European Polymer Journal 49 (2013) 3630–3641

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European Polymer Journal

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

Tough blends of poly(lactide) and amorphous

poly([R,S]-3-hydroxy butyrate) – morphology and properties
Zbigniew Bartczak a,⇑, Andrzej Galeski a, Marek Kowalczuk b, Michal Sobota b, Rafal Malinowski c
a
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
b
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 41-819 Zabrze, Poland
c
Institute of Engineering of Polymer Materials and Dyes, 87-100 Torun, Poland

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

Article history: Polylactide (PLA), a biodegradable polymer, produced from annually renewable natural
Received 14 March 2013 resources, has a glass transition temperature in the range of 50–60 °C and is stiff and brittle
Received in revised form 17 June 2013 at room temperature. In this communication we demonstrate that blending of PLA with
Accepted 22 July 2013
atactic poly([R,S]-3-hydroxy butyrate) (a-PHB) leads to significant improvement of draw-
Available online 2 August 2013
ability and impact strength. The blends of PLA with a-PHB are biodegradable, similarly
to plain PLA, and can be considered as a potential material for packaging, especially for
Keywords:
food.
Polylactide (PLA)
Blends
The compositions containing up to 20 wt.% of a-PHB were prepared and characterized by
Toughening various techniques, including DSC, TGA, SEM, WAXS, DMTA and tensile tests. PLA and a-
Crazing PHB appeared partially miscible and form phase-separated blends. Tg of PLA in blends
decreases slightly with increasing content of a-PHB. SEM observations revealed sub-micron
a-PHB droplets with diffuse interphases, dispersed well in the PLA matrix. Partial miscibil-
ity results in a slight modification of cold crystallization and melting temperatures of PLA.
Foils produced from the blends by either compression molding or extrusion appeared
completely amorphous. Tensile experiments revealed a small decrease of the elastic mod-
ulus and the yield stress, while an increase of the ultimate strain with increasing content of
a-PHB. These were related to the change of the deformation behavior from brittle to ductile
and its micromechanisms. Easily cavitating a-PHB inclusions initiate numerous crazes in
PLA matrix. These crazes become diffuse, frequently deflected and terminated by other
a-PHB inclusions. At higher content of a-PHB the dense collections of diffused crazes merge
to form deformation bands and eventually a macroscopic neck. Along with improvement of
drawability at low deformation rate also the impact properties, probed in tensile impact
test, are substantially improved. The thin-film tensile impact resistance increases from
about 50 kJ/m2 in plain PLA to nearly 120 kJ/m2 in 80:20 PLA/a-PHB blend.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction resources with a potential to replace petrochemical poly-

Increasing concern on environmental impact and sus-
tainability of conventional petroleum-based polymers has
motivated researchers and engineers to considerable ef-
forts to develop thermoplastic polymers from renewable
⇑ Corresponding author. Tel.: +48 42 680 3314; fax: +48 42 684 7126.
E-mail address: bartczak@cbmm.lodz.pl (Z. Bartczak).
mers. Among a few currently commercially available bio-
based polymers polylactide (PLA) is the most promising
and investigated. Due to advances in polymerization tech-
nology, which led to significant reduction of production
costs, PLA has rapidly evolved into a competitive commod-
ity material over the last decade.
PLA is a biodegradable polymer and is produced entirely
from annually renewable natural resources. Despite
numerous advantages it suffers from a major drawback –

