We have investigated structural changes in a poly(vinyl alcohol) (PVA) film during uniaxial
stretching in water by conducting simultaneously the tensile stress−strain measurement with small-angle X-ray
scattering (SAXS) using our newly developed drawing apparatus for the in situ SAXS measurements. Below the
strain of 70%, the crystalline lamellae orient to the direction perpendicular to the stretching direction and the
intervening amorphous regions are elastically expanded with the film drawing in proportion to the macroscopic
deformation. Beyond the strain of 70%, the molecular chains in the intermediate amorphous region are relaxed
with the lamellar breakup. Above 180% strain, the structural transition of the lamellar structure to the microfibrillar
one takes place, as suggested by appearance of the transversal streak with an intensity maximum on each streak
and the mechanical transition. Moreover, interfibrillar interaction of the adjacent microfibrils decreases with the
film stretching by the pulling-out of the tie chains, which are interpenetrating to the adjacent microfibrils, leading
to the macroscopic plastic deformation of the PVA film and stress relaxation of most of the microfibrils, which
is shown by the continuous longitudinal long period decrease. In the final stage of deformation, the networking
with a long-range connectivity composed of the microfibrils and the interfibrillar extended amorphous chains
proceeds associated with the sliding between the adjacent microfibrils with successive drawing. However, the
network of the interfibrillar extended amorphous region is considered to be an origin of the strain-induced hardening,
which occurs above 180% strain up to a break, because most of the microfibrils are relaxed with strain.
We propose a structure model of a poly(vinyl alcohol) (PVA) film during uniaxial stretching in
water. In addition to the relaxation of microfibrils and the extension of interfibrillar amorphous regions shown in
our previous paper, it was described that the strain-induced crystallization takes place in the interfibrillar extended
amorphous regions, which bear the increasing stress with strain, by conducting simultaneously the tensile stress−strain measurement with the wide-angle X-ray diffraction (WAXD) measurements for the film stretched in water.
Furthermore, we examined the dissolution behavior of the PVA film in water by using in-situ WAXD and small-angle X-ray scattering. It was concluded that the dissolution of crystallites in the lamellar stacks, which are
considered to be precursors of the microfibrils formed with film stretching, softens the system, as shown with the
stress−strain measurement in water above 333 K, leading to the ineffective amorphous chain extension of PVA
molecules.
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