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ELSEVIER Solar Energy Materials and Solar Cells 36 (1995) 311-322

Low chain esters of stearic acid as phase change materials

for thermal energy storage in buildings
D. F e l d m a n *, D. B a n u , D. H a w e s
Centre for Building Studies, Concordia University, Montreal, Qui., Canada H3G 1M8
Received 20 December 1993

Abstract

Esterification of different commercial mixtures of stearic and palmitic acid with methyl,
butyl and propyl alcohols was undertaken at the laboratory scale and the thermal properties
of the esters were determined by Differential Scanning Calorimetry (DSC).
Twelve products were obtained with melting points in the interval of 17-34°C and
freezing points in the range of 20-32°C. About half of them are characterized by a latent
heat of transition of 140-150 J / g and the other half by a latent heat of transition of
180-190 J/g.
Even at the incipient phase, research concerning the esterification of different commer-
cial grades of stearic acid has demonstrated the ability to tailor PCM's with specific
transition temperature.

1. I n t r o d u c t i o n

One of the most important aspects of energy conservation is that of thermal

storage. In addition to the traditional use of stored heat for space heating there
are a number of other applications which are gaining in importance. These
include;
- - time shifting of maximum demand in energy supply systems which renders
feasible the use of low-cost, off-peak electrical powers, gas, steam, etc.;
- - use of internal heat gains which would otherwise be wasted such as that
derived from solar radiation, lights a n d appliances, as well as periodic building
load surges such as the heat generated for relatively short periods of time in
auditoria and public buildings;

* Corresponding author.

0927-0248/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0927-0248(94)00186-3
312 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322

- -improving the efficiencies of burners, chillers and heat pumps by the reduction
of short cycle operation.
It will also be noted that the thermal storage function of building materials can
apply to a wide temperature range, depending upon the heat source and mode of
application. In the last forty years, a considerable amount of work has been
accomplished in respect to the use of PCM's for energy conservation in buildings.
PCM's are materials which absorb heat while melting and release it when freezing.
Those selected for thermal storage applications normally perform these functions
within a few degrees and at an appropriate range in the temperature scale.
The esters of long chain carboxylic acids, or fatty acids, are considered promis-
ing PCM's candidates in building applications, since they can be impregnated, or
directly incorporated into conventional building products at some stage of their
manufacture [1-4].
These materials, in their liquid phase, have a surface tension in the order of
20-30 dyne/cm [5,6] and this is high enough so that they are retained in the
structure of the host material. They possess an elevated latent heat of transition
and high specific heat (mostly in the range 1.9-2.1 J/g°C) [7] for absorbing
sensible heat. They also exhibit small volume changes during melting or freezing
(ex: melting dilatation is around 0.1-0.2 ml/g). In addition, little or no supercool-
ing occurs during the phase transition with these materials which give them an
important advantage over many other PCM's.
Because of the protected carboxyl group, they are chemically, heat and color
stable and have low corrosion activity. In addition, they are non-toxic. As in the
case of other combustible building materials, due care must be exercised in their
formulation and application. A fire rating will be obtained in the near future.
Some PCM's have an odour in their raw state. Fortunately, this can be
neutralized by the utilization of newly developed deodorizing products, such as the
family of synthetic molecular sieves which have a strong affinity for organic odour
molecules [8].
The fatty acid esters are currently produced by direct esterificafion of fatty acids
separated from vegetable oils and fats. However, methyl esters can be produced
with less thermal energy expenditure than can fatty acids e.g. by ester interchange
from vegetable oils and fats and methyl alcohol [9]. It has been known since the
early 50's that for the production of certain fatty esters (by ester interchange),
methyl esters give superior results in comparison with the parent fatty acids [5].
The raw materials of fatty esters are derived from renewable vegetable and
animal sources that grow with increasing world food production. This assures a
continuing non-pollutant source of supply which is independent of the world's
dwindling reserves of mineral feed stock.
For example, in 1984-1985 the world production of principal fats and oils was
59,620 thousand metric tons, representing a 5.9% increase over the production of
1983-1984. This include: soy, palm, sunflower, rapeseed, cottonseed, coconut,
olive, palm kernel, linseed, fish, butter, tallow and grease [10].
The purpose of this paper is to present the thermal characteristics of a series of
fatty esters, prepared in our laboratory by esterification of different mixtures of
 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322 313

stearic and palmitic acid, which are commercially available with methyl, propyl and
butyl alcohols and to demonstrate the ability to tailor phase change materials for
specific needs starting from fatty chemicals. The mixtures of stearic and palmitic
acids were chosen because they are manufactured in large quantities and their
prices are the lowest in the industrial fatty acid series [13]. Commercially, these
acids are typically produced and sold as mixtures, along with other minor fatty acid
constituents. They are obtained from the mixed fatty acids derived from animal
tallow after nearly complete separation of unsaturated liquid oleic acid by different
procedures. The remaining crude stearic and palmitic acid are then refined to
produce resulting mixtures with a high content of stearic acid (more than 50%)
where the stearic:palmitic ratios are between 50:50 and 90:10. These mixtures are
known as "stearic acid". For mixtures with more than 60% palmitic acid content
the term "palmitic acid" is usually applied.
A literature survey of the thermal characteristics of the esters of these acids
indicated interesting melting and freezing intervals for heat storage in buildings.
For esterification, short chain alcohols (1-4C) were chosen in order to obtain
esters with high latent heat. Ethyl esters were not taken into consideration because
they are generally dimorphic [7] and hence not suitable for a single transition
temperature range.