0014-3057/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.eurpolymj.2013.07.033
 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
brittleness at room temperature – that substantially im-
pedes its development in many potential applications. Sig-
nificant engineering effort was made to improve
mechanical performance of PLA. Many strategies have been
followed: copolymerization, plasticization, addition of ri-
gid fillers, and blending with a variety of flexible polymers
or rubbers [see reviews, e.g. 1,2]. A common, relatively
simple approach is tuning of physical and mechanical
properties of PLA by blending with various substances
(low molecular or polymeric) which act as plasticizers
[3,4] or with other polymers or rubbers, immiscible with
PLA, acting as impact modifiers [5–11]. Plasticization by
modifiers fully miscible with PLA results in substantial
lowering of the glass transition temperature (usually by
10–30 °C), which in turns leads to large improvement of
drawability and impact strength of the material, yet at
the expense of serious reduction of stiffness and plastic
resistance [2]. Poly(ethylene glycol) (PEG) is one of the
most widely used materials blended with PLA for its plas-
ticization [4,12–15].
Blending of PLA with other polymers, immiscible or
only partially miscible with PLA, can also lead to significant
improvement of drawability and impact strength, yet
without harmful reduction of the glass transition tempera-
ture, thus the stiffness of PLA can be retained [1,2]. Tough-
ening can be achieved then by modification of deformation
micromechanisms promoted by phase separation, pro-
vided an appropriate modifier is selected and composition
balanced.
The important aspect of PLA toughening is retaining
biodegradability of the material. Consequently, the modi-
fier was preferentially selected from the class of biodegrad-
able polymers. The PLA-based blends with several
biodegradable polymers: aliphatic polyesters (including
poly(e-caprolactone) [16,17], poly(e-caprolactone-co-d-
valerolactone) [11], poly(butylene succinate-co-lactate)
[18], poly(butylene succinate) [18–20], poly(butylene suc-
cinate-co-ethylene succinate) [21], poly(3-hydroxybuty-
rate-co-4-hydroxybutyrate) [22]), aliphatic–aromatic
copolyesters(like poly(butylene adipate-co-terephatalate)
[23], poly(trimethylene carbonate) [24], poly(trimethylene
carbonate-co-e-caprolactone) [25]), polyamide elastomer,
[26] poly(ether)urethane elastomer [27], and natural rub-
ber (poly(1,4-cis-isoprene) [5]), were investigated. These
systems demonstrated frequently improved ductility and
toughness. Increase of the strain at break required incorpo-
ration of at least 10–20 wt.% of the second component.
Higher contents of rubbery modifiers, usually at the level
of 20–40 wt.%, were, however necessary to improve signif-
icantly the impact strength.Regrettably, this was accompa-
nied by an unwanted notable decrease of the elastic
modulus and tensile strength [23,27].
Modification of PLA with polymers being neither bio-
based nor biodegradable, like ethylene copolymers,
[6,28,29] thermoplastic polyurethane [30], acrylonitrile–
butadiene–styrene copolymer [31], and hydrogenated sty-
rene–butadiene–styrene block copolymer (SEBS) [32] was
also examined. To control the interface, reactive blending
was frequently employed [6,29,31,32]. That approach led
to a materials with high toughness, though sacrificing
biodegradability.
3631
The goal of the presented study was modification of PLA
towards its toughening in order to obtain material suitable
for food packaging. Such a material should be not brittle at,
and advantageously also below, room temperature. When
the new material is intended to be used in contact with
food (e.g. in packaging), its components as well as possible
products of their degradation must be either inert or bio-
compatible, a property that must be maintained also after
blend formulation. Biodegradation is also highly desirable
due to environmental issues.
In this communication we present our study on binary
blends of PLA with an atactic poly([R,S]-3-hydroxy buty-
rate) (a-PHB), a synthetic analog of bacterial PHB. Atactic
PHB was selected with the aim to improve mechanical per-
formance of PLA, primarily its drawability and impact
resistance. a-PHB is a low glass transition (around 0 °C)
amorphous polymer and behaves as an elastomer at room
temperature. The miscibility of PHB (both bacterial and
synthetic) with PLA depends on the molecular weight
[33]: PLA is fully miscible with low molecular weight
PHB [33–35], while immiscibility was observed for high
molecular weight PHB and PHBV [33,36,37]. An interesting
feature of a-PHB is that it is environmentally biodegrad-
able [38,39] and biocompatible, i.e. its hydrolytic degrada-
tion products (R)- and (S)-3-hydroxybutyrates are
nontoxic compounds safe for live tissues [40]. The blends
of PLA with a-PHB are thus expected to be fully biodegrad-
able and biocompatible, similarly to plain PLA, and can be
considered as a potential material for food packaging.
2. Experimental details
2.1. Materials and sample preparation
Polylactide used in this work was a commercial PLA,
grade 2002D (Nature WorksÒ), with Mw = 114,000,
Mn = 87,000, D-lactide content below 3.5%, density 1.24 g/
cm3 and MFR(210 °C, 2.16 kg) = 5–7 g/10 min (data pro-
vided by manufacturer).
Poly(R,S-3-hydroxybutyrate) (a-PHB) was synthesized
by bulk anionic ring opening polymerization of racemic
mixture of R and S isomers of b-butyrolactone initiated
with tetrabutylammonium acetate [41,42]. The process of
random polymerization takes place with 100% inversion
of monomer configuration with the same reactivity of
two antipodes [43]. Thus, obtained poly([R,S]-3-hydroxy-
butyrate) is atactic polymer. Molecular mass determined
by GPC was Mn = 100,000. 13C NMR and 1H NMR spectros-
copy showed that the polymer obtained was atactic [44].
Blends containing 2, 5, 10, 15 and 20 wt.% of a-PHB
were prepared using three different protocols: (i) First,
used for preparation of small quantities of blends for a
few pilot experiments was mixing in solution. CH2Cl2
was used as a common solvent. Films were cast from 5%
