Rheol Acta (2010) 49:315–321
DOI 10.1007/s00397-009-0425-1
ORIGINAL CONTRIBUTION
Thermo-thickening during melting of dibenzylidene
sorbitol fibre networks
Martin Kühne · Jonathan Wurth · Christian Friedrich
Received: 12 June 2009 / Accepted: 16 December 2009 / Published online: 27 January 2010
© Springer-Verlag 2010
Abstract Gels of dibenzylidene sorbitol (DBS) in
poly(propylene oxide) (PPO) show an increase in vis-
cosity in a certain temperature range during melting.
This so-called thermo-thickening behaviour is quite
uncommon. In the few already known cases, the
thermo-thickening is caused by simple thermodynamic
processes that result in the formation of structures.
We show for the first time that, in the case of PPO-
DBS gels, experimental parameters like sample volume
and heating rate play an important role and indicate
non-equilibrium behaviour. It turns out that the pecu-
liar thermo-thickening is the result of a reformation
of the fibre network structure, which was destroyed
earlier due to a strong temperature gradient within the
sample.
Keywords Rheometry · Dynamic mechanical
properties · Thermoreversible gelation ·
Temperature effect · Rate dependence
Introduction
A promising route to new and tailor-made polymers
is the modification of already existing ones, either by
M. Kühne · J. Wurth · C. Friedrich (B )
Freiburger Materialforschungszentrum (FMF) and Institute
of Macromolecular Chemistry, Albert-Ludwigs-Universität,
Stefan-Meier-Str. 21, 79104 Freiburg, Germany
e-mail: chf@fmf.uni-freiburg.de
mixing certain polymers, thus creating a blend, or by
using additives to make a compound. If the additive
self-assembles into fibres, a network structure might
be formed, which leads to strong modifications of the
polymer properties.
Thereby one has to distinguish between covalent in-
teractions, which result in chemical networks, and phys-
ical interactions (like H-bonds), which result in physical
networks. Because of the characteristics of physical
interactions such networks are thermoreversible, i.e.
they melt above a characteristic temperature and form
again during cooling.
One example of additives that are able to form phys-
ical networks are organogelators. These substances of
low molecular weight build up network structures in
certain organic liquids and polymers. The formation
of the network induces a gelation of the surrounding
matrix—hence the name organogelators.
Such organogelators can be amino acid or steroid
derivates or even two-component systems, for example
(Terech and Weiss 1997).
Another example of an organogelator is diben-
zylidene sorbitol (DBS) (Fig. 1), which was used in
this work. DBS can gel organic liquids like p-xylene
or ethylene glycol (Yamasaki and Tsutsumi 1994,
1995) and certain polymers like poly(dimethyl silox-
ane) or poly(propylene oxide) (PPO) (Ilzhoefer and
Spontak 1995; Ilzhoefer et al. 1995; Nunez et al. 1996;
Fahrlaender et al. 2000; Mercurio et al. 2001; Mercurio
and Spontak 2001). In other polymers like polypropy-
lene (PP), DBS and its derivates are used as a nucleat-
ing agent (Jin et al. 2007; Dobreva et al. 2008).
Gels of DBS in polymers have been investi-
gated extensively (Wilder et al. 2002). Concerning
the temperature-dependent properties of such gels,