The
standard route toward high-performance polyethylene fibers
involves “ultra-drawing”: large-strain solid-state uniaxial
plastic deformation at elevated temperatures of precursor ultra-high
molecular weight polyethylene (UHMWPE) fibers to achieve crucial near-to-perfect
orientation of macromolecular chains. It is well accepted that the
drawability (and therewith orientation) of UHMWPE is largely determined
by the entanglement density. This research evaluates the effect of
solvent quality and crystallization conditions on ultra-drawability
of UHMWPE by several independent experimental methods. Rheological
and mechanical evaluation of the elastic properties of UHMWPE solutions
and the resulting gels cast from good and poor solvents show that
at a given UHMWPE concentration, the entanglement density in solution
and the connectivity in the resulting gels are similar if not identical,
suggesting that the entanglement density is not directly influenced
by solvent quality. Nevertheless, at a given concentration, dried
films obtained from poor solvents depict a twofold higher drawability,
resulting in improved fiber properties. The observed correlation of
the maximum draw ratio with lamellar thickness of films cast from
poor and good solvents at a given polymer concentration suggests that
polymer crystals formed at low undercooling have a higher maximum
draw ratio. In addition, this study presents two new methods that,
by solely changing the crystallization conditions of UHMWPE solutions
at a given polymer concentration, result in an increase in the maximum
draw ratio of the produced UHMWPE precursor films and ultimately leading
to improved fiber properties.