Polymer Testing 49 (2016) 22e28

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material properties

Fully bio-based and biodegradable polylactic acid/poly(3-

hydroxybutirate) blends: Use of a common plasticizer as performance
improvement strategy
D.A. D'Amico, M.L. Iglesias Montes, L.B. Manfredi, V.P. Cyras*
Institute of Materials Science and Technology (INTEMA), University of Mar del Plata e National Research Council (CONICET), Av. Juan B. Justo 4302, 7600
Mar del Plata, Argentina

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

Article history: Biodegradable polymeric blends based on poly(3-hydroxybutyrate) (PHB) and polylactic acid (PLA) were
Received 16 September 2015 prepared by melt mixing. Trybutyrin, a bio-based plasticizer, was added at a fixed proportion in all
Accepted 3 November 2015 blends. Crystal structure, percent crystallinity, miscibility, mechanical properties and permeation of fully
Available online 10 November 2015
biodegradable PHB/PLA blends were investigated in detail by Differential Scanning Calorimetry (DSC),
Fourier Transformed Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electron Microscopy
Keywords:
(SEM), tensile tests and water vapor permeation tests. From the thermal test, two glass transition
Blends
temperatures were found for the whole range of compositions, which reveals the immiscibility between
Polylactic acid (PLA)
Poly(3-hydroxybutyrate) (PHB)
PHB and PLA. Moreover, the biphasic melt further confirms this fact. Tensile tests showed an increase in
Processing the elongation at break with the PLA content. SEM images reveal debonding between the interfacial
Bio-based polymers surfaces, which justifies the increase in the elongation at break. Water vapor permeation values for
blends were slightly higher than that of the plasticized pristine polymer. The plasticized polymer blends
showed valuable properties to extend the applications of PHB and PLA.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction and degradation temperatures [1,2]. Different strategies have been

studied with the aim of improving its mechanical and thermal
In recent years, there has been an expansion of biopolymer properties, such as the preparation of nanocomposites with nano-
research activities in order to overcome the environmental impact fillers [3,4] or the addition of another polymer to obtain blends [5].
produced by petroleum-based plastic residue. Among the vast Polymer blends represent an interesting strategy to adjust certain
number of biopolymers studied, two of the most promising are properties of the polymers. However, it is generally very difficult to
poly(3-hydroxybutyrate) (PHB) and polylactic acid (PLA), both improve a property without detriment of others. PLA appears as a
biodegradable and biocompatible polyesters that can be produced good alternative for blending with PHB.
from renewable resources. PLA is a semi-crystalline polyester derived from lactic acid, ob-
PHB is a natural polymer synthesized by different species of tained entirely from renewable resources such as corn, sugar beet
bacteria as an intracellular storage material with a remarkable and wheat. The glass transition temperature of PLA is in the range
stereo-regularity of the perfectly isotactic chain configuration, of 50
Ce80
C while the melt temperature is in the range of
which gives it unusually high crystallinity. It is a crystalline ther- 130
Ce180
C. It has greater mechanical strength and easier pro-
moplastic polyester with similar properties to those of synthetic cessability than PHB. Although PLA is compatible with many cur-
polypropylene; it presents a high melting point (173e180
C) and a rent processing techniques, the fact that it has a high glass
glass transition temperature around 5
C. The main drawbacks of transition temperature leads to brittleness in the final products [6].
PHB are that it is mechanically fragile and shows a narrow window From this viewpoint, a good balance of amorphous and crystalline
for the processing conditions due to the proximity of the melting domains (45e50%) along with low Tg (10
C) is an ideal target to
aim for. Therefore, a lowering of Tg and crystallization temperature
(Tc) as well as an increase in crystallinity are goals for improved in
* Corresponding author. PLA based materials. Changes in PLA packing structure to shift Tc
E-mail address: vpcyras@fi.mdp.edu.ar (V.P. Cyras). have been reported [6]. Conventionally, addition of a nucleating

http://dx.doi.org/10.1016/j.polymertesting.2015.11.004
0142-9418/© 2015 Elsevier Ltd. All rights reserved.
 D.A. D'Amico et al. / Polymer Testing 49 (2016) 22e28 23

