Polymer Degradation and Stability 97 (2012) 1822e1828

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Thermal, mechanical and morphological characterization of plasticized PLAePHB

blends
Mohamed A. Abdelwahab a, b, Allison Flynn b, Bor-Sen Chiou c, Syed Imam c, William Orts c,
Emo Chiellini a, *
a
Laboratory of Bioactive Polymeric Materials for Biomedical and Environmental Applications (BIOlab), UdR INSTM, Department of Chemistry & Industrial Chemistry,
University of Pisa, Via Risorgimento 35, 56126 Pisa, Italy
b
Lapol, LLC, 55 Castilian Dr., Santa Barbara, CA 93117, USA
c
USDA, Agricultural Research Services, WRRC-BCE 800 Buchanan Street Albany, CA 94710, USA

a r t i c l e i n f o a b s t r a c t

Article history: A blend of poly(lactic acid) (PLA) (75% by weight) and poly(3-hydroxybutyrate) (PHB) (25% by weight)
Received 23 April 2012 with a polyester plasticizer (Lapol 108) at two different concentrations (5 and 7% by weight per 100 parts
Received in revised form of the blends) were investigated by TGA, DSC, XRD, SEM, mechanical testing and biodegradation studies.
25 May 2012
PLA/PHB blends showed a good distribution of the major components and absence of phase separation.
Accepted 28 May 2012
XRD showed that the original crystal structure of PHB in the PLA75/PHB25 blend had been disturbed.
Available online 4 June 2012
DSC curves of PLA or PHB with plasticizer exhibited one Tg value, indicating that both major blend
components are miscible. The Tg values also decreased with increased amount of plasticizer and showed
Keywords:
Poly(lactic acid)
good correlation to the Fox Equation, The melting temperature of PLA and PHB blends mostly did not
Poly(3-hydroxybutyrate) change with an increase in plasticizer content, and the thermal stability of PLA and PHB was not affected.
Blend Also, the elongation at break of the PLA/PHB blend was greatly improved with the addition of plasticizer.
Plasticizer In addition, in preliminary biodegradation studies carried in natural compost neat PHB showed some
Thermal stability biodegradation, whereas the samples containing PLA did not experience a substantial biodegradation.
Mechanical properties This last aspect is worthy of further investigation in a more comprehensive and detailed approach.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, sustainability, environmental concerns and
green chemistry have played a big role in guiding the development
of the next generation of materials, products and processes. The
persistence of plastics in the environment, dwindling petroleum
resources, shortage of landfill space and the concerns over emis-
sions of toxic gases during incineration have fuelled efforts to
develop biodegradable polymers from renewable resources.
Particularly, renewable agricultural and biomass feedstock have
shown much promise for use in eco-efficient packaging to replace
petroleum feedstock without competing with food crops [1].
Poly(lactic acid) (PLA) is a biodegradable and biocompatible
crystalline polymer that can be produced from renewable resources
which is of great interest to the packaging industry due to its
* Corresponding author. Tel.: þ39 050 2210301; fax: þ39 050 2210332.
E-mail addresses: m_abedelwahab@ns.dcci.unipi.it (M.A. Abdelwahab),
emochie@dcci.unipi.it (E. Chiellini).
URL: http://syed.imam.ars.usda.gov
availability and low cost [2e5]. The properties of PLA are dependent
on the ratio between the two enantiomers D and L. PLA can show
crystalline polymorphism, which can lead to different melting peaks
[6,7]. Poly(3-hydroxybutyrate) (PHB) is a typical biodegradable
thermoplastic polymer produced by microorganisms. PHB is highly
crystalline polyester (80%) with a high melting point (173e180
C)
and a glass transition temperature (Tg) of approximately 1e5
C
[8e10].
Both PLA and PHB are biodegradable polyesters and are used in
consumer products by several industrial sectors due to their
biocompatibility, biodegradability and sustainability. They have
comparable thermal and mechanical properties to those of some
conventional polymers and this has generated much interest in
exploring their physical and processing properties for potential
applications [6,11,12].
It is noteworthy that both PLA and PHB have poor processing
properties and are brittle at room temperature [13]. Thus, several
modifications have been proposed to improve their processing and
mechanical properties, which include the preparation of copoly-
mers containing monomeric units derived from hydroxyl alkanoic
acids and blending these with PLA and PHB.

