Microencapsulated Phase Change Material

E. Jahns

BASF AG
Kunststofflaboratorium
ZKD/A – B1
67056 Ludwigshafen, GERMANY
Phone: +49 621 60 48372, Fax: +49 621 63 50843
E-mail: ekkehard.jahns@basf-ag.de

BASF is one of the world’s leading chemical companies. Our products range from natural gas, oil,
petrochemicals and innovative intermediates to high-value-added chemicals, crop protection
agents and pharmaceuticals. Our hallmarks are our comprehensive know-how, our highly
developed integrated systems, which we call Verbund, and a significant proportion of specialties.
BASF's current product range covers the entire spectrum of chemical products. This is the result of
more than 130 years' continuous development, in the course of which the company has written
chemical history with a wide variety of pioneering achievements.
Our dispersions segment produces acrylic acid and esters, acrylic and styrene-butadiene
dispersions, raw materials for coating application and adhesives, colorants and process
chemicals for the paper industry and super absorbants. Microcapsules are produced since more
than 15 years for use in carbonless copy paper, which is known for everybody in daily life.

Phase change material

Since two years research was done at BASF in the field of phase change materials concerning
microcapsules. What is meant by phase change materials? Major phase changes of a substance
are their melting/freezing point (solid-liquid pahse change) and the boiling/condensation point
(liquid/gas). These phase changes have in common the highest values in enthalpy during phase
change. Additional some substances have solid/solid phase changes with noticable enthalpies.
Solid/solid and solid/liquid phase changes can be used preferentially to store energy, because
changes in volume during these phase changes are small. The enthalpy which is stored during
phase change of a substance is called latent heat in contrast to the direct heat storage in a
substance during heating due to its heat capacity.
To demonstrate the amount of heat storage due to direct and latent heat, water is choosen as
example. One has to heat up water from 0°C to 80°C to store 336 KJoule in 1 kg water. The same
amout of energy, 333 Kjoule, is stored during melting of 1 kg of ice. Please notice, that during
melting of the ice the temperature stays constant at 0°C! Water has an unusual high heat capacity
and heat of melting due to hydrogen bonding effects. But there are organic and inorganic
substances which exhibit heats of melting from about one half the value of water up to the value of
water itself.

Temperature stays constant during phase transition

Besides the ability to store energy in a phase transition it is noteworthy that the temperature stays
nearly constant during this process. This is a major feature for some applications of phase change
materials. They may be used to keep food and drinks cold or warm, dependend on the phase
change temperature choosen. Or they may increase comfort of people when incorporated in their
clothes or their homes. Think about the sun, which is shining in your home through the windows.
She will warm up the room in which you stay. In winter time this is wanted as additional
seasonal heating. If it gets too hot, you open the window and the heat is gone fast. In summer the
only way to get rid of excessive heat without air-conditioning (energy consumption!) is the storage
in your building material due to the heat capacity of these wooden or inorganic substances. But
the storage capacity is limited. Its about one KJoule per kg of conventional building material.
Therefore the comfortableness of your house depends on its thermal mass which is very near to
the mass of the building. The mass smoothes possible peak temperatures during hours up to a few
days.
The specific heat capacities of a few building materials as examples are: Timber 1,3 KJ/kg.K,
concrete 0,92 KJ/kg.K and a brick wall 0,84 KJ/kg.K. One way to increase the ability to store heat is
the integration of phase change materials in the house. This is very effective, because the range of
comfort is really small, lets say between 20 and 24°C. When we choose a PCM with heat of melting
of e.g. ∆H=200 KJ/Kg with a melting point of 22°C, take 30% of this PCM in concrete, we yield
between 20 and 24°C 30% of 200 KJ = 60 KJ + 4 times 0,92 KJ = 63,7 KJ/kg for the modified
concrete instead of 3,7 KJ/kg for concrete alone.
Modern strategies of passive cooling of buildings e.g. with cold air ventilation over night or from
an underground heat exchanger is impossible without thermal mass of the building. Phase
change materials as described above improve the thermal mass in a defined temperature range
with only small volume and mass requirements. They are best used to keep a certain temperature
constant as it is needed e.g. in buildings in moderate climate with changes in outdoor temperature
between day and night and seasonal changes. The cooling and heating loads and the variable
costs therefore are reduced because of balancing energy losses and yields. Additionally the
thermal insulation of a building may be improved due to storage effects of the PCM’s.