wt./vol. solution and after solvent evaporation dried 4 h
at 105 °C under vacuum. Next, several dry films were
stacked together and compression molded at 180 °C to ob-
tain foils approx. 0.4 mm thick. (ii) The second method was
melt blending in the internal mixer (PlastiCorder W50E,
Brabender, Germany; T = 180 °C, 60RPM, 10 min). Samples
3632 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
in the form of 0.4 mm thick foils were prepared again by
compression molding at 180 °C. Finally, larger quantities
of blends were prepared by (iii) melt-mixing with co-rotat-
ing twin-screw extruder (BTSK 20, Buehler, Switzerland;
D = 20 mm, L/D = 40, T = 190 °C, and 200 RPM). The blend-
ing was followed by extrusion of foils with single-screw
extruder (PlastiCorder PLV 151, Brabender; D = 19.5 mm,
L/D = 25, T = 190 °C, and 60 RPM) equipped with the
170 mm wide adjustable slit die. Foils were cast on a
chill-roll (three rolls setup, diameter 200 mm each, and
T = 55 °C). Foils approximately 0.3 mm thick and 140 mm
wide were obtained.
2.2. Characterization
The following experimental methods were employed
for characterization of obtained blends:
DSC: Thermal behavior of samples was probed with DSC
2920 differential scanning calorimeter (TA Instruments) at
heating from 50 °C to 190 °C with the rate of 10 °C/min.
Samples of the 5–8 mg mass were cut from the compres-
sion molded foils and crimped in standard Al pans. The
DSC cell was purged with nitrogen during measurements
(20 ml/min).
Microscopy: Morphology of blends was observed with
scanning electron microscopy (SEM). Samples were pre-
pared either by freeze–fracture under liquid nitrogen con-
ditions or by exposing an internal surface with an
ultramicrotome (Power Tome XL, Boeckeler Instruments,
Inc.) equipped with a freshly prepared glass knife. Samples
were cut at room temperature. Samples were coated with a
fine gold layer by ion sputtering (JEOL JFC-1200) and then
examined with the JEOL JSM-5500 LV scanning electron
microscope. All microscopic observations were made in
the high-vacuum mode and at the accelerating voltage of
10 kV. Images were created using signal from the second-
ary electron detector (SEI).
SEM and optical microscopy were also used for inspec-
tion of tensile specimens after their deformation in order
to assess deformation mechanisms involved. For this pur-
pose samples were only coated with the gold layer prior
to SEM examination.
WAXS: Wide-angle X-ray scattering was used for exam-
ination of structure of samples and possible preferred ori-
entation in extruded foils. 2-D WAXS images were
registered with flat X-Ray camera equipped with imaging
plates (Fuji) and coupled to Cu Ka source (sealed tube
operating at 30 kV and 50 mA, PANalytical). Supplemen-
tary measurements were performed with a diffractometer
(DRON, Russia) set in the reflection mode with an extruded
foil sample oriented with the machine direction parallel or
perpendicular to the diffraction plane.
Thermal shrinkage: Shrinkage of extruded foils was mea-
sured to evaluate their possible orientation. Strips, 100 mm
long, were cut from extruded foils along the machine
direction (MD) or transverse direction (TD) and annealed
above the glass transition temperature, at 75 °C, by
10 min. From the measured length before (lo) and after
annealing (l) the shrinkage was calculated as s = (lo l)/
lo * 100%, independently for MD and TD directions.
Mechanical properties: Tensile measurements were per-
formed according to the ISO 527-2 standard. Specimens of
the gauge length of GL = 25 mm and the width of 5 mm
(ISO 527-2, type 1BA) were cut from the compression
molded foils and from extruded foils using a steel tem-
plate. For extruded foils specimens oriented along the
loading and transverse directions (LD, TD, respectively)
were prepared and tested. Samples were tested at room
temperature (22 °C) using an universal testing machine In-
stron, Model 5582. Clip-on extensometer (GL = 25 mm)
was used for strain measurement. The crosshead speed
was constant and set to 1.25 mm/min, i.e. the initial defor-
mation rate was 5%/min. For each composition and orien-
tation of the sample at least five specimens were tested.
From obtained nominal stress–strain curves the modulus
of elasticity, yield stress and the ultimate stress and strain
were evaluated.
Impact properties were probed by tensile impact test,
performed according to the ISO 8256 standard (method
A) at T = 22 °C. Specimens of the type 3 (GL = 25 mm,
width = 10 mm) were cut from the foils similarly to tensile
specimens. Instrumented impact tester Resil 5.5 (CEAST,
Italy), measuring stress and energy absorbed, was used.
The hammer striking the specimen with the speed of
2.6 m/s was able to deliver the energy of 1 J. The mass of
the anvil attached to the specimen was 15 g. At least seven
specimens were tested for each sample. Necessary instru-
mental corrections were applied to the raw energy data
according to the ISO 8256 standard prior to evaluation
the impact strength.
DMTA: Dynamical mechanical thermal analysis was
used to determine relaxation temperatures related to the
glass transition. Samples, cut from the compression
molded foils, in the form of 10  50  0.4 mm3 strips (the
length of both bent sections of the specimen was 5 mm)
were tested in the double cantilever bending mode using
DMTA Mk III instrument (Rheometric Scientific) in the
temperature range of 80 to +140 °C, with a heating rate
of 2 °C/min. The frequency of strain oscillations was 1 Hz
and the amplitude set to ±16 lm.
3. Results and discussion
3.1. Morphology and phase structure
The morphology and phase structure of studied blends
were probed with scanning electron microscopy (SEM),
thermal analysis (DSC) and dynamic mechanical analysis
(DMTA).
The morphology was observed with SEM. Two method
of specimen preparation was used to expose phase mor-
phology: freeze–fracture and cutting with a microtome.
Fig. 1 shows representative SEM micrographs of freeze–
fracture surface of PLA and 8:2 PLA/a-PHB blend samples
obtained by mixing either in solution or in the molten
state. The fracture plane of plain PLA (Fig. 1a) shows fea-
tures typical for brittle fracture of amorphous glassy poly-
mer. Fractured 8:2 blend samples revealed more