0141-3910/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.05.036
 M.A. Abdelwahab et al. / Polymer Degradation and Stability 97 (2012) 1822e1828
Blending is much easier and faster than copolymerization
methods [14e27]. Previous studies on PLA/PHB blends showed that
the miscibility between these two polymers depended on the
molecular weight of the second component [13,17,19,28]. PHB is
miscible with low molecular weight PLA (Mw < 18,000) in the melt
over the whole composition range, whereas the PHB blends with
high molecular weight PLA (Mw > 18,000) show biphasic separa-
tion [17,19]. Similarly, the PLA component is miscible with low
molecular weight PHB (Mw ¼ 9400) in the melt with the PHB
content up to 50 wt-%, and is immiscible with high molecular
weight PHB and commercial-grade bacterial PHB [13,28]. PLA/PHB
blends properties also depend on composition, chemical or phys-
ical cross-links and processing conditions. Zhang et al. [27] inves-
tigated the morphology, structure, crystallization behaviour,
thermal properties, mechanical properties, and biodegradation of
PLA/PHB blends, which were prepared by using melt compounding.
The PLA/PHB 75/25 blend showed improved mechanical properties
and heat distortion temperature and presence of some interactions.
Another way to improve blend compatibility is by using a compa-
tibiliser as a third component. Such compatibilisers include glycidyl
methacrylate (GMA) [29], poly(ethylene glycol) (PEG) [26] and
poly(vinyl acetate) (PVAc) [25].
PLA can be plasticized using oligomeric lactic acid (OLA), citrate
ester or low molecular weight additives [7,30,31]. Plasticization
increases the chain mobility and favours PLA crystallization. After
plasticization, the crystallinity is in the range between 20 and 30%.
The drawback of using these low molecular weight additives is that
they leach out of the PLA matrix, resulting in a brittle plastic over
time.
PHB can be plasticized with dioctyl phthalate, 1,4-
cyclohexanedimethanol dibenzoate, tert-butylphenyl phosphate,
PEG, triacetyl glycerol, tributyrin, dodecanol, lauric acid, trilaurin
and low molecular weight poly(adipate) [32e34]. Grillo Fernandes
et al. [35] blended PHB with polyols containing different amounts
and types of hydroxyl groups. Glycerol and PEG200 have been
shown to decrease the thermal stability of PHB. In contrast, tri(-
ethylene glycol) bis(2-ethylhexanoate) (TEGB) and pentaerythritol
had no effect on thermal stability of PHB. The mechanical testing
showed all samples were brittle, especially with PHB containing
20 wt-% of PEG. DSC results indicated that PEG200 and TEGB are the
most compatible with PHB.
At the USDA, a new polyester plasticizer has been developed
from mostly renewable resources. This plasticizer is in commer-
cial development and goes by the commercial name of Lapol 108
[36]. This plasticizer has high molecular weight (>80,000 Da), is
highly branched and is derived from more than 50% renewable
resources.
In this paper, we studied the effects of Lapol 108 on PHB, PLA
and PLA/PHB blends to create a new type of eco-friendly blend
material suitable for single-use applications, such as fast-food
packaging.
2. Experimental
2.1. Materials
The PLA (4032D, NatureWorksÒ Co. LLC, USA) had an average
molecular weight of 52,000 g mol1, a polydispersity (Mw/Mn) of 1.9
and a high optical purity with 98% L-lactide content. The poly(3-
hydroxybutyrate) (PHB) was BiocyleÒ (average molecular weight
(Mw) of 425 kDa and polydispersity of 2.51 supplied in kind by PHB
Industrial, SA, Serrana, SP, Brazil. Lapol 108 (Mw) of 80 kDa and
polydispersity of 26.6) was purchased from Lapol, LLC, Santa Bar-
bara, CA, USA. It was prepared according to the procedure described
previously [36].
1823
2.2. Preparation of the blends
The materials were pre-treated by drying at 85
C over drierite
for 24 h to eliminate possible absorbed water on the surface of the
particles. Blends were melt processed at 175
C for 5 min at 45 rpm
using a Haake Rheomix 600 with roller type blades. About 5 g of the
obtained blend was compression moulded on a laboratory Carver
press to obtain films of w300e500 ɲm. Moulding conditions were
set at 180
C for 3 min at 200 Bar.
2.3. Scanning electron microscopy (SEM)
Blend materials were fractured in liquid nitrogen to observe the
interior of the unstressed composite. A sample was dropped directly
into liquid nitrogen and fractured with a pre-chilled razor blade held
in a vice-grip. The fractured pieces were picked out of the liquid
nitrogen using pre-chilled forceps and placed in a desiccator to thaw
and reduce the condensation of water on the surface of the material.
All specimens were coated with gold-palladium for 45 s in a Denton
Desk II sputter coating unit (Denton Vacuum USA, Moorestown, NJ).
Specimens were viewed in a Hitachi S4700 field emission scanning
electron microscope (Hitachi HTA, Japan) at 2 kV.
2.4. Tensile properties
Young’s modulus, tensile strength, and elongation at break were
determined according to ASTM method D638M under ambient
conditions, using an Instron 5500R Universal Testing Machine
(Instron Corp., Canton, MA). Prior to testing, samples were equili-
brated at 50% relative humidity in a chamber containing saturated
solutions of calcium nitrate. The testing conditions used were: cross
head speed of 5 mm/min and load cell of 0.1 kN. Dumbbell samples
(0.2e0.5 mm thick) were tested with a gauge length of 20 mm. The
reported values were the average of at least 6 measurements. Data
points were the mean value of each measurement, with error bars
in each graph representing 95% confidence intervals.
2.5. Thermal properties
Thermogravimetric analysis (TGA) was performed under nitrogen
atmosphere in a TA Instruments TGA 2950. The samples were heated
from room temperature to 510
C at a heating rate of 10
C/min and
a nitrogen gas flow rate of 60 mL/min. The derivative of TGA curves
(DTG) was obtained using TA analysis software. Differential scanning
calorimetry (DSC) was performed with a Perking Elmer Jade DSC
8000 instrument calibrated with indium (T, DH) and zinc (T). DSC
samples of 10e15 g were weighed in a 40 ɲl stainless steel pan and
measured against an empty pan as reference. Measurements were
carried out under 80 ml min1 nitrogen flow rate according to the
following protocol: first and second heating from 20 to
200
C.min1; first cooling (quenching after first heating) from 200
to 20
C at 100
C.min1 and 2 min of isotherm at the end. In
particular, the first heating scan was used to erase any prior thermal
history of the sample and the second heating scan was used to
evaluate melting temperature (Tm) and crystallinity (Xc). The degree
of crystallinity Xc was calculated from DSC curves as follows (Eq. (1)):
DHm
Xc ¼  100 (1)
ð1  fÞDHm

