Poly
methyl methacrylate (PMMA) has many uses, including as plexiglass, high-speed
optic cable, teeth filling material and bone cement. It is generally an
amorphous material, lacking strength and features of semi-crystalline
polymers. However the mixture of stereoregular PMMA (i.e. mixture of isotactic
and syndiotactic PMMA), forms a supramolecular structure. This structure
is called a "stereocomplex". The syndiotactic PMMA wraps around
the isotactic chain, forming a 9/1 double stranded helix, having an asymmetric
unit consisting of 1 isotactic unit and 2 syndiotactic units. Thus formed
physical gels has "physical" crosslinks that improve the mechanical
properties of PMMA. We study the properties of this gel, and are developing
the gel spinning technology to make these stereocomplex fibres with much
better mechanical properties. The goal is to then use these fibers in
PMMA matrix to form self-reinforced composites.
The stereocomplex forms only in a certain solvents. In these solvents, a viscosity drop is observed when dilute solutions of isotactic and syndiotactic PMMA are mixed. This suggests a reduction in the number of chains present in the solution. When such solutions are evaporated, the PMMA residue has crystalline regions with a rather high melting point (180 C). X-ray data as well as NMR and IR data in the literature suggest that a helical structure is responsible for this behavior. We are interested in the rheology of such physical gels, as well in understanding how and why stereocomplex forms. We mix the isotactic and syndiotactic PMMA in a stereocomplex forming solvent (DMF). If the concentration of the polymer is high enough, a physical gel forms. We have used this dope to make PMMA fibers by the gel-spinning method. |
The gel
spinning set-up. A: heated syringe with the stereoregular PMMA solution
in DMF. B:methanol cooling bath at -20C . C: pick-up reel. D: heating
zone. E: stretching reel. |
The
crucial feature of this method is gel formation in the polymer solution
right as it flows out of the spinneret. This is achieved by heating the
solution in the syringe above its gel-temperature (A). Once the polymer
solution exits the spinneret, it cools down and forms a gel. To further
promote gel formation, the resulting fiber is dragged through a cooling
bath (B) and picked up at a set pick-up rate (C). Furthermore, the fiber
is heated (D) and stretched (E). We are currently investigating the rheology
of the dope solutions and of gels formed and the mechanical and thermal
properties of the fibers formed.
The resulting high-strength semi-crystalline PMMA fibers will be used to make self-reinforced composites. In a regular fiber-reinforced composite, high-strength fibers are embedded in a polymeric matrix. The key feature that dictates the resistance to stress fracture failure is the fiber-matrix interface. This interface is governed by adhesion forces, which are in turn dependent on material similarity. The more chemically similar the two materials, the better the adhesion and therefore tighter fiber-matrix interface. In a self-reinforced composite, the fibrous and non-fibrous materials are chemically identical, thus providing a very good fiber-matrix interfacial interaction. |
Idealized
view of the fiber-matrix interface in self-reinforced composites. It should
be noted, that the fibers are not as perfectly aligned in a realistic
composite. The colors reflect the similarity of the materials used and
black lines denote phase boundaries. Note that there is no phase boundary
between the fiber and the matrix in a self-reinforced composite. |
We
also investigate the thermal properties of these composites and observe
the melting point of stereocomplex fiber is around 180 C. This is very
high compared to the melting point of either of the stereoregular PMMA
and is correlated to the degree of crystallinity and the method of stereocomplex
preparation. The mechanical properties of the fibers are being investigated.
Young's modulus of the fibers needs to be higher than the regular PMMA
in order for the fiber to have any reinforcing effect on the composite.
Furthermore, the mechanical properties of the composite as a whole will
be investigated as related to Young's modulus and fracture toughness,and
being a self reinforced composites we expect remarkable improvements in
obtainable mechanical properties. |