agent is the simplest way to induce crystallization [7]. In addition, 2.3. Characterization techniques
the use of PLA is limited by its low heat resistance [8] and poor
barrier properties [9]. X-ray diffraction (XRD) analysis was performed on the blend
In order to overcome the aforementioned difficulties, several films using an X-Pert pro diffractometer, operating at 40 kV and
authors have formulated blends of PHB/PLA by using limonene [5], 40 mA, with CuKa radiation (l ¼ 1.54 Å), at a scanning speed of 1.5
/
polyethylene glycol (PEG) [10] as plasticizers and also by blending min. The crystallinity index was calculated by dividing the crys-
PLA with atactic PHB [11] and other PHB copolymers [12,13]. While talline area by the total area (crystalline þ amorphous) [15].
some improvement has been obtained, parameters such as the Scanning differential calorimetry (DSC) was carried out on a
elongation at break have not shown significant improvements, and Pyris 1, Perkin Elmer. The mass of each sample was 10e12 mg and
the influence on the barriers properties when a hydrophilic plas- the carrier gas was nitrogen at a flow rate of 20 mL/min. The
ticizers is added, such as PEG, has not been extensively studied. scanning process comprised initial heating from 50
C to 190
C at
In this work, different PHB/PLA blend compositions were pro- 10
C.min1 followed by cooling from 190
C to 50
C at
cessed. A natural hydrophobic plasticizer, tributyrin (TBL), was used 80
C.min1 and, finally, a second temperature scanning
to facilitate the polymer processability. TBL is a natural triglyceride from 50
C to 190
C at 10
C min1. The glass transition tem-
present in fats and oils that has shown to be a good candidate as perature (Tg), cold crystallization temperature (Tcc) and melting
plasticizer for bio-based polymers [14]. temperature (Tm) of both polymers were determined. The degree of
The aim of this work is to obtain and characterize PHB/PLA crystallinity (Xc) was calculated using the following Equation (Eq.
blends with improved mechanical properties, through the addition (1)):
of a natural mutual hydrophobic plasticizer, without altering
considerably the good properties of the pristine polymers. This DHm:i  DHcc:i
Xci ¼ (1)
should be important to modify the properties and extend the DHm:i
0 $f
i
practical application of these biodegradable polymers. Finally,
concern was given to understand the relationship between struc- where i subscript indicates the polymer in the blend, f is the mass
ture, composition and properties of the blends. fraction of the polymer in the blend, DHm.i is the melting enthalpy,
DHcc.i is the enthalpy of cold crystallization, DHm0 is the melting