where f is the weight fraction of the dispersed phase in the blends,
DHm is the melting enthalpy (J/g) that was calculated from the
fusion peak in the DSC curve and DH*m is the heat of fusion for
completely crystallized PLA (93.1 J/g) and for completely crystal-
lized PHB (146 J/g) [37,38].
1824 M.A. Abdelwahab et al. / Polymer Degradation and Stability 97 (2012) 1822e1828
2.6. X-ray diffraction
X-ray diffraction (XRD) analyses were performed with a Philips
1820 diffractometer operated at 45 kV and, 40 mA using Cu-Ka
radiation with a graphite diffracted beam monochromator. Data
were acquired in a 2q scale from 2
to 40
.
2.7. Biodegradation test
A Micro-Oxymax Respirometer System (Columbus Instruments
Inc., Columbus, OH) was used to monitor biodegradation of the neat
PHB, neat PLA, PLAePHB blend and PLAePHB-7%Lapol samples.
Pregelatinized wheat starch was used as a positive control. Each
sample (0.2 g) was mixed with 20 g of compost and kept in a 250-
mL sample chamber connected to a fully computerized, closed-
circuit system. Carbon dioxide evolution from each sample was
measured every 6 h for a total of 56 days at room temperature.
3. Results and discussion
3.1. Morphological properties
The morphologies of the fracture surfaces were investigated by
SEM, as shown in Fig. 1. Neat PLA presents a smooth and uniform
surface of an amorphous polymer containing some holes [Fig. 1(a)],
Fig. 1. SEM images of PLA (a), PHB (b), PLA-7%Lapol (c), PHB-7%Lapol (d), PLA75-PHB25 (e), PLA75-PHB25-Lapol5 (f) and PLA75-PHB25-Lapol7 (g).
whereas neat PHB shows an irregular fracture surface due to its
crystalline structure [Fig.1(b)]. PLA and PHB with 7 wt-% Lapol did not
show phase separation [Fig.1(c & d)]. Coarseness was observed on the
fracture surface of PLA75/PHB25, and the fractures in the blend
mainly developed along the same direction, indicating the resistance
to the development of fractures was quite low [Fig. 1(e)]. On the other
hand, the surfaces of specimens with Lapol were rougher than those
without Lapol, and fractures developed in different directions, as
shown in Fig. 1(f & g). Shear-yield and plastic deformation formed on
the fracture surfaces of blends with Lapol, especially for the blend
with high plasticizer content [(Fig. 1(g)]. Plastic deformation and the
different fracture directions required more energy and thus the
materials with Lapol should have better toughness.
3.2. XRD analysis
X-ray diffraction analysis was used to determine crystalline
structure and degree of crystallinity in the blends. PHB is a highly
ordered polymer and is known to crystallize in an orthorhombic
cell [39,40]. The lattice parameters of PHB are: a ¼ 0.572 nm and
b ¼ 1.312 nm with its chain conformation in the left-handed 21
helix. In the orthorhombic cell, the three axis are mutually
perpendicular (¼b ¼ g ¼ 90
) and of unequal length (a s b s c)
[37]. PLA can be crystallized from the melt as an orthorhombic unit
cell with lattice parameters of a ¼ 1.037 nm and b ¼ 0.598 nm2.
 M.A. Abdelwahab et al. / Polymer Degradation and Stability 97 (2012) 1822e1828 1825