developed and rough fracture plane in which numerous
round features with diffused edges can be observed. Such
a morphology is characteristic for phase separated blends
and the round objects visible in micrographs represent
 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
Fig. 1. SEM micrographs of freeze–fractured surfaces of plain PLA (a) and PLA/aPHB 8:2 blend mixed in solution (b) and in the molten state with internal
mixer (c) or co-rotating twin-screw extruder (d).
inclusions of a-PHB, dispersed in PLA matrix. Very similar
matrix–inclusions morphology was observed also in blend
samples of smaller a-PHB concentrations (5–15 wt.%).
Fig. 2 shows micrographs recorded for the same materi-
als, yet specimens were prepared for observation by micro-
tome cutting at room temperature. In this case the phase
structure of the blends is revealed due to different compli-
ance of PLA and a-PHB. At room temperature PLA is a stiff
glass thus is cut by a microtome knife with little of elastic
or plastic distortion and the cut surface is smooth and flat
(cf. Fig. 2a). At the same conditions a-PHB is in rubbery
state and much more compliant than PLA. Therefore, in
phase separated blend a-PHB inclusions are slightly de-
formed by the cutting edge of knife, which results in for-
mation of hollows on the flat surface left after cutting the
PLA matrix. The contour shape and size of such depressions
reflect the shape and size of actual cross-section of a-PHB
inclusions.
The micrographs presented in Fig. 2 confirm the phase
separation and the matrix–inclusions morphology in 8:2
PLA/a-PHB blend. Again, observations of 95:5, 90:10 and
85:15 blends revealed the same morphology (micrographs
not shown here).
Another observation is that the size of a-PHB inclusions
strongly depends on the method of blend preparation. In
both, freeze–fractured and microtomed samples we ob-
served that a-PHB inclusions are significantly smaller in
samples prepared by melt mixing than in that mixed in
solution, especially when a twin-screw extruded was em-
3633
ployed for mixing. Average size of a-PHB inclusions in
the sample of 8:2 blend cast from solution is around
2 lm while in the sample of the same composition pre-
pared by melt-mixing in extruder is approx. 0.4–0.5 lm.
Much smaller size of inclusions in melt-mixed sample is
apparently enforced by high shear forces during melt-mix-
ing with a twin-screw extruder.
Additional information on phase behavior of PLA/a-PHB
blends can be obtained from DSC and DMTA data. Fig. 3
shows DSC scans recorded on heating of blend samples
prepared by melt-mixing. The numerical data evaluated
from those thermograms are presented in Table 1.
The first observation is that in samples containing 15–
20 wt.% of a-PHB two separate glass transitions related to
a-PHB and PLA can be identified. For lower a-PHB concen-
trations the low-temperature glass transition related to a-
PHB becomes too small to be distinguished, and only that
of PLA can be observed. The temperature of that glass tran-
sition decreases with increasing a-PHB content, initially
faster for concentrations below 10 wt.%, and then stabilizes
for higher a-PHB concentrations. Such a behavior can indi-
cate a partial miscibility of a-PHB and PLA, most probably
limited to a few percent of a-PHB in the blend.
All samples demonstrate cold crystallization of PLA
component on heating. Crystallinity estimated from area
under crystallization and melting peaks, respectively, are
very close each to the other, which demonstrates that all
initial samples were completely amorphous, indepen-
dently on composition. This conclusion was confirmed
3634 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
Fig. 2. SEM micrographs of surfaces exposed with a microtome of plain PLA (a) and PLA/aPHB 8:2 blend mixed in solution (b) and in the molten state with
the Brabender mixer (c) or co-rotating twin-screw extruder (d).
Fig. 3. DSC heating scans of PLA and PLA/a-PHB blend samples, prepared
by melt-mixing and compression molding of the foils. Heating rate of
10 °C/min. Curves shifted vertically for clarity of presentation.
independently by X-ray diffraction measurements – see la-
ter. Temperature of cold crystallization decreases with
increasing a-PHB concentration, which follows the trend
observed in Tg. The reason of such a variation is probably
partial miscibility, decreasing Tg, and consequently lower-
ing the transport barrier for crystallization, which in turn
results in a lower crystallization temperature.
The melting consists of two peaks. The temperature of
the lower melting peak (related to the melting and recrys-
tallization of original crystals into more stable form)
changes in similar fashion to glass or crystallization tem-
peratures, while the temperature of the upper peak, related
to melting of more stable crystals, decreases only slightly
with composition. Such a melting behavior suggests some
reduction of thickness of those crystals formed in blends
comparing to plain PLA. It is consistent with the formu-
lated hypothesis of limited partial miscibility of a-PHB
and PLA.
Partial miscibility of blend components was confirmed
also by dynamic mechanical analysis. Fig. 4 presents the
temperature dependence of loss modulus determined by
DMTA measurements. It can be seen that curves obtained
for blends show two separate peaks. The first, smaller peak
is observed around 4 °C and is related to the a relaxation
process of a-PHB. The upper, much bigger peak at 55–
60 °C is related to the a relaxation of PLA. The presence
of two separate peaks confirms phase separation. While
the position of the lower peak seems more or less stable,
the upper peak shifts continuously down from 60 °C in
plain PLA to slightly above 55 °C in the PLA/a-PHB 8:2
blend. Such shift must be related to partial miscibility, sim-
ilarly to changes in Tg observed by DSC.
The conclusion on partial miscibility of PLA with a-PHB
is in line with results of Ohkoshi et al., [45] who studied
the miscibility and phase structure of binary blends of
PLA with a-PHB of different molecular weight using DSC
and optical microscopy.
 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641 3635