2. Experimental

2.1. Materials

(a) Fatty acids: four commercial mixture of different grades of stearic acid ob-
tained from Henkel Canada Inc. were utilized as raw materials, i.e. Emersol
132, Emersol 150, Emersol 153 and Emery 420. Their characteristics are
illustrated in Table 1.
(b) Alcohols: methyl, propyl and butyl alcohols were all reagent grade (Anachemia)
and the water content was 0.2% for methyl and propyl alcohols and 0.1% for
butyl alcohol.
The fatty acids will be designated in the text only by their identification number
i.e. 132, 150, 153 and 420 and the esters by the first letters of the alcohol (Me, Pr,
B) and the corresponding identification number of the acid i.e. 132B designates
the butyl ester of Emerest 132.

2.2. Procedure

The esters preparation was done in accordance to existing methods of esterifica-

tion of fatty acids [12] utilizing a 5:1 molar excess of alcohol to fatty acid. Sulfuric
acid was utilized as catalyst and the esterification was undertaken by refluxing the
fatty acid-alcohol mixture for 48 hrs. Then half of the alcohol was removed by
distillation and an equivalent quantity of water was added to the remaining
mixture. After this, the ester layer was separated and washed several times with
314 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322

water until neutral. Finally, the purification of crude ester was carried out by
dissolution in acetone or alcohol, followed by crystallization and filtration. The
yield of ester was approximately 94-95% of the theoretical one.

2.3. Testing

A 912 Du Pont Dual Sample DSC provided with a Du Pont Mechanical Cooling
Accessory and connected to a Du Pont 2100 Thermal Analyzer was used for the
determination of the thermal properties of crude esters, i.e. latent heats and
transition temperatures. The 912 DSC cell calibration was done in accordance to
the instrument manufacturer's specifications, with certified Indium etalon samples
at the working rate of 2°C/min., under nitrogen atmosphere.
In a previous study [13] it was demonstrated that a 2°C/min. heating and
cooling rate can be considered optimal for DSC testing of materials with relatively
broad melting and freezing peaks, as in the case of fatty acids and their derivatives.
This slow heating and cooling rate was found to provide a good resolution of the
peaks and a clearer extrapolated base line.
Latent heats were obtained by numerical integration of the area between the
heat flow curve and extrapolated base line. Melting and freezing points were taken
at the intersection of the extrapolated base line and the tangent to the heat flow
curve drawn at the inflection point on the appropriate side of the peak. In
addition, melting or crystallization peak temperatures are defined as those points
which are located furthest from the base line.

3. Results and discussions

The thermal characteristics of the methyl, propyl and butyl esters prepared in
the laboratory are presented in Table 2. The progressive increase of melting/freez-
ing temperatures was taken into consideration in editing the table while the
designation of the products is in accordance with Section 2.1.
In the majority of cases the profile of DSC curves shows a principal peak which
is quite sharp and well defined in both melting and freezing. When integrated in
the temperature region of interest, these peaks give a satisfactory latent heat of
approximately 80% of the total heat of transition.
For some products, a subsidiary peak can be seen in the DSC curve below the
temperature region of interest. In these cases, only the integrated value for the
main peak in the temperature region of interest is used and it was found to equal
70-80% of the total latent heat.
Table 2 also indicates the type of the principal peak, i.e. broad or sharp, the
presence of a subsidiary peak when that is the case, as well as the percentage of
effective latent heat, i.e. the latent heat corresponding to the area of the principal
peak located in the temperature interval of interest.
Fig. 1 illustrates the DSC curve of the compound 150B. If integrated in the
entire interval of melting or freezing, the latent heats are 138 J / g for melting and
D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322 315

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316 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322

',.) Z Z ~ Z ~ Z Z ~ Z Z

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 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322 317

::~. 77"C

24.33eC
1t3.5 (t39.0) d/g
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,-i
h

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Temperature (~C)
Fig. 1. DSC curve of 150 B scanned at 2°C/rain.