Neat PLA is usually formed from the -type helix 103. PLA can form
two types of crystals, depending on the crystallization conditions.
These are the form with a 103 helical shape and the b form with
a spiral shape 31 [2,22,41e43]. PHB has reflection peaks at 13.5
and
16.8
, corresponding to the (020) and (110) planes, and three weak
peaks at 19.1
, 22.2
and 25.5
, with the first two peaks typical of
the form orthorhombic structure [2]. The PLA had only one broad
diffraction peak at 2 of 15
corresponding to the (110/200) reflec-
tions (d ¼ 0.536) and smaller peaks at 19.1
and 32
corresponding
to (010) and (203), respectively.
In general, the patterns of PLA and PHB with Lapol blends are
very similar to that of neat PLA and neat PHB (Fig. 2). It can be
observed that diffraction at 2 ¼ 13.5
and 16.9
for PHB-7%Lapol
had increased in intensity. For the PLA75/PHB25 blend, the peak
located at 16.9
is too weak to be observed in the pattern.
Furthermore, the presence of amorphous PLA significantly reduces
the crystallinity of the PLA/PHB samples. This is due to the reduc-
tion in the PHB content and the PLA interfering with crystallization
of PHB. For the PLA75/PHB25 blend, as shown in Fig. 2, the intensity Fig. 3. DSC traces of the 2nd heating scan of PLA, PHB, Lapol and PLAePHB-Lapol
blends.
ratio I(020)/I(110) is different from that of neat PHB. This indicates
that the crystal structure of PHB in the PLA75/PHB25 blend has
and a melting temperature of 178.5
C. These values were similar to
been altered from interactions between PLA and PHB. Since the
those reported in literature [35]. As summarized in Table 1, Lapol
crystallinity and the crystal growth rate of PHB are higher and faster
had only one Tg at 0.7
C. In general, the DSC curves of PLA or PHB
than those of PLA, the reflection peaks of PHB are observed even
with plasticizer (Lapol) blends exhibit one Tg value, which indicates
with higher PLA content. PLA75/PHB25/7Lapol did not have a peak
that both blend systems are miscible systems [44e47]. The
(110) at 16.9
and had a weak peak (020) at 13.5
. This implies that
dependence of Tg, blend (glass transition temperature of the blend)
the addition of Lapol significantly improves the crystallinity and
on the composition of the blends follows the Fox relationship [44]
crystallization rate of the PLA75/PHB25 blend.
(Eq. (2)):