Table 1
Temperatures of transitions and degree of crystallinity, evaluated from DSC curves of Fig. 3.
a b
Sample Tg1 (°C) Tg2 (°C) Tc (°C) Tm (°C) Xc-cryst (wt.%) Xc-melt (wt.%)
PLA – 57.3 112.4 154.9 30.9 31.8
95:5 – 51.6 102.3 155.3 32.5 34.3
90:10 – 48.6 99.8 154.2 32.4 34.2
85:15 0.0 48.3 100.6 154.3 32.7 34.1
80:20 0.1 48.2 100.7 154.2 33.7 35.1
a-PHB 1.7 – – – – –
a
The crystallinity of PLA in the blend estimated on the basis of the cold crystallization peak. The value of DHf = 93 J/g [44] was assumed for calculations.
b
The crystallinity of PLA in the blend estimated on the basis of the melting peak; DHf = 93 J/g [44].

Fig. 4. The dependence of the loss modulus on temperature determined

by DMTA in the double cantilever bending mode at the frequency of 1 Hz.
Temperatures of the a relaxation of PLA component indicated.

X-ray diffraction measurements did not reveal any trace

of crystallinity regardless of blend composition and prepa-
ration protocol. This is illustrated in Fig. 5, presenting
exemplary X-ray scattering pattern obtained for extruded
sample of the 8:2 PLA/a-PHB blend. It shows a typical
amorphous halo, with no crystalline peaks superimposed.
This confirms the previous conclusion drawn from DSC re-
sults on fully amorphous structure of blends. The scatter-
ing intensity is independent on azimuth angle (cf.
Fig. 5b), which indicates a lack of preferred orientation.

3.1.1. Extruded foils – morphology, structure, orientation

We examined also the phase structure and morphology
of foils prepared from blends by continuous extrusion. SEM
micrographs of cross-section of the foils are presented in
Fig. 6. The plane of observation, perpendicular to the ma-
chine direction, was exposed by microtoming.
Fig. 5. Exemplary 2-D X-ray scattering pattern and related diffractograms
In addition to a-PHB inclusion some structural flaws can recorded in transmission mode along machine direction (MD) and
be observed in these micrographs. In the core of the foil transverse direction (TD) for PLA/a-PHB 8:2 blend sample prepared by
these flaws have the form of circular cavities, approx. melt-mixing and foil extrusion.
0.3 lm in diameter, i.e. comparable in size with a-PHB
inclusions (0.4–0.5 lm). When moving from the core to
the skin layer the flaws change from circular holes to elon- that they were formed most probably at the final stage of
gated micro-cracks or fissures, up to 10 lm long, oriented the foil extrusion process, when the already solidified foil
along transverse direction (parallel to the foil surface). was rolled up on take-up roll of relatively small diameter.
The number of these micro-cracks increases when Stresses produced by foil bending were apparently high
approaching the skin of the foil. Taking into consideration enough to induce such a damage in the structure of the
the shape, distribution and size of flaws it can be derived blend film. The voids and micro-cracks were probably
3636 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
Fig. 6. Series of consecutive SEM micrographs of the cross-section of the
8:2 PLA/a-PHB foil prepared by foil extrusion. The micrograph in (a)
shows a top skin layer (an epoxy embedding the specimen for micro-
toming is visible at the top), (b) presents an intermediate region, beneath
the skin and (c) shows the central core region of the extruded foil. The
plane of observation is perpendicular to the machine (extrusion) direc-
tion. The normal direction is vertical and the transverse direction is
horizontal. The cutting direction, approx. 45° from ND, visualized by knife
marks, was selected to minimize damage during microtoming.
initiated inside rubbery a-PHB inclusions or at interfaces
due to stress concentrations. No such defects were ob-
served in foils extruded from plain PLA.
In order to find out whether the extruded foils show any
orientation, which could be produced upon processing,
they were examined with X-ray and their thermal shrink-
age was monitored. For every composition tested 2-D
WAXS patterns recorded with a flat camera demonstrated
an uniform amorphous halo. Independence of scattering
intensity on azimuth angle was confirmed with diffrac-
tometer measurements along various direction. These fea-
tures, evidenced by representative pattern and diffraction
curves shown in Fig. 5, indicate that the preferred molecu-
lar orientation of extruded foils, if any, is negligible small.
Thermal shrinkage of the extruded foils after annealing
above glass transition temperature (Ta = 75 °C) was moni-
tored in two perpendicular directions: along MD and TD.
Results (not shown) demonstrated that samples shrunk
similarly in both MD and TD directions, by approx. 1.4–
2%. That results confirm previous conclusion on nearly iso-
tropic structure of the foils.
3.2. Tensile properties
Tensile properties of PLA-based materials were probed
at the low deformation rate of 5%/min, and the results
are shown in Fig. 7 and Table 2. Independently of process-
ing conditions the plain PLA displays a Young’s modulus of
Fig. 7. Representative tensile stress–strain curves determined for sam-
ples of PLA/a-PHB blend prepared by melt-mixing (a). Curves are shifted
along the strain axis (10% increment) for clarity of presentation.
Deformed samples are shown in the photograph (b).
 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641 3637

