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Article history:
Received 11 February 2014
Received in revised form
29 April 2014
Accepted 2 May 2014
Available online 29 May 2014
Nanocomposite lms based on poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends and synthesized cellulose nanocrystals (CNC) or surfactant modied cellulose nanocrystals (CNCs), as bio-based
reinforcement, were prepared by melt extrusion followed by lm forming. The obtained nanocomposites are intended for short-term food packaging. Thus, the mechanical, optical, barrier and
wettability properties were studied. Functionalized CNCs contribute to enhance the interfacial adhesion
between PLA and PHB, leading to improved mechanical stiffness and increased lm stretchability. The
synergic effects of the PHB and CNCs on the PLA barrier properties were conrmed by increases in
oxygen barrier properties and reductions in surface wettability of the nanocomposites. In addition, the
measurements of the viscosity molecular weight for ternary systems showed practically no degradation
of PLA and smaller degradation of PHB during processing due to nanocrystal presence. The disintegration
process in composting conditions of PLA was delayed by the addition of PHB, while CNC speeded it up.
PLA-PHB-CNCs formulations showed enhanced mechanical performance, improved water resistance,
reduced oxygen and UV-light transmission, as well as appropriate disintegration in compost suggesting
possible applications as packaging materials.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Poly(lactic acid)
Poly(hydroxybutyrate)
Modied cellulose nanocrystals
Nanocomposites
Biodegradation
Barrier properties
1. Introduction
Many positive characteristics of PLA have situated it as the most
used biopolyester for biodegradable food packaging industry.
Among other properties, PLA compared to other biopolymers
shows easy processability [1], superior transparency, availability in
the market [2], excellent printability [3], high rate of disintegration
in compost [4]. Conversely, the use of PLA lms for food packaging
has been strongly limited because of their poor mechanical and
barrier properties [5]. Moreover, for large-scale industrial production PLA must guarantee adequate thermal stability or low thermal
degradation during processing and use [6].
Initially, the materials for food applications were semi-rigid or
exible monolayer systems. Afterward, to improve the barrier
properties they were replaced by more complex multilayer systems, which are still used in the market. However, its difculty of
recycling and the worldwide trend to reduce the polymer consumption per package unit, demand the development of simplest
packaging formulations particularly focused on blending strategies
[7]. Thus, melt blending PLA with another biopolymer can lead to
signicant improvement of the nal properties through a cost
effective, easy and readily available processing technology [8].
Food packaging, besides containment and information, should
provide foodstuff protection against water, light or oxidative process [9]. It is known that the crystalline phase has an important
impact on mechanical and permeation properties; as a result,
considerable academic and industrial research efforts have been
focused to increase PLA crystallinity. In this sense, the addition of
poly(hydroxybutyrate) (PHB), a highly crystalline biopolymer, to
the PLA matrix by melt blending has been considered as an easy
way to increase PLA crystallinity and regulate its properties [10].
PHB, the most common representative of poly(hydroxyalkanoates)
(PHA), with a high degree of crystallinity, has been also proposed
for short-term food packaging applications [11]. PHB has a similar
melting temperature to PLA, allowing blending both polymers in
the melt state. In a previous work, PLA was melt blended with 25 wt
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M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
141
Table 1
PLA and PLA-PHB nanocomposite lm formulations and their viscosity molecular weight (Mv).
Film formulations
PLA
PLA-CNC
PLA-CNCs
PLA-PHB
PLA-PHB-CNC
PLA-PHB-CNCs
Materials (wt %)
PLA
PHB
CNC
CNCs
100
95
95
75
71.25
71.25
e
e
e
25
23.75
23.75
e
5
e
e
5
e
e
e
5
e
e
5
h K MVa
(1)
were K and a are 1.53 102 and 0.759 for PLA, respectively [27] as
well as K and a for PHB are 1.18 102 and 0.780 in that order [28].
The mechanical behaviour was investigated by tensile test in a
digital Lloyd instrument LR 30K, performed on rectangular probes
(100 mm 10 mm) at room temperature by following the UNE-EN
ISO 527-3 standard [29] with a crosshead speed of 5 mm/min, a
load cell of 500N and an initial gauge length of 50 mm. Average
tensile strength (TS), percentage elongation at break (b %) and
Young's modulus (E) were calculated from the resulting stressestrain curves as the average of ve measurements of each
composition.
The absorption spectra of nanocomposites, obtained in the
700e250 nm region, were investigated by a PerkineElmer (Lambda
35, USA) UVeVIS spectrophotometer. Nanocomposite lm colour
properties were evaluated in the CIELAB colour space by using a
KONICA CM-3600d COLORFLEX-DIFF2, HunterLab, Hunter Associates Laboratory, Inc, (Reston, Virginia, USA). The instrument was
calibrated with a white standard tile. Yellowness index (YI) and
colour coordinates, L (lightness), a* (red-green) and b* (yellowblue) were measured at random positions over the lm surface.