3.3. Thermal and crystallization behaviour 1 W W

The thermal properties of the blends could be significantly
affected by the crystallization characteristics of PHB and PLA. DSC
traces recorded during the second heating cycle of the polymer
samples are presented in Fig. 3. The measurements were performed
immediately after the melt-quenching scans, thus the samples had
the same thermal history and could be compared directly. The
curves revealed similar thermal events for all samples, as follows:
the glasserubber transition (characterized by Tg), cold crystalliza-
tion process (characterized by Tcc and the cold crystallization
enthalpy (DHcc)), and the melting process (characterized by Tm and
the melting enthalpy (DHm)). The neat PLA sample showed a Tg of
63
C, an exothermic crystallization peak at 113
C and an endo-
thermic melting peak at 173
C. Similarly, the neat PHB sample
showed a Tg of 5.2
C, an exothermic crystallization peak at 48
C
¼ 1þ 2 (2)
Tg;blend Tg1 Tg2
where W1 is the mass fraction of component 1, W2 is the mass
fraction of component 2, Tg1 is the glass transition temperature of
component 1 and Tg2 is the glass transition temperature of
component 2. Using Tg values of 62.9
C, 5.2
C and 0.7
C for neat
PLA, PHB and Lapol, respectively, we calculated theoretical Tg, blend
values of 59
C for PLA with 5 wt-% Lapol, 57.5
C for PLA with 7 wt-
% Lapol, 4.9
C for PHB with 5 wt-% Lapol and 4.78
C for PHB with
7 wt-% Lapol. These values are in good agreement with the exper-
imental values.
On the other hand, the DSC curves of PHB75/PLA25 blends
exhibit two Tg values, which indicates that these blends are
immiscible systems. However, addition of Lapol to the PLA75-
PHB25 sample resulted in disappearance of the Tg of Lapol
and a decrease in Tg values of PHB and PLA. These behaviours
suggest that Lapol has a significant effect on the PLAePHB
macromolecules.

Table 1
DSC parameters (2nd heating) of PLAePHB/Lapol Blends.a

Code Tg1 Tg2 Tcc Tm DHcc DHm Xc

(
C) (
C) (
C) (
C) J/g J/g (%)
PLA e 63 115 173 30 33 35
Lapol 0.7 e e e e e e
PLA-5%Lapol e 60 110 173 29 31 35
PLA-7%Lapol e 58 110 172 29 31 37
PHB 5.2 e 48 179 22 72 49
PHB-5%Lapol 5.8 e 49 177 25 69 50
PHB-7%Lapol 4.6 e 50 178 25 63 48
PLA75-PHB25 1.7 62 115 173 16 13 36
PLA75-PHB25-Lapol 5 2.7 59 125 172 24 26 40
PLA75-PHB25-Lapol 7 0.6 58 120 173 24 24 38
a
Tg, Tm are the glass crystallization and melting peak temperatures, respectively,
DHm is the enthalpy of melting, DHcc is the cold crystallization enthalpy and Xc is the
Fig. 2. XRD of PLA, PHB and PLAePHB-Lapol blends. degree of crystallinity.
1826 M.A. Abdelwahab et al. / Polymer Degradation and Stability 97 (2012) 1822e1828