139 J / g for freezing. If integrated in the temperature interval close to the peaks,
the latent heats are 113 J / g both in melting and freezing, representing a little
more than 80% of the entire latent heat.
Fig. 2 represents the DSC curve of the compound 150 Pr which presents a sharp
principal transition peak as well as a subsidiary peak. For the entire interval of
melting or freezing the latent heats are 180 and 178.5 J / g respectively. If
integrated in the temperature interval close to the peaks the latent heats are 125.5
J / g for the melting and 125.8 J / g for the freezing i.e. a little more than 70% of
the entire latent heat.
The DSC curves of the products analyzed do not indicate any supercooling
phenomenon, excepting for the 153Me. However the appearance of melting above
the initial freezing points in this case is at a scan rate of 2°C/min. The same
sample scanned at one tenth of this rate, i.e. 0.2°C/min. indicates a lesser degree
of supercooling as can be seen in Figs. 3 and 4.
For the efficient utilization of a PCM its melting/freezing range and the
associated latent heat must be optimized. They must be specifically chosen for
each climate and for the intended utilization to obtain maximum efficiency during
the dominant season or period of comfort conditioning.
For example, in a heating dominant climate such as Canada, the winter-time
indoor temperature may range from 18-22°C. However, depending on the location
of the room, (above or below the main floor) and purpose of the room (bedroom or
living room) the comfort temperature range may differ by a few degrees.
318 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322

L::~. 54"C

/ 26.80°C
52.87 125.5 (178.3) d/g
.~. 0 r
2,6.31oc
tL 12"$, 0 (IBO. I) d/g
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Te,ml~e'rat up e (°C)
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3-
30 .~9°C

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I .f ~.~.c "X~ f- i~
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Temperai:ure (=C}
Fig. 3. DSC curve of 153 Me scanned at 2°C/min.
 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322 319

33. O0
1.0-

o" 0.5-
Lt.

0.0-

~a. td/g

36.12"C

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t0
Temperature (~C)
Fig. 4. DSC curve of 153 Me scanned at 0.2°/rain.

By comparison, in a cooling dominant climate as in the southern regions of

U.S.A., the summer time temperature in a house may be considered comfortable
between 22-26°C with some acceptable variations.
Investigation of the thermal performance of an outdoor test room with and
without PCM gypsum wallboard [14] during the wintertime in Montreal (45 °
latitude) has shown that, at noon on sunny days, the maximum surface temperature
of an ordinary sun-facing wallboard was close to 28°C, while that of a sun-facing
PCM wallboard was considerably lower at 24°C. The PCM used in the wallboard
for this test was 25% (by weight of wallboard) Emery 2325, a mixture of 49% butyl
stearate and 48% butyl palmitate; freezing point 21°C; melting point 17°C; latent
heat of freezing 141 J / g and latent heat of melting 138 J/ g. From these investiga-
tions one may make the following observations:
In the cooling mode, two very important characteristics are required of a PCM.
Firstly, it must have sufficient latent heat capacity to absorb the amount of heat
necessary to maintain comfort. Secondly, its melting point must be such as to
ensure the absorption of this heat at the desired temperature. In the heating
mode, on the other hand, the capacity must be adequate to provide for the release
of enough heat to meet the comfort requirements and the PCM must also have a
freezing point such that this process begins and the heat is released before the
temperature drops below the comfort level. Since most buildings have both cooling
and heating requirements, it follows that both transition points must fall within the
comfort zone.
320 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322

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 D. Feldman et al. / Solar Energy Materials and Solar Cells 36 (1995) 311-322 321

From this it will be seen that the aforementioned process of tailoring PCM's to
meet specific requirements will permit the production of a broader range of PCM's
to provide the designer with a much greater selection of PCM's from which to
choose in order to obtain the desired thermal storage and release performance.
This will not only facilitate the selection of an appropriate PCM for a wide range
of climate and comfort temperature requirements but will also facilitate the design
of a range of PCM building materials for different applications within the same
climate or even within the same structure and also for areas where unusual
conditions occur such as short-time surge loading as in an auditorium, stadium or
theatre.
Table 3 shows several categories of short chain esters of different grades of
stearic acid prepared on a laboratory scale. These are representative of PCM
modification for use in some of the applications previously discussed.

4. Conclusions

Although in its incipient phase, research concerning the esterification of differ-

ent commercial grades of stearic acid has demonstrated the ability to tailor PCMs
with specific transition temperatures and high latent heats. The thermal properties
of these esters could be improved in order to meet more specific transition
intervals. This improvement could be achieved by a further specific purification
based on the results of thermal! analysis combined with the results of other
analytical methods, for example high performance liquid chromatography. All
these data will serve to tailor specific mixtures of fatty acids which could be
obtained, probably without extra cost, taking into account the flexibility of existing
separation methods in the fatty acid industry. A very interesting method, and one
which is probably less expensive, will be the production of several fractions of fatty
esters by interchange with methyl esters which can be obtained directly from
vegetable oils and fats as was indicated in the introduction.

Acknowledgements

The authors wish to thank the Natural Sciences and Engineering Research
Council of Canada (NSERC) for financial support Thanks are also extended to
Henkel Canada for providing us the samples of different grades of stearic acid as
well as for its continuous support with materials and technical information for the
last ten years.

References

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[3] D.W. Hawes, D. Banu and D. Feldman, Sol. Energy Mater. 21 (1990) 61-80.
[4] D.W. Hawes, D. Banu and D. Feldman, Sol. Energy Mater. Sol. Cells 27 (1992) 103-118.
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[11] Emery Stearic and Palmitic Acids, Emery Industry (1975).
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[13] D. Feldman, M.M. Shapiro, D. Banu and C.J. Fuks, Sol. Energy Mater. 18 (1989) 201-216.
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Conversion Engineering Conf., August 8-13, 1993, Atlanta, pp. 2.143-2.148.