3.3. Mechanical characterization
The mechanical property of fiber as a reinforcement in polymeric
matrices is directly concerned with the overall performance
of the composite. In this study, the mechanical performance of
a-CNFs and r-CNFs mats was first compared (see Supporting information)
and had demonstrated obviously different results. Aligned
cellulose nanofibrous mats showed a substantially high tensile
strength, which was approximately 7 times that of nanofibrous
mats with a random fiber orientation. The uniaxial orientation of
electrospun cellulose fibers positively influenced on the improvement
of mechanical strength. Therefore, a-CNFs were used as the
reinforcements to further reinforce the PVA resin matrix in the
following experiment.
The tensile property of a-CNFs@PVA was measured by cutting
the composite film into strips along the impregnated fiber direction.
As shown in Fig. 5, the fiber content influences the tensile
properties. The pure PVA film showed poor mechanical properties,
and the tensile strength and modulus were ∼25 MPa and
∼129 MPa, respectively. The tensile strength of the composite evidently
increases when the cellulose fibers are embedded in the
PVA matrix. The maximum mechanical strength of ∼39 MPa was
achieved for the a-CNFs@PVA composite with CNFs content of 32%.
This value is 1.6 times that of neat PVA film, whereas the modulus
significantly increased from 129 MPa to 1.1 GPa. The modulus
of composite films increases substantially with fiber content in
the range studied in this work. Notably, the increase in modulus
is not in accordance with the moderate gain of tensile strength.
A similar finding was also reported in the literature (Bergshoef &
Vancso, 1999; Tang & Liu, 2008). These results demonstrate that
electrospun cellulose nanofibers provide effective reinforcement,
as explained by strong intermolecular forces between the CNFs and
PVA matrix. As such, a large amount of hydroxyl groups on CNFs
surfaces forms strong hydrogen-bonding with PVA matrices. This
formation consequently results in intimate adhesion force at the
CNFs@PVA interfaces, as evidenced in the fractured SEM images
(Fig. 4). When a PVA composite film was stretched, this interaction
structure can lead to stress transfer from PVA to CNFs. The occurrence
of nanofiber bowing derived from the stress transfer, and in
turn it improves the mechanical properties of the composite. With
further increase in a-CNFs content, the tensile strength of the composite
film gradually decreased, but remained higher than those of
pristine PVA film. Given that the strength of the CNFs is smaller
than that of PVA matrix, the excessively high content of CNFs is not
expected to effectively reinforce the composite film. Instead, it was
J. Cai et al. / Carbohydrate Polymers 140 (2016) 238–245 243
Fig. 5. Mechanical performance of a-CNFs@PVA composite films corresponding
with the changes of fiber content.
possible to weak the overall mechanical properties of the composite
film. Fig. 5 also shows a decrease in strain at break values after
CNFs were impregnated into PVA matrix. The unexpected decrease
in stain originates from the rigidity effect of the cellulose fiber.
To further examine the effects of the CNFs embedding into
matrix on the mechanical property of the composite film, aCNFs@PVA
was subjected to dynamical mechanical analysis (DMA).
Fig. S7 (in the Supporting Information) shows the storage modulus
(E0) of the a-CNFs@PVA as a function of temperature and fiber content.
The studied pure PVA shows a typical mechanical behavior
of an amorphous polymer material. With increasing temperature,
the E0 of samples decreased because of the easier movement of
polymer chains at elevated temperature. Compared with the fairly
low E0 of neat PVA, the value significantly increased for composite
films, such as those with increasing a-CNF content. This finding
suggests that the incorporation of aligned nanofibers in the matrix
enhances the stiffness and thermal stability. The shift of Eo to a
higher value could be explained by intimate fiber/PVA interfaces,
which impart mechanical limitations to the matrix and reduces
mobility and deformation. The height of tanı peaks substantially
declined for CNFs@PVA composite films, indicating that the dampening
effect decreased with the loading of fibers into the matrix
(see Supporting information) (Liao, Wu, Wu, Zhan, & Liu, 2012).
This finding is ascribed to the composition of neat PVA and strongly
bonded fiber–PVA interfacial materials, leading to effective load
transfer from the PVA matrix to the fibers. Moreover, broad rather
thansharp tanı peaks were observed for CNFs/PVAcompositefilms,
suggesting that the PVA in the composite films is heterogeneous,
and strong interfacial bonds form between the reinforcing cellulose
fibers and the PVA matrix