Table 2
Mechanical parameters of PLA/a-PHB blends obtained by solution- or melt-
mixing. Tensile specimens cut from compression molded foils.

Sample Young Yield Stress at Strain at

modulus stress break break (%)
(MPa) (MPa) (MPa)
Solution-mixed blends
PLA 3.54 ± 0.06 51.7 ± 2.0 49.0 ± 2.0 7±2
98:2 3.50 51.8 47.8 7
95:5 3.20 52.6 46.0 8
90:10 3.10 49.1 41.8 10
85:15 2.77 39.5 34.5 12
80:20 2.72 36.1 30.5 27 ± 10
Melt-mixed blends
PLA 3.50 ± 0.06 57.6 ± 2.0 49.3 ± 2.0 6±2
98:2 – – – –
95:5 3.38 55.2 46.0 6
90:10 3.24 52.4 43.5 7
85:15 2.91 46.2 38.3 9
80:20 2.75 40.8 30.5 21 ± 10

about 3.5 GPa, the maximum stress of 57 MPa and an elon-

gation at break of 4–6%, i.e. values typical for a rigid and
brittle material. Adding the rubbery a-PHB into PLA results
in a minor decrease in Young’s modulus recorded accom-
panied by a moderate decrease of the yield stress and an
increase in the elongation at break up to around 30% for
80:20 blend (an average value; few specimens actually de-
formed up to 60%). All parameters evaluated are presented
in Table 2. Comparing the shape of the respective stress–
strain curves as well as the derived mechanical parame-
ters, determined for samples prepared by solution-mixing
(curves not shown here) and melt-mixing (Fig. 7) one can Fig. 8. The stress–strain curves of samples cut from the extruded PLA/a-
notice that differences between both sets of samples are PHB foils and tested along the machine direction, MD (a) and the
minor, irrespective of difference in morphology, i.e. aver- transverse direction, TD (b). Curves are shifted along strain axis (1%
increment) for clarity of presentation.
age size of a-PHB inclusions larger in samples prepared
by solution than by melt-blending as reported in the previ-
ous section. Slightly lower values of the yield stress of solu- modulus and characteristic stresses are comparable for
tion-blended samples might reflect a trace of solvent in both directions and are similar to melt-mixed samples pre-
these specimens (although DSC measurements did not re- pared by compression molding, although yield stress and
veal any solvent-related depression of Tg). stress at break decrease with increasing content of a-PHB
Observation of the deforming specimens revealed a
gradual change in the deformation and fracture habit with
increasing content of a-PHB in the blend: from occasional Table 3
isolated crazes resulting in a semi-brittle fracture observed Mechanical parameters of PLA/a-PHB blend samples obtained by foil
extrusion.
in neat PLA, through densified crazing and beginning of
formation of deformation bands at 5–10 wt.% of a-PHB to Sample Young Yield Stress at Strain at
a clear macroscopic neck accompanied by very intense modulus stress break (MPa) break (%)
(MPa) (MPa)
stress whitening in samples containing 15–20 wt.% of a-
PHB. This is illustrated by photograph of deformed tensile Tested along MD
PLA 3.49 51.7 48.7 6.6
samples shown in Fig. 7b.
98:2 3.48 51.4 46.5 4.7
Tensile properties of foils extruded from PLA/a-PHB 95:5 3.31 50.5 46.5 12.5
blends were probed in the machine (MD) and the trans- 90:10 3.21 49.2 45.1 7.7
verse (TD) directions of foils. Results are presented in 85:15 3.11 47.5 42.5 7.8
Fig. 8 and Table 3. 80:20 2.91 43.9 37.3 11.8
Tested along TD
It can be observed that samples prepared from extruded PLA 3.54 55.7 50.1 4.2
foils show slightly different mechanical response when 98:2 3.46 53.5 47.0 3.5
tested along machine and transverse direction, as derived 95:5 3.36 50.5 45.6 3.5
from different shape of the stress–strain curve – the force 90:10 3.13 47.5 42.2 3.8
85:15 2.79 38.3 36.0 3.8
maximum near the yield point is more prominent in sam-
80:20 2.66 36.1 31.5 4.0
ples tested along TD than those tested along MD. Elastic
3638 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641