Average values of ve measurements were calculated. Total colour
difference (DE) was calculated with respect to the control pure PLA
lm or PLA-PHB lm as:
p
DE Da*2 Db*2 DL*2
(2)
PLA Mv (g mol1)
PHB Mv (g mol1)
e
e
e
224,300 45,150
231,700 46,400
233,000 44,700
90,600
86,200
81,100
91,900
95,000
95,600
10,700
18,800
14,400
19,000
19,500
18,800
mi m
1 e1t50 =dt
(3)
where mi and m are the initial and nal mass values measured
respectively at the beginning of the exposition to compost and after
the nal asymptotes of the disintegrability test, and t50 is the time
at which materials disintegrability reaches the average value between mi and m, known as the half-maximal degradation, dt is a
parameter that describes the shape of the curve between the upper
and lower asymptotes [32].
Photographs of recovered samples were taken for visual comparison. Surface microstructure of PLA and PLA-PHB nanocomposites before and after 3 days of incubation in composting
were studied by optical microscopy using a LV-100 Nikon Eclipse
equipped with a Nikon sight camera at 20 magnications using
the extended depth of eld (EDF-z) imaging technique to obtain a
tridimensional vision of lms surfaces. This technique uses a
motorized z-axis (height of focus) to take images at different height
planes. Subsequently, by means of a dedicated algorithm installed
in the NIS-Elements software a 3D image is reconstructed following
the original texture of sample.
The relationship between meso-lactide and L,D-lactide form in
the polymer after compost incubation was also studied by
Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) by
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Signicance in the mechanical, wettability and colour parameters differences were statistically by one-way analysis of variance
(ANOVA) using OriginPro 8 software. To identify which groups were
signicantly different from other groups, means comparison were
done employing a Tukey's test with a 95% condence level.
As it can be seen from tensile curves (Fig. 1-a), the neat PLA
lm showed a characteristic plastic deformation that it was
reduced with both, PHB and CNC incorporation. CNC and PHB
proved to be effective to increase PLA modulus (Fig. 1-b), but no
signicant differences were observed between the Young's
modulus of PLA-CNCs and PLA lms. While CNCs or PHB produced
a decrease on the tensile strength (TS) of PLA, the combination of
PHB and CNCs produce a nanocomposite (PLA-PHB-CNCs) with
comparable TS with respect to PLA. This behaviour can be related
with the more efcient dispersion of functionalized cellulose
nanocrystals (CNCs) [3] resulting in an enhancement in the
interfacial adhesion and therefore in a better interaction between
PLA and PHB [25]. Moreover, the PLA-PHB-CNCs lm revealed the
highest deformation at break, showing an increase of 175% with
Fig. 1. Tensile test results of PLA, PLA-PHB and nanocomposite lms: a) Stress-strain curves, b) Young's Modulus (E), c) Tensile strength (TS) and d) Elongation and break (B).
aed
Different letters on the bars within the same image indicate signicant differences between formulations (p < 0.05).
M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
Fig. 2. PLA, PLA-PHB and nanocomposite lms: a) UVeVis spectra, b) Visual appearance, c) contact angle measurements. aedDifferent letters on the bars within the same
image indicate signicant differences between formulations (p < 0.05).
143
Table 2
Colour parameters from CIELab space and YI of PLA, PLA-PHB and nanocomposite lms.
Samples
PLA
PLA-CNC
PLA-CNCs
PLA-PHB
PLA-PHB-CNC
PLA-PHB-CNCs
94.64
93.57
94.28
93.79
93.55
93.69
a*
0.01a
0.01b
0.01c
0.01d
0.01e
0.01f
0.98
1.08
1.01
1.07
0.91
1.04
b*
0.01a
0.02b
0.01c
0.01b
0.01d
0.01c
0.76
0.62
0.83
1.54
1.03
1.48
0.02a
0.02b
0.01c
0.01d
0.01e
0.01f
Different superscripts within the same column indicate signicant differences between formulations (p < 0.05).
DE
YI
e
1.08
0.37
1.15
1.12
1.19
0.70
0.52
0.82
2.14
1.29
2.07
0.01
0.01
0.01
0.01
0.01
0.03a
0.02b
0.02c
0.02d
0.01e
0.03f
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M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
Fig. 3. a) Visual appearance of lm samples before and after different incubation days under composting conditions. b) Degree of disintegration of lms under composting
conditions as a function of time.
M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
145
146
M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
Fig. 5. Optical micrographs (20) of PLA, PLA-PHB and nanocomposite lms and their EDF-z proles.
