A
Annealing of Polymer Membranes
Maria Luisa Di Vona
Dip. Di Scienze Technologie Chimiche,
University of Rome Tor Vergata, Rome, Italy
Annealing can be defined as a process where a
material undergoes a heat treatment to a certain
temperature, is kept there for a definite time, and
is then cooled to room temperature in order to
alter the material properties. The annealing pro-
cess is time and temperature dependent.
Annealing of polymers is a heating of a poly-
meric part to below its glass transition tempera-
ture in order to relieve the internal stresses
introduced during its fabrication (molding,
cooling after molding, machining, welding, etc.).
Annealing of conjugated polymers and poly-
mer blend films is a widely used process that
achieves optimal film morphology and therefore
improves material properties, such as electrical
mobility for photovoltaic devices and other appli-
cations. Annealing of ion-conducting polymers
reduces the excessive swelling observed in pres-
ence of water.
In particular, annealing is used (Young and
Lovell 1991):
(a) To increase the melting point of some poly-
mers because it facilitates the melting of
small and irregular crystals in favor of larger
and better formed ones
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_627-1
(b) To reduce or cancel deformations previously
provoked at higher temperature which
remain as frozen (permanent) deformations
when the material is cooled to room
temperature
(c) To increase crystallization
(d) To decrease the free volume between poly-
meric chains thus inducing a mechanical sta-
bilization of polymeric materials
Annealing of liquid crystalline polymers
between the glass transition temperature and the
melting temperature leads to an increased level of
crystallinity and increased crystalline perfection
analogous to the behavior of conventional semi-
crystalline polymers. Annealing at or above the
melting point also leads to enhanced crystallinity
and crystalline perfection.
The annealing of semicrystalline polymers
may change the crystal structure, the degree of
crystallinity, the perfection of the crystals, the
orientation of both crystalline and amorphous
phases, their contiguous structural morphology,
and the number of tie chains between the crystal-
lites. Morphological changes are also observed
on annealing bulk-crystallized samples. Poly-
morphism may result due to annealing crystalline
polymers as its one crystalline form transforms
into another. The concept that mechanical stabi-
lization was due to a generic decrease of the free
volume between ionomer chains when thermally
treated was abandoned and replaced by the con-
sideration that the mechanical stabilization was
2 Annealing of Polymer Membranes
induced by an increased crystallization of a
preexisting semicrystalline phase (Alberti
et al. 2013).
Thermal annealing is a simple route for stabi-
lizing glassy polymers via the densification of
their polymer chains and is accomplished through
thermal treatment of the glassy thermoplastics.
For amorphous polymers, the thermal treatment
can play a very important role in changing the
morphology. If the temperature is lower than the
glass transition temperature Tg, the polymer
chains are mainly immobile, thereby maintaining
the existing morphology; however, if the
annealing temperature is greater than the Tg, the
polymer chains will relax. It has been found that
the morphology can be modified upon annealing
at a temperature higher than the Tg, thus changing
the physical properties of the polymers.
A certain amount of molecular rearrangement
must take place during crystallization but this
rearrangement cannot arise through large-scale
molecular diffusion as the process is occurring
in the solid state. Thermal treatments were
believed to be more and more efficient as the
temperature increases and therefore empirical
short treatments were performed at high temper-
atures. Thus, the annealing temperature (Tann)
was connected with the crystallization tempera-
ture (Tc) and it became clear that the annealing
temperature cannot be higher than the melting
temperature (Tm) of the semicrystalline phase.
References
Alberti G, Narducci R, Di Vona ML, Giancola S (2013)
Annealing of Nafion 1100 in the presence of an
annealing agent: a powerful method for increasing
ionomer working temperature in PEMFCs. Fuel Cells
13:42–47
Young RJ, Lovell PA (1991) Introduction to polymers,
2nd edn. CRC Press, Boca Raton