faster in samples tested along TD than MD. The strain at

break is notably lower than observed in compression
molded samples, especially when tested along TD. All sam-
ples developed crazes during their deformation with the
number increasing with increasing content of a-PHB. Mac-
roscopic necking was not observed in any of extruded
samples.
Different mechanical response along MD and TD of ex-
truded foils might be related to some molecular orienta-
tion along MD. That orientation had to be rather small as
it was detected neither by WAXS nor shrinkage measure-
ments, as discussed previously. More probably however,
these differences are related to voids and cracks present
in extruded samples, as evidenced by SEM observations.
These defects can lead to some reduction of the overall
stress and to premature fracture of extruded samples as
well as to slight anisotropy of mechanical response, since
cracks are usually longer in the transverse direction than
in the machine direction.

3.3. Impact properties

Fig. 9 presents results of the tensile impact test (striker

speed of 2.6 m/s) performed for three sets of samples stud-
ied in this work. It can be observed that blend samples pre-
pared with different protocols show a different mechanical
response. Samples prepared by either solution or melt mix-
ing, both followed by compression molding, behave in a
similar fashion and demonstrate a clear brittle-to-ductile
transformation, accompanied by substantial increase of
the impact resistance, at concentration of a-PHB around
10 wt.% (see Fig. 9a). The impact resistance was deter-
mined as the total energy dissipated during deformation
and fracture of the specimen per area unit of the cross-sec-
tion. Toughening observed in melt-mixed samples of high-
er concentrations of a-PHB was stronger than in respective
solution-mixed samples – for 80:20 composition the im-
pact resistance was 117 kJ/m2 and 81 kJ/m2, respectively,
compared to 53 kJ/m2 for plain PLA. The maximum stress
at impact for both sets changes with composition in similar
way – initially increases slightly with increasing content of
a-PHB and then begins to decline slowly at concentrations
above 10 wt.%. As a result, at 20 wt.% of a-PHB the maxi-
mum stress of solution blended sample is practically equal
to stress of plain PLA while that of melt-mixed 80:20 blend Fig. 9. The dependencies of impact resistance (a) and maximum stress at
tensile impact (b) on content of a-PHB in the blend. Photograph (c) shows
is even slightly lower. That decrease reflects a lowering of melt-mixed compression molded samples broken in tensile impact test.
the yield stress in blends compared to plain PLA as ob-
served in tensile test.
Examination of broken specimens revealed a brittle
fracture of samples containing less than 10 wt.% of modi- sets show phase separation, yet the average size of
fier, ductile fracture and a relatively narrow deformation a-PHB inclusions dispersed in PLA matrix is much smal-
zone around fracture plane in 90:10 blend and ductile frac- ler in melt-mixed blends than in those blended in solu-
ture preceded by an extensive plastic deformation accom- tion. The significantly smaller inclusion size in samples
panied by widespread and strong stress whitening of mixed in the melt is a result of high shear stresses
almost entire gauge section of the specimen in blends of within the melt during compounding. It is well estab-
a-PHB content higher than 10 wt.% (see Fig. 9c presenting lished that smaller inclusions of rubber generally have
a photograph of melt-mixed samples; solution-mixed sam- a better toughening effect than large particles [46],
ples demonstrated very similar features). and it is clear that the system PLA/a-PHB follows this
The better toughening in melt-mixed blends com- rule. The dispersion of a-PHB and therefore mechanical
pared to solution-mixed ones is a consequence of their performance of the blend could be possibly improved
different morphologies. As discussed in Section 3.1 both by either optimization of the blending protocol or by
 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
Fig. 10. SEM micrographs of the surface of deformed tensile specimens of
PLA (a), 9:1 (b) and 8:2 (c) PLA/a-PHB blends. For blends micrographs
were taken away from the main, stress-whitened, deformation zone or
neck. Direction of tension is horizontal.
addition of compatibilizer, e.g. respective block copoly-
mer. The latter strategy, using block copolymers of nat-
ural PHAand synthetic a-PHB, has been recently
reported by us [47]. Synthesis of block copolymer of
3639
PLLA and a-PHB for use in PLA/PHB blends are under
way in our laboratory.
At low concentrations of a-PHB in the blend, up to
5 wt.%, the impact resistance of blends, only a little higher
than PLA, does not depend on method of preparation. Such
a behavior is probably related to partial miscibility of com-
ponents which causes some plasticization of PLA and con-
sequently increases slightly the toughness of the material,
independent from the preparation protocol. On the other
hand, due to low concentration of a-PHB and its partial sol-