Material
Nearly all possible phase change materials were tested in the past for building application in
certain containments and building materials. Paraffinic hydrocarbons, fatty acids and eutectic
mixtures, fatty alcohols, neopentyl glycol and inorganic PCM’s. Paraffinic hydrocarbons, fatty
acids and fatty alcohols are substances with low solubility or zero solubility in water. Therefore
they are preferencial for use in building materials. They exhibit melting enthalpies between 150
and 220 KJ/kg. Mixtures of paraffins can be prepared to have melting temperatures of 15 to 30°C
that include all needs of building applications.
Phase change materials in classical formulations have some disadvantages. Salt hydrates are
mobile in common building materials and may sweat out at the surface or wash out in moist
climate. Their crystal water content may change due to humidity changes. Hydrocarbons melt to
low viscous liquids that are mobile and may diffuse throughout the building material.
Hydrocarbons may evaporate independent to their molecular weight into the ambient air and
thus increase the volatile organic content (VOC) of the air. Their are legal regulations in many
countries to reduce VOC contents of ambient air in buildings which must be followed with new
materials to develop. Therefore the use of phase change materials without containers is often not
recommended.

Microcapsules
Microcapsules are tiny little containers which pack the core material individually with a hard
shell. Microcapsules can therfore handle even liquids as solid material. They tolerate phase
changes including volume changes in their core and can handle phase change materials as core.
Microcapsules may be processed as aqueous dispersion or powder and improve the formulation
of phase change materials as many building materials go through a powder state during
processing. Phase change temperatures between –10°C and 80°C are possible to manufacture with
microcapsules. The standard processes for microencapsulation need hydrophobic, mainly water
insoluble core materials. Paraffin waxes are best appropriate for microencapsulation.

What is microencapsulation?
Microencapsulation is a physical or chemical process to engulf small solid or liquid particles of
1 to 1000µm diameter with a solid shell. Physical processes to get microencapsulation are spray-
drying, centrifugal and fluidized bed processes or coating processes e.g. in rolling cylinders.
Chemical processes describe in-situ encapsulations like complex coazervations with gelatine,
interfacial polycondensations to get polyamides or polyurethanes as shells, precipitations due to
polycondensation of amino resins and other special in-situ processes. The in-situ processes have
the ability to yield microcapsules with the best quality in termes of diffusion-tighness of their
walls. These microcapsules are widely used in carbonless copy paper world-wide.

Melamine resin process

water-soluble
pH melamine resin

Oil

5 - 20 µm
water and
protective colloid

Figure 1: Graphic representation of the melamine resin microencapsulation process

The figure 1 describes a typical microencapsulation process using melamine resins. An oil-phase
is emulsified in water using water-soluble polymers and high shear mixers yielding a stable
emulsion of wanted size. A water-soluble melamine resin is added. Due to added acid the
polycondensation is started which yields crosslinked resins that deposit at the interface between
the oil droplets and the water phase. During hardening of the wall material the microcapsules
form and the aqueous dispersion of polymer-encapsulated oil droplets is received.

State of the art in microencapsulated PCM’s

During the 80th there was intensive activity in America in developing phase change material and
first microencapsulations of this materials are reported. From literature a multitude of capsule
trials is described in building materials, including microencapsulation. Obviously the market
success was small. Scince a few years there is renewed interest in using microencapsulated phase
change materials for clothing application. Two very active companies from America are marketing
microencapsulated PCM’s in form of fibers, fabrics and breathable foams: Frisby Technologies
from Winston-Salem, NC and Outlast Technologies from Boulder, CO (www.frisby.com;
www.outlast.com). The next transparencies from the internet show some of the products where
the microencapsulated PCM’s are incorporated. Some of them are in the stores in Europe already.

Focus BASF
What is our focus in phase change materials? We want to use our microencapsulation know-how
and technology for developing microencapsulated phase change materials. We synthesize
microcapsules and modify them for certain applications. This year we have started a participation
in a joint german project on “Microencapsulated phase change materials for building
application” together with partners. The joint project is funded by the Federal Ministry of
Economics and Technology under sign 0329840A.

Results
Microcapsule dispersions were synthezised with paraffin waxes as phase change materials with
melting temperatures between 6°C and 60°C and dried to powder. We found them suitable for
different applications including building applications.
Figure 2
Microencapsulated Phase Change Material b

Results
l Microcapsule dispersions with paraffins as PCM were synthesized with melting
temperatures between 6 and 60°C and dried to powder
l DSC-Results:

Paraffin 62/64°C Microencapsulated Paraffin 62/64°C

Figure 2

Figure 2 shows for example the differential calorimetry results of a paraffin wax mixture of
62/64°C melting point alone and the dried microcapsule with the paraffin wax. The heat
enthalpies are 183 KJ/kg and 143 KJ/kg respectively.

Summary
It was shown that phase change materials can be used to increase the thermal mass of buildings
and even clothing without increasing their real mass very much. I showed you that paraffinic
hydrocarbons can be microencapsulated successfully. These microencapsulated phase change
materials are advantegous in handling of the paraffins, which stay in liquid state from time to
time. The use of microencapsulated phase change materials show increasing interest for clothing
application, where products are already on an increasing market. BASF undertakes research in
the field of microencapsulated phase change material and in this respect is member of a joint
german project on “Microencapsulated phase change material for building application”.