enthalpy of PHB or PLA 100% crystalline (146 J/g and 93 J/g,

2. Materials and methods respectively) [16]. Reported values were the average of at least 3
scans.
2.1. Materials Fourier Transform Infrared spectroscopy analysis in attenu-
ated total reflectance (FTIR-ATR) was performed using a Thermo
PHB (kindly supplied by PHB Industrial S. A., Brazil) Scientific Nicolet Instrument 6700 in the range 400e4000 cm1 by
(Mw ¼ 2,46,000) and PLA, with a molecular weight Mn ¼ 88,500, performing overlapping 32 scans at a resolution 4 cm1, at room
(NatureWorks®) were used as polymeric hosts. TBL was purchased temperature.
from Fluka and was employed as plasticizer for both polymers. Mechanical properties of the samples were determined using a
universal testing machine, INSTRON 4467. Uniaxial tensile tests
were performed at a traverse rate of 1 mm/min, using dumbbell
specimens (ASTM D1708-93). Reported values were the average of
2.2. Preparation of the blends at least 5 valid tests.
Scanning electron microscopy (SEM) was employed using a
In order to obtain the blends, the raw PHB and PLA pellets were microscope JSM 6460. In order to observe the morphology of the
mechanically mixed with the TBL prior to melting in a Haake mixer samples, fracture surface from films broken in liquid nitrogen were
at 185
C and a screw rotation speed of 50 rpm for 3 min. Blends analyzed. All the samples were coated with a thin gold foil.
were then molded into films (thickness: 100 mm) at 190
C in a hot Water vapor permeation (WVP) of the materials was deter-
press. The materials were kept between the plates at atmospheric mined according to ASTM E 96-9500e1. CaCl2 was used as a drying
pressure for 1 min until melting and then for 2 min at 5 MPa. The agent, previously dried in an oven as detailed in the standard.
PLA and PHB pellets were previously dried in a vacuum oven at Teflon capsules of 5 cm of diameter were used. The capsules were
80
C overnight. The proportion polymer blend/plasticizer was placed in a chamber at 65% relative humidity at an average tem-
remained at 80/20wt.% in the different blends of PHB/PLA ratios: perature of 18
C. Until steady state was reached, weight mea-
100/0, 70/30, 60/40, 50/50, 40/60, 30/70 and 0/100. The samples surements were performed at regular time intervals. The WVP of
were designated as listed in Table 1. In the same way, in order to the films was calculated according to Equation (2):
determine the miscibility between the plasticizer and each poly-
mer, blends of polymer/TBL in 90/10, 85/15, 80/20 and 75/25 wt. WVTR$d
ratio, were prepared. The pure polymers without TBL were also WVP ¼ (2)
DP
processed in order to be used as reference materials.
where WVTR is water vapor transmission rate through the film (g/
m2.s), d is the average film thickness (m) and DP is the difference in
Table 1
partial vapor pressure (Pa) between both sides of the film. Reported
Name and description of the composition of the materials studied.
values were the average of at least 3 tests.
Name PHB/PLA/TBL (wt.%)

PHB-TBL20 80/0/20
3. Results and discussions
PHB/PLA (70/30) 56/24/20
PHB/PLA (60/40) 48/32/20
PHB/PLA (50/50) 40/40/20 In order to investigate the crystalline structure and to calculate
PHB/PLA (40/60) 32/48/20 the degree of crystallinity of PHB/PLA blends, XRD tests were per-
PHB/PLA (30/70) 24/56/20 formed. The diffractograms of PHB/PLA blends in the whole range
PLA-TBL20 0/80/20
of compositions are shown in Fig. 1a. PHB is a highly ordered
24 D.A. D'Amico et al. / Polymer Testing 49 (2016) 22e28

Fig. 1. a) DRX diffractograms for PHB, PLA and theirs blends. b) Shoulder in PHB/PLA (70/30) blend.