ubility in PLA the number of separated a-PHB inclusions is
apparently too small to produce any serious toughening as
that observed in blends of elastomer concentrations above
10 wt.%.
In contrary to the above, the impact resistance of blend
samples produced by melt-blending and film extrusion
changes very little with composition and stays at low level
characteristic for PLA (see Fig. 9a). Concurrently, the max-
imum stress observed at impact decreases slightly with
increasing a-PHB concentration (Fig. 9b). Examination of
broken specimens revealed brittle fracture of all speci-
mens, in the entire composition range studied. That brittle
behavior, different than that reported previously for sam-
ples formed by compression molding, can be attributed
to voids and microcracks found in extruded samples. These
defects cause a premature fracture of blend samples so
their toughness appears even lower than plain PLA.
3.4. Deformation habits
As already reported both solution- and melt-mixed
samples formed by compression molding revealed a grad-
ual change in the deformation and fracture behavior with
increasing content of a-PHB from semi-brittle fracture
due to crazing at low a-PHB content to ductile behavior
with a macroscopic neck formation and widespread and
intense stress whitening in samples containing 15–
20 wt.% of a-PHB (cf. Fig. 7b). The same behavior was ob-
served in low- (1.25 mm/min) and high-rate (2.6 m/s) ten-
sile experiments. SEM examination of surface of slowly
deformed tensile samples revealed that crazing was an ac-
tive deformation mechanism in all samples, independently
of the content of a-PHB. However, as illustrated in Fig. 10
the character of crazes changed with increasing concentra-
tion of a-PHB: in plain PLA and blends of low content of a-
PHB (2-5 wt.%) crazes were sharp, long and straight (cf.
Fig. 10a). At higher content of a-PHB (10–20 wt.%) crazes
were much more numerous, frequently deflected and rela-
tively short. Their edges appeared increasingly diffused.
Crazes tend to concentrate in a broad deformation zone,
where dense and frequently deflected crazes start to merge
to form a deformation band. With an advance of strain
intersecting deformation bands spread out and eventually
transform into a macroscopic neck. Such a behavior resem-
bles a common picture of deformation of brittle glassy
polymer toughened with rubber particles. It can be de-
duced, that a-PHB inclusions dispersed in PLA matrix play
a typical role of craze initiators and are able also deflect,
blunt and terminate crazes. Easy cavitation of a-PHB inclu-
sion, modifying locally the stress field, plays an important
role in these processes. It is also possible that cavitating
3640 Z. Bartczak et al. / European Polymer Journal 49 (2013) 3630–3641
inclusions can additionally initiate also some shear be-
tween crazes. Such shear is probably easier than in plain
PLA as both polymers show a limited miscibility which re-
sults in a slight plasticization of PLA, manifesting in reduc-
tion of glass transition temperature and yield stress,
reported earlier. These local shear events lead to formation
of micro- and then, by their coalescence, macroscopic
deformation bands and finally a macroscopic neck. The
beginning of formation of a micro-band can be observed
in the center of Fig. 10c.
Modification of PLA with elastomeric a-PHB particles
results in transition from semi-brittle to ductile behavior
and consequently to significant toughening of the material,
with over two-fold increase of tensile impact strength: im-
pact resistances of 53 kJ/m2 vs. 117 kJ/m2 were observed
for plain PLA and 80:20 blend, respectively. Very strong
and diffused whitening of the blend at impact loading indi-
cates a widespread cavitation of a-PHB inclusions accom-
panied by formation of rather short crazes in PLA matrix
prior to fracture.
4. Conclusion
The following conclusions can be drawn from the study
reported:
 PLA and atactic PHB, both of moderate molecular
weight around 100,000 are partially miscible and
form phase-separated blends. Blends show two sepa-
rate glass transitions and Tg of PLA-rich phase
decreases slightly with an increasing content of a-
PHB, which reflects minor plasticization of PLA
matrix. As a consequence a small depression of cold
crystallization and melting temperatures of PLA is
also observed in blends.
 Microscopic observations revealed sub-micron a-PHB
droplets with diffused interphases dispersed well in
the PLA matrix. The size of inclusions depends on the
method of preparation. Inclusions of a-PHB in blends
prepared by melt-mixing, when high shear forces were
applied, are much smaller than in solution-mixed sam-
ples (for 80:20 blends the average diameter around
0.5 lm and 2 lm, respectively).
 Partial miscibility results in diffuse interphases and
consequently in good adhesion between PLA matrix
and a-PHB inclusions.
 Elastomeric a-PHB inclusions well adhering to PLA
matrix are very susceptible to cavitation. This feature
can show up even already at processing: voids and
microcracks due to cavitation in these inclusions devel-
oped