in the infrared at different
wave numbers (cm1), therefore they can be distinguished
easily. FTIR bands obtained in the interval between 2000
and 500 cm1 are the bands that distinguish morphological
phases that may have D-mannitol (Burger et al., 2000).
The bands selected by Burger et al. (2000) to character-
ize each crystalline phases are listed in Table 1. These
phases are compared with results obtained by infrared
spectroscopy (Table 1). The results obtained in the infrared
spectroscopy analysis agree perfectly with results obtained
by Burger et al.
The three different thermal behavior obtained by DSC
(Fig. 2) can be correlated with the bands and phases char-
acterized by infrared spectroscopy. The first thermal
behavior (Fig. 2a) corresponds to b-form and has the melt-
ing temperature at 167 °C. The second one is the transition
between d and b-forms (Fig. 2b). For this reason, there is a
double peak at 156 °C and 167 °C The third thermal behav-
ior corresponds to the d-form and the phase change occurs
at 157 °C (Fig. 2c). Nevertheless, values of the enthalpy of
fusion of the three different behaviors are very similar,
being melting enthalpy of b and d transition mixture smal-
ler than pure phases analyzed.
3.3. Analysis of occurrences
Based on DSC analysis, the percentage of occurrences of
each thermal behavior obtained depending on how many
times the sample has been cycled were calculated following
Eq. (1) where ni is number of DSC experiments obtained
with each thermal behavior, N is total number of DSC
experiments and % is the percentage of occurrences. Fur-
thermore, results are shown in Table 2.
ni
% ¼  100 ð1Þ
N
The average values of melting temperature in the cases
with a single peak (Tm, d and Tm, b) and in the cases with
two peaks are also included in Table 2. In this last case, the
value of melting temperature of each peak found is
distinguished.
When the sample was analyzed once, all the samples
solidified as b-phase. After the second cycle, the metastable
d-phase formation started. When the samples were cycled
three times, 50% presented a double peak (transition
between phases) and 50% solidified as d-phase. Then, all
samples showed a double peak during the fourth cycle.
Finally, the b-phase is formed again 33.3% of the time
348 C. Barreneche et al. / Solar Energy 94 (2013) 344–351

δ phase: Hm=-109.17 J·g-1

β and δ phases transition: Hm=70.03 J·g-1

β phase: Hm= -197.29 J·g-1

Fig. 3. DSC curve integration of b and d phases mixture observed in sample 2.

 C. Barreneche et al. / Solar Energy 94 (2013) 344–351 349

Sample 1: 215 J·g-1 (119 ºC)

Sample 2: 210 J·g-1 (118 ºC)
Sample 3: 215 J·g-1 (118 ºC)

Fig. 4. Three different thermal behaviors obtained through DSC analysis of D-mannitol during solidification process.

Fig. 5. On the left FTIR bands of D-mannitol with no cycles of DSC; on the right FTIR bands of D-mannitol cycled 5 times by DSC.

because this phase is more stable than the other one and its
formation is favored.
Due to these irregular results, two working ranges were
analyzed. The first working range studied was between 135
and 200 °C being the average value of melting enthalpy
338 ± 21 kJ kg1. This value is close to the reported value
(Zalba et al., 2003), being this the reason why this working
range was studied. This temperature range includes the
heat stored as latent heat as well as the sensible stored.
Nevertheless, the temperature gradient was large (65 °C)
and depending on the application this could be a problem.
The second working range analyzed was shorter:
between 135 and 175 °C, with 233 ± 15 kJ kg1 as melting
enthalpy average. This working range includes the phase
change transformation of the two morphological phases
under analysis (d and b), it is shorter than the first one,
and it is within the temperature range of solar cooling
applications (Chidambarama et al., 2011). These are the
350 C. Barreneche et al. / Solar Energy 94 (2013) 344–351

Table 1
Comparison of FTIR characteristic bands of D-mannitol with the selected bands obtained.
b-phase Characteristic bands (cm1) 1210 1081 1019 959 930
Burger et al., 2000
Selected bands (cm1) 1209 1081 1018 959 929
1
d-phase Characteristic bands (cm ) 1193 1088 1025 968 932
Burger et al., 2000
Selected bands (cm1) 1193 1088 1020 967 930

Table 2
Percentage of cases where the D-mannitol has a single peak or double peak performance.
1 Peak 2 Peaks
Tm, d (°C) Tm, b (°C) Tm, d (°C) Tm, b (°C)
1st Cycle 0% 100% 0%
– 168.5 ± 1 – –
2nd Cycle 18% 18% 64%
157 ± 0 166 ± 0 152 ± 3 167 ± 2
3rd Cycle 50% 0% 50%
156 ± 0.0 – 153 ± 2 167 ± 1
4th Cycle 0% 0% 100%
– – 152 ± 2 164 ± 0
5th Cycle 0% 33,33% 66,66%
– 164 ± 0 149 ± 1 164 ± 0

reasons which were taken under consideration to select this
temperature working range to be studied. Subsequently,
this interval is more appropriate to be considered as a real
working range (Pitkanen et al., 1993). Within this working
range (135–175 °C), the D-mannitol could be used as PCM.
It includes the different thermal behaviors observed by
DSC due to the transition of crystalline phases (b and d).
Thermal properties during this working range are appro-
priated and regular. Furthermore, these do not depend
on the thermal performance or the morphological changes.
4. Conclusions
Three different thermal behaviors were observed by
DSC analysis: the first one corresponded to b-form and
had the melting temperature at 167 °C. The second one is
the transition between d and b-forms, presenting a double
peak at 156 °C and at 167 °C. The third thermal behavior
corresponded to the d-form and the phase change occurred
at 157 °C.
It was possible to identify and characterize the morpho-
logical phases of the D-mannitol (b and d) through FTIR
spectroscopy analysis and to correlate them with their ther-
mal behavior. Values obtained from the melting tempera-
ture, Tm, of the stable phase b and d metastable phase
are 157 °C and 167 °C, respectively.
There is an occurrence trend of the D-mannitol different
phase formation. Initially, all samples presented one single
peak corresponding to b-phase. After the second cycle, the
metastable d-phase formation started. When the samples
were cycled three times, 50% presented a double peak
(transition between phases) and 50% solidified as d-phase.
Then, all samples showed a double peak during the fourth
cycle. Finally, the b-phase is formed again by 33.3% of the
time.
Furthermore, by the thermal characterization, it was
possible define a working range where D-mannitol could
be used as PCM for energy storage, for example, in solar
cooling applications. This range is between 135 °C and
175 °C. The melting temperatures of the two phases are
included in this working range and the melting enthalpy
is 233 ± 15 kJ kg1. The cooling process conditions are
constant but DSC results demonstrate that this material
presents subcooling behavior. The solidification tempera-
ture is found at 118 °C ± 1 °C.
To summarize, D-mannitol can be used as PCM because
has good thermophysical properties for energy storage, but
the polymorphism has to be taken into account. The poly-
morphism does not affect the thermal behavior under the
working temperature range defined in this paper (135 and
175 °C).
Acknowledgements
The work is partially funded by the Spanish government
(ENE2011-22722) and the European Union (COST Action
TU0802). The authors would like to thank the Catalan
Government for the quality accreditation given to their re-
search group GREA (2009 SGR 534) and research group
DIOPMA (2009 SGR 645). A. Gil would like to thank
 C. Barreneche et al. / Solar Energy 94 (2013) 344–351
the Collegi d’Enginyers Industrials de Catalunya for his
research appointment.
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