polymer and crystallizes in an orthorhombic cell form. Character- Fig. 2 shows the first heating scan for all the materials processed.
istic PHB diffraction peaks appear at 13.5
, 16.9
and three weak at The glass transition temperature is one of the most important
19.9
, 22.3
(typical structure of orthorhombic form) and 25.5
[16], miscibility criteria in polymer blends [18]. When each polymer was
which almost coincides with the PLA diffraction peaks. In this case, mixed with TBL, a single Tg was observed, which was reduced by
for pure processed PLA no diffraction peaks were observed, which 30
C and 25
C for PHB and PLA, respectively. Therefore, in both
indicates that the PLA displays amorphous structure. However, cases, it can be inferred that the plasticizer chosen was miscible
when 20wt.% of TBL was added to PLA, a diffraction peak at around [19].
16.6
appears. That peak also appeared in all blends, like a shoulder To further deepen the study of the compatibility PHB/TBL and
on the highly intense diffraction peak at 16.9
of the PHB, which PLA/TBL, the Nishi and Wang model was used [20], which is based
becomes broader than in the pure PHB diffraction pattern. The on the Flory-Huggins Theory. According to Flory-Huggins theory,
presence of that shoulder was more clearly shown in the dif- the melting point depression is related to the interaction parame-
fractogram of PHB/PLA (70/30) blend (Fig. 1b) in the range from 14 ters, c1,2, through the following relation:
to 22
. Also, the pattern of the blends showed that the intensity of
the diffraction peaks at 16.9 and 16.6
, representative of PHB and 1 1 RV2
 0 ¼ $c f2 (3)
PLA, respectively, varied in the same way than the composition of Tmi Tmi DHmi $V1 12 1
each polymer, revealing that PHB and PLA crystallize separately in
the blends. Therefore, blending two plasticized semicrystalline where subscripts 1 and 2 represent the pure and the plasticized
polymers, PHB and PLA, the crystal structure of the each polymer polymer, respectively, and subscripts i represent each polymer; Tmi
0 are the equilibrium melting point of the crystallizable
and Tmi
was not modified but the intensity of the XRD diffraction peaks
were reduced in the blends [17]. component in the pure state and the blend, respectively; R is the
Crystallinity plays a very important role in the physical prop- universal gas constant; Vi is the molar volume of the respective
erties of biodegradable polymers, such as thermal and mechanical, component (VPHB ¼ 75 cm3 mol1 VPLA ¼ 57.7 cm3 mol1,
and also affects biodegradability. The degree of crystallinity was
calculated only for pure and plasticized polymers (Table 2) because
the diffraction peaks of PHB and PLA overlapped each other
(Fig. 1b). As expected from the diffractograms, the index of crys-
tallinity of plasticized PLA was three times higher than the pure
polymer, while the crystallinity of PHB, a highly crystalline polymer,
does not change with the addition of plasticizer.
Due to the difficulty in accurately estimating the crystallinity
values of each component with XRD tests, DSC experiments were
used because they represent an excellent alternative to assess this
parameter. From these experiments, important thermal properties
of each blend, such as glass transition temperature, cold crystalli-
zation temperature and melting temperature can be obtained.
Additionally, the miscibility between both polymers can be
evaluated.

Table 2
Index of crystallinity for pure and plasticizer polymers.

Material Index of crystallinity (%)

PHB 74.9
PHB-TBL20 75.9
PLA-TBL20 12.9
PLA 4.0
Fig. 2. First DSC scans for PHB, PLA and theirs blends.
 D.A. D'Amico et al. / Polymer Testing 49 (2016) 22e28 25

Table 3
Thermal properties of PLA, PHB and theirs blends.

Material Tg (
C) Tcc (
C) Tm (
C) DHcc (J/g) DHm (J/g) Xc (%)

1a 2 1a 2 1 2 1a 2a 1 2 1 2

PHB 2.2 e 53 e 176 e 35 e 91 e 62 e

PHB-TBL20 27 e 19 e 165 e 18.5 e 73 e 60.3 e
PHB/PLA(70/30) 27 3.6 e 62.4 166 142 e 2.1 50 10 60.9 35.2
PHB/PLA(60/40) 27 3.2 e 62.2 166 142 e 3.3 42 13 60 31.7
PHB/PLA(50/50) 30 2.5 17.5 62.1 165 142 4 3.1 36 14 61.2 29.5
PHB/PLA(40/60) 23 19 23.7 70.3 167 146 5.5 7.7 28.5 16 61 18.4
PHB/PLA(30/70) 28 12 21 62.1 165 144 2 7 22 18 62.8 21.7
PLA-TBL20 e 28 e 75.8 e 150 e 18 e 28 e 13.7
PLA e 53 e 114 e 155 e 25 e 27.4 e 2.7

1: PHB, 2: PLA.
a
Second scan.