The cold crystallization temperature (Tcc) of PLA decreased and

that of PHB increased with an increase in plasticizer content. This
corresponded to a decrease of DHcc in PLA blends and an increase of
DHcc in PHB blends. However, PLA75/PHB25 had higher cold crys-
tallization temperature and its peak became broader with an
increase in Lapol concentration. This is possibly due to the small
finely dispersed PHB crystals acting as nucleating agents in PLA. The
presence of one crystallization temperature suggested that the PLA/
PHB blend has a significant single homogeneous phase through the
heating process. These results agree with previous studies by Hu
et al. [20], Zhang et al. [48] and El-Hadi [25]. From Table 1, the shifts
in the cold crystallization peaks (by approximately 11
C and 7
C
for 5 wt-% and 7 wt-% of Lapol, respectively) is related to the
difference in flexibility of the chains and their ability to form
a crystalline structure.
Melting temperature (Tm) of the PLA and PHB blends mostly did
not change with increasing amount of plasticizer. It is interesting to
note that the PLA/PHB blend exhibits two melting peaks at 169
C
and 173
C (Table 1 shows only one melting peak for the blends),
which are attributed to recrystallization or two different lamella
thickening. These results are in agreement with the results of
Gunaratne et al. [49]. However, the presence of double melting
temperatures in the PLAePHB-Lapol blends corresponds to the
melting of “as formed” and recrystallized PHB crystallites. Ikehara
et al. [50] stated that when miscible crystalline/crystalline blends
are crystallized from a homogeneous melt, the crystallization
behaviour largely depends on the difference in the melting point of
the two components. When the Tm difference is large, the
component with higher Tm crystallizes first, and its spherulites
usually fill the whole volume. The lower Tm component crystallizes
at a lower temperature in spatially limited regions inside the
spherulites of the other component. When the difference in Tm is
small enough, both components have a high possibility to crystal-
lize simultaneously. The Tm difference in most of the miscible
crystalline/crystalline blends reported so far was approximately Fig. 4. a) TGA of PLA, PHB, PLAePHB based blends and b) DTG of PLA, PHB and
PLAePHB based blends.
100
C. In these cases, the two components crystallize at different
temperatures. In this study, the Tm difference between PHB and PLA
is about 5.8
C, indicating that simultaneous crystallization has
occurred. for the 5 and 7 wt-% Lapol samples. PHB and PLA thermally degrade
The degree of crystallinity (Xc) of PLA and PHB based blend was to produce polymeric chains terminated with carboxyl and vinyl
basically uniform. A higher value of Xc was observed for PLA with groups [53]. Carboxyl end groups of polyester catalyse hydrolysis
7 wt-%Lapol and for PHB with 5 wt-%Lapol. According to Azuma reaction. In the present study, it is feasible that a synergistic effect
et al. [51] and Janigova et al. [52], an increase in crystallinity is due occurred to accelerate thermal degradation of PLA by moisture and
to higher chain mobility and a better packing of segments. The polyol [54,55]. The Tonset of PLA75/PHB25 blend was between those
incorporation of Lapol in PLA75-PHB25 slightly increased Xc by 4% of PLA and PHB. The addition of Lapol led to a slight shift in Tonset of
for the 5 wt-% Lapol sample and by 2% for the 7 wt-% Lapol sample, PLA/PHB blend to a higher temperature, as shown in Table 2. This
as shown in Table 1. This behaviour could be dependent on the phenomenon was attributed to the higher thermal stability of
chain mobility of the polymer. Also, the interface interactions Lapol.
between PHB and PLA with Lapol could influence nucleation as Another important thermal property is the temperature corre-
supported by the XRD results presented in Fig. 2. In addition, the sponding to the maximum rate of weight loss (Tp), which is defined
decrease in DHm values of all blends might imply formation of
a more stable structure, perhaps due to increased movement of the Table 2
polymer segments that facilitate polymer chain mobility. TGA data of PLA/PHB/Lapol blends.a

Code Tonset (
C) Tp PHB (
C) Tp PLA (
C) R500 (%)

3.4. Thermogravimetric analysis (TGA)
PLA 324 e 357 0.12
Lapol 278 e 340 8.94
Thermal degradation of plasticized PLA and PHB samples is PLA-5%Lapol 313 e 356 0.16
shown in Fig. 4(a & b). In general, the thermal weight-losses of PHB PLA-7%Lapol 312 e 357 0.86
and PLA were quite sensitive to temperature, with narrow PHB 260 279 e 0.25
PHB-5%Lapol 264 281 e 0.54
decomposition temperature ranges. The temperature correspond-
PHB-7%Lapol 264 282 e 0.53
ing to the onset of decomposition (Tonset) for a polymer is essential PLA75-PHB25 270 283 356 0.10
for evaluating its thermal stability and is summarized in Table 2. PLA75-PHB25-Lapol 5 273 284 357 0.86
PLA is more thermally stable than PHB. Lapol decreased the Tonset of PLA75-PHB25-Lapol 7 271 283 341 0.93
PLA by 11
C for the 5 wt-% Lapol sample and by 12
C for the 7 wt-% a
Td is the onset temperature; Tp is the first derivative peak; and R500 is the
Lapol sample. In contrast, Lapol increased the Tonset of PHB by 4
C residual weight at 500
C.
 M.A. Abdelwahab et al. / Polymer Degradation and Stability 97 (2012) 1822e1828 1827

as the peak value of the first derivative of the TGA curve. The first
and second derivatives curves for neat PLA, neat PHB and PLAePHB
based blends are shown in Fig. 4(b) and their Tp values are listed in
Table 2. All neat polymers exhibited a single peak, indicating that
the PLA and PHB degraded in only one step. In addition, the Tp of
PLA and PHB with Lapol shifted slightly to higher temperature.
However, the Tp value of PLA75/PHB25 showed a decrease with
increasing amounts of Lapol. All samples had less than 1 wt-%
residue at 500
C and this value increased with increasing plasti-
cizer content.

