Experimental results from the literature and from this work show
the reliability of the
dynamic mechanical spectroscopy as a complementary tool to follow the
crystallization of polymers from
the melt. However the problem of the interrelation between the
transformed fraction and the mechanical
data is not simple and remains a topic open to discussion. To get
a better understanding of these relations,
the method was applied to the study of two polyolefins which show very
different morphologies during
their crystallization from the melt. Their morphological study has
shown that, though they both crystallize
in a well-defined spherulitic structure, because of the differences of
size of the crystalline entities, one
can be considered as a suspension of spherical particles in a liquid
matrix whereas the other behaves as
a colloid of small particles. The study of the rheological
behavior of the suspension-like material shows
the existence of two critical values of the volume fraction. In
agreement with the percolation theory, the
first value is related to the appearance of a yield effect and the
second indicates the maximum packing.
Moreover, in this case, throughout the crystallization, the
relaxation times depend on the filler content
and the zero-shear viscosity varies upon the
−3/2 exponent of the volume fraction.
The colloid-like material
behaves in a completely different way since a yield effect appears in
the earliest stage of the crystallization.
For both materials, the use of an equilibrium modulus is able to
characterize the yield effect, and in both
cases, it is described by the same type of expression with a universal
exponent equal to 3 in agreement
with theories for physical gels. Unfortunately, these results show
that a unique expression can hardly
be used to relate the transformed fraction to the rheological data and
that such a derivation always
requires an additional investigation of the morphology.
The manufacturing of composites of ultra high molecular weight polyethylene and ceramics with conductive properties has been investigated. Attention has been focused on the lowering of the amount of filler necessary to achieve low resistivity. Using segregated networks, mixing large polymer particles and submicron metal or conductive ceramic particles may be an interesting route, provided that the processing method enables to generate the desired structures. Because sintering avoids the intimate blending of the components, it is a suitable technique for this aim. The combined effects of temperature, pressure and sintering time have been investigated. The influence of the blending of the solids on the covering of the polyethylene particles before the sintering has also been pointed out. The typical features related to the concept of a segregated network are discussed in connection with the morphologies of the polymer and ceramic particles. The successful application of the reduction of the percolation threshold by a segregated network in conductive composites of polymer and metallic particles is described.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.