In the present study,
three different newly developed copolymers
of poly(3-hydroxybutyrate-
co
-3-hydroxyvalerate) (PHBV)
with 20, 40, and 60 mol % contents in 3-hydroxyvalerate (3HV) were
produced by the biotechnological process of mixed microbial cultures
(MMCs) using cheese whey (CW), a by-product from the dairy industry,
as feedstock. The CW-derived PHBV copolyesters were first purified
and then processed by solution electrospinning, yielding fibers of
approximately 2 μm in cross-section in all cases. The resultant
electrospun PHBV mats were, thereafter, post-processed by annealing
at different temperatures, below their maximum of melting, selected
according to their 3HV content in order to obtain continuous films
based on coalesced fibers, so-called biopapers. The resultant PHBV
films were characterized in terms of their morphology, crystallinity,
and mechanical and barrier properties to assess their potential application
in food packaging. The CW-derived PHBV biopapers showed high contact
transparency but a slightly yellow color. The fibers of the 20 mol
% 3HV copolymer were seen to contain mostly poly(3-hydroxybutyrate)
(PHB) crystals, the fibers of the 40 mol % 3HV copolymer a mixture
of PHB and poly(3-hydroxyvalerate) (PHV) crystals and lowest crystallinity,
and the fibers of the 60 mol % 3HV sample were mostly made of PHV
crystals. To understand the interfiber coalesce process undergone
by the materials during annealing, the crystalline morphology was
also assessed by variable-temperature both combined small-angle and
wide-angle X-ray scattering synchrotron and Fourier transform infrared
experiments. From these experiments and, different from previously
reported biopapers with lower 3HV contents, all samples were inferred
to have a surface energy reduction mechanism for interfiber coalescence
during annealing, which is thought to be activated by a temperature-induced
decrease in molecular order. Due to their reduced crystallinity and
molecular order, the CW-derived PHBV biopapers, especially the 40
mol % 3HV sample, were found to be more ductile and tougher. In terms
of barrier properties, the three copolymers performed similarly to
water and limonene, but to oxygen, the 40 mol % sample showed the
highest relative permeability. Overall, the materials developed, which
are compatible with the Circular Bioeconomy organic recycling strategy,
can have an excellent potential as barrier interlayers or coatings
of application interest in food packaging.