3.5. Mechanical properties

Young’s modulus, strain at break and stress at break values of

melt-mixed PLA, PHB and PLAePHB based blends are presented in
Table 3. The mechanical behaviour of the neat PLA showed char-
acteristics of glassy polymers with low deformation at break. In
contrast, the neat PHB has a low melt viscosity and is a brittle
material with a higher modulus. The blends of PLA and PHB with
Lapol showed different behaviour. PLA with 5 wt-% Lapol had
a higher Young’s modulus (YM) than that for neat PLA. However, Fig. 5. Carbon dioxide evolution of the pregelatinized wheat starch, neat PHB, neat
PHB with 5 wt-%Lapol had a lower YM than that of neat PHB. The PLA, PLAePHB blend and PLAePHB-7%Lapol samples as a function of time.
YM of the PLA75/PHB25 sample was lower than that of neat PLA
and addition of plasticizer resulted in even lower values. The tensile
strength was significantly reduced by addition of Lapol, but the comparison, the samples containing PLA did not generate much
elongation at break increased in value. Tensile strength of PLA75/ carbon dioxide, indicating these samples did not degrade much
PHB25 was lower than those of PLA and PHB, with no change in the under the experimental conditions. This last aspect is worthy of
elongation at break (w7%). The addition of Lapol markedly changed further investigation in a more comprehensive and detailed
the stress-strain behaviour of the PLA75/PHB25 blend. The PLA75/ approach.
PHB25 blend with 5 wt-%Lapol had a higher elongation at break
value than neat PLA and neat PHB. However, its tensile strength was
4. Conclusions
lower than neat PLA and neat PHB. The PLA/PHB/Lapol samples
showed some characteristics of flexible materials. These improve-
Biodegradable PLAePHB blends have been successfully
ments might be due to the finely dispersed Lapol acting as fillers,
prepared by melt mixing PLA, PHB and a new type of plasticizer
which enhanced the properties of neat polymer. They can also be
(Lapol 108). This compounding technique is easy and potentially
due to possible interactions between PHB and PLA, with Lapol
commercially viable. SEM showed that PLA and PHB with plasti-
causing strong interfacial bonding.
cizer exhibited a homogeneous distribution of Lapol 108 in the
polymer matrix. Samples of ternary blends also showed homoge-
3.6. Biodegradation results
nous distribution. XRD data showed that Lapol 108 was affecting
the interlayer space of the blends. Moreover, Lapol 108 essentially
The data herewith reported are referred to a preliminary study
decreased the Tg for all of the binary and ternary blends. Also,
relevant to the biodegradation of PHB, PLA and two blends of PLA/
crystallinity in the PLA75-PHB25 sample slightly increased with
PHB.
increased loading of Lapol 108. On the other hand, thermal
The neat PHB sample showed some biodegradation during the
decomposition properties of the blends were not affected by Lapol
measurement time period, whereas the other polymer samples did
108. The addition of Lapol caused the elongation at break to
not degrade much. This is shown in Fig. 5, which displays carbon
increase and the Young’s modulus to somewhat decrease compared
dioxide evolution of the samples as a function of time. The starch
with neat PLA and neat PHB. Also, the neat PHB sample showed
sample seemed to degrade the fastest since it generated the largest
some biodegradation, whereas the samples containing PLA did not
amount of carbon dioxide. Meanwhile, the neat PHB sample
degrade much during the experimental time period.
exhibited an increase in carbon dioxide content up to approxi-
mately 40 days, but this content levelled off thereafter. In
Acknowledgement
Table 3
Tensile properties of PLA/PHB/Lapol blend films.a The work reported here is part of the activities performed by
Code Young’s Tensile Elongation M.A. Abdelwahab for the achievement of the PhD title in Bioma-
modulus (MPa) strength (MPa) at break (%) terials as granted by the University of Pisa (Italy).
PLA 1400  130 42  18 7.2  2
PLA-5%Lapol 1450  180 14  2 14.4  1
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