M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
147
Fig. 6. Infrared spectra (2000e1200 cm1) of PLA, PLA-PHB and nanocomposite lms before and after different time of incubation under composting conditions.
of crotonic acid (6.7 min, m/z 39, 41, 68, 69, and 86) [12,36], while
nanocomposte lms showed a peak at 22.5 min assigned to thermal
degradation products of the cellulose structure (m/z 55, 69, 87
and 103) [47]. The groups of small peaks appearing at retention
times between 19 min and 22 min were assigned to the thermal
degradation products of PLA with the characteristic series of signals
at m/z 56 (n 72) attributed to PLA degradation products such
as dimers (n 2) and trimers (n 3) [32]. In general, the intensity
of peaks decreased with composting time. However, the mesolactide intensity showed a lower decrease with respect to the (D,L)lactide equivalent. The ratio meso-lactide:lactide has been used as a
semi-quantitative sign of the degradation of PLA [12,32,36,48,49].
Fig 7(b) shows the reduction of (D,L)-lactide with respect to mesolactide after the pyrolysis of the recovered samples. No signicant
differences were observed between PLA and PLA-PHB blend until 7
days in composting, but after 10 days, the PLA relationship [lactide/
meso-lactidet10 days/lactide/meso-lactidet0 days] highly decreased.
Nanocomposites showed similar reduction in 3 days of composting,
but higher times revealed higher reduction for unfunctionalized
nanocomposites (PLA-CNC and PLA-PHB-CNC). The estimated
reduction of the (D,L)-lactide form with respect to the meso-lactide
followed a similar tendency that the disintegrability test. In this
sense, PLA-CNC and PLA-PHB-CNC showed the highest degradation
rate suggestive of the polymer shortening by the hydrolysis
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M.P. Arrieta et al. / Polymer Degradation and Stability 107 (2014) 139e149
Fig. 7. a) Py-GC/MS chromatogram of PLA-PHB-CNCs nanocomposite lm, b) mesolactide:lactide ratio loss of PLA, PLA-PHB and nanocomposite lms.
resulted in a higher amount of lactic acid. It is known that microorganisms prefer the L-lactide form of lactic acid rather than the Dform, thus there was a higher enzymatic degradation of L-lactide
inuencing the formation of a higher amount of meso-lactide form
during the pyrolysis test [48].
4. Conclusions
PLA-PHB based nanocomposite lms reinforced with synthesized CNC and functionalized CNCs intended for food packaging
were developed and characterized. A reduction of the viscosity
molecular weight of PLA, by approximately 5%, occurred due to
thermal processing reaching higher reduction with the presence of
CNC (10%) and CNCs (15%). Higher detriment of the viscosity molecular weight was observed for PHB after processing in PLA-PHB.
Conversely, in the case of PLA-PHB-CNC and PLA-PHB-CNCs, the
addition of nanocellulose improve the thermal stability leading to a
lesser reduction of PHB viscosity molecular weight and practically
unaffected the viscosity molecular weight of PLA. The combination
of PHB and the better dispersed CNCs demonstrated the reinforcing
effect increase simultaneously the Young modulus and elongation
at break, with comparable tensile strength to those of neat PLA. PHB
and functionalized CNCs showed a slight UV blocking effect on the
virtually transparent PLA matrix. Although the addition of PHB led
to a decrease in PLA high transparency, it did not compromise the
ultimate optical properties due to the low lm thickness achieved.
The presence of PHB increased the crystallinity of PLA and its
nucleation effect reduced the polymer chains mobility enhancing
the oxygen barrier performance of nal PLA-PHB blend lms while
the wettability was reduced. Moreover, functionalized CNCs, which
increases the polymer-nanoparticle interfacial adhesion, also
reduced the oxygen transmission at the same time as it decreased
the surface adhesive forces improving the water resistance. Finally,
CNC based nanocomposites showed the highest rate of disintegration in compost, while the surface hydrolysis of functionalized
CNCs nanocomposite lms started somewhat later and the presence of crystalline PHB delayed the disintegration process.
The results of this research suggest that the novel combination
of PLA-PHB blends and functionalized CNCs opens a new perspective for their industrial application as short-term food packaging.
Acknowledgements
This research was supported by the Ministry of Science and
Innovation of Spain (MAT2011-28468-C02-01 and MAT201128468-C02-02). M.P. Arrieta thanks Generalitat Valenciana (Spain)
for Santiago Grisola Fellowship (GRISOLIA/2011/007) and
cnica de Vale
ncia for the Development Support
Universitat Polite
Programme PAID-00-12 (SP20120120). The Authors acknowledge
Gesenu S.p.a. for compost supply. Authors gratefully thank Prof.
nez (University of Alicante, Spain) and Prof. Mara
Alfonso Jime
cnica de Vale
ncia) for
Dolores Salvador Moya (Universitat Polite
their assistance with OTR measurements and optical microscopeEDF measurements, respectively.
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