VTBL ¼ 292 cm3 mol1 [21,22]); DHmi is the heat of fusion per mole of
repeat unit and fi is the volume fraction of each polymer compo-
nent in the blend obtained as the ratio between the mass fraction
and the density of the amorphous phase of each polymer
(dPHB ¼ 1.15, dPLA ¼ 1.25 dTBL ¼ 1.032 g/cm3 [21,22]). A plot of the left-
hand side of Equation (3) versus the square of the PHB or PLA vol-
ume fraction fi in the blend can be used to estimate the PHB/TBL
and PLA/TBL interaction parameters c12. This should give a straight
line passing through the origin if c12 is independent of the
composition and the melting point depression is not influenced by
morphological effects.
The c12 values found to PHB/TBL and PLA/TBL were 8.6
and 2.2, respectively, which indicates miscibility between both
polymers and TBL.
The miscibility between PHB and PLA has been studied. PLA and
PHB were reported immiscible unless the molecular weight of PLA
and/or PHB is very low [23,24,25]. DSC experiments reveal two Tg
for blends PHB/PLA/TBL (Table 3), one for each biopolymer, indi-
cating the immiscibility between them. However, the Tg values of
the PLA in the blends were lower than that of PLA-TBL20 (Table 3). Fig. 3. FTIR spectra of PHB/PLA/TBL blends.
This could be due to the partial miscibility between PHB and PLA,
which would be evident in the further reduction in the Tg of each
polymer [13]. A reduction of 10
C was found in the melting tem- Table 4
Mechanical properties for the materials.
perature of each plasticized polymer matrix, which is further evi-
dence of miscibility between the polymer and the plasticizer. Material E (GPa) sb (MPa) εb (%)
Moreover, regardless of the composition of the blends, two Tm, PHB 2.23 ± 0.20 34.6 ± 2.6 4.1 ± 1.5
corresponding to each polymer were found. Tm values in the PHB-TBL20 0.82 ± 0.07 11.2 ± 0.8 2.2 ± 0.2
mixtures did not vary significantly compared to plasticized PHB/PLA(70/30) 0.5 ± 0.07 11.0 ± 0.6 12.5 ± 5.2
polymers. PHB/PLA(60/40) 0.35 ± 0.02 9.5 ± 0.8 30.7 ± 9.7
PHB/PLA(50/50) 0.33 ± 0.04 9.0 ± 1.7 45.1 ± 34.7
The two endothermic peaks corresponding to the melting of PHB/PLA(40/60) 0.53 ± 0.15 13.7 ± 0.9 148.8 ± 19.4
each polymer, and the exothermic peak of cold crystallization of PHB/PLA(30/70) 0.07 ± 0.01 14.4 ± 1.8 193.2 ± 51.0
PLA, were considered to calculate the degree of crystallinity in the PLA-TBL20 1.85 ± 0.20 27.4 ± 3.3 5.2 ± 1.7
blends (Table 3). PLA 2.80 ± 0.20 55.9 ± 2.9 4.8 ± 2.2
PLA crystallinity increased with the PHB content, as was shown
in the XRD test, probably due to the PHB crystals that may act as
nucleating agents [26]. This is evidenced by reductions of 14
C and corresponding to the asymmetric stretching of the carbonyl group
50
C in the cold crystallization temperatures of PLA in the blends in C]O near 1720 cm1 was observed for all compositions [5]. It was
relation to those of the plasticized and pure polymer, respectively found at 1747 cm1 and 1718 cm1 for pure PLA and PHB, respec-
[27]. Also, the increment in the polymer chain mobility, displayed tively. As expected, that peak shifted from 1747 cm1 to 1718 cm1
by a reduction in Tg, favored the crystallization process, as shown as PLA content decreased in the blends. It can be seen that the in-
by the higher degree of crystallinity of the plasticized PLA tensity of these peaks increases with the composition of each
compared to the pure PLA (Table 3) [7,28]. polymer, which suggests that the material is macroscopically
PHB crystallinity remained nearly constant. The same behavior homogeneous.
was found in our previous work, where the crystallinity does not From the uniaxial tensile tests, mechanical properties of the
change despite the addition of another phase, even if that phase can different materials were obtained (Table 4). Both pure polymers are
act as a nucleating agent [3,29]. rather hard and brittle materials and not very useful for many ap-
In order to analyze the polymer structure in the blends FTIR plications. The pure PLA had higher values of ultimate stress and
spectra of PHB/PLA/TBL samples were done and are shown in Fig. 3 elastic modulus compared to PHB. The addition of TBL reduced in
in the 1650e1800 cm1 range. The characteristic peak both polymers the maximum stress value (sb) and the tensile
26 D.A. D'Amico et al. / Polymer Testing 49 (2016) 22e28

showed elastomeric behavior, stretching 85 times more than

plasticized PHB, as shown in Fig. 4.
In general, as the elongation at break increased, both the
maximum tension and the elastic modulus decreased (Fig. 5).
However, this was not the case for PHB/PLA (40/60), that not only
showed an elastic modulus and a maximum stress similar to those
of the blends with less PLA content, but also a larger elongation at
break. Probably, from 50/50 to 30/70 blend, the continuous matrix
is PLA, with PHB plasticized as the dispersed phase. The plasticized
PHB dispersed phase would induce deformation mechanisms that
the PLA and the PLA-TBL20 cannot generate at room temperature,
resulting in improvement in ductility of blends [12].
In order to analyze the effect of the PHB dispersed phase, SEM
microscopy for pure PLA and the PHB/PLA (50/50) blends was done.
Fig. 4. Specimens from tensile test: PHB, PHB-TBL20, blends PHB/PLA: 70/30,60/40,50/ Fig. 6a shows that the pure PLA has a smooth and uniform fracture
50,40/60,30/70, PLA-TBL20 and PLA. surface characteristic of a brittle polymer, while the PHB/PLA (50/
50) blend (Fig. 6b) reveals an irregular fracture surface with two
types of microstructure. The elongated fibrils were clearly seen
(inset), indicating that fibrillation and interfacial debonding are
mainly responsible of the improved ductility [12,18].
As it was mentioned previously, another important property
that deserves being evaluated in materials with potential

Fig. 5. Curves strain-stress for PHB, PLA and theirs blends.

modulus (E); the same behavior was observed for all blends. No
significant changes were observed in the elongation at break (εb)
for plasticized pure polymers, finding values of 2% and 5% for PHB-
TBL20 and PLA-TBL20, respectively.
Regarding the polymer blends, it was found that the elongation
at break increased from 6 to 70 times up to 60% PLA content with
respect to PHB-TBL20. Moreover, the PHB/PLA (30/70) blend
Fig. 7. WVP of PHB, PLA and theirs blends with TBL.

Fig. 6. SEM micrograph of fracture surface: a) PLAx1000 b) PHB/PLA(50/50)x1000 and inset PHB/PLA(50/50)x10,000.
 D.A. D'Amico et al. / Polymer Testing 49 (2016) 22e28 27

application in packaging is WVP. In semicrystalline polymers such incorporation of the plasticizer, which increases the free volume
as PHB and PLA, the crystalline regions are commonly considered and mobility of the polymer chains of the matrix causing a less
impenetrable for small molecules such as H2O, CO2, with a low dense structure, allowing water to diffuse through the matrix.
number of exceptions [30]. For this reason, it is assumed that The obtained results are advantageous because it was possible
semicrystalline polymers are predisposed to exhibit better barrier to modify the polymer performance in order to extend the practical
properties than amorphous polymers. In the most extensively application of these biodegradable polymers. Therefore, it could be
accepted view of the diffusion process in semicrystalline polymers, concluded that plasticized PHB/PLA (30/70) and PHB/PLA (40/60)
the diffusivity is considered to be reduced with respect to the fully blends, may be considered a sustainable alternative to current non-
amorphous polymer by a geometric impedance factor and a chain natural and non-biodegradable materials for food packaging films
immobilisation factor. The former is related to the more tortuous considering their flexibility, transparency, possibilities for pro-
path that the penetrant molecules must follow in order to bypass cessing at the industrial level and compostable in terms of their
the impermeable crystals, and the latter is connected to the final disposition.
crosslinking effect of the crystallites of the amorphous chains that
restricts their mobility [31]. Acknowledgments
The calculated values of WVP for all materials studied are
summarized in Fig. 7. The authors gratefully acknowledge the support from the Na-
The WVP value of PHB-TBL20 was found to be an order of tional Research Council of Argentina, CONICET (PIP 014, PIP 0527)
magnitude higher than that of pure PHB. Miguel et al. (2001) [32] and ANCyPT (PICT 1983) and the National University of Mar del
studied the barrier properties of PHB blends with amorphous Plata.
polymers; they found a lineal increase in the diffusion coefficient
with the amorphous polymer content. It is shown in Table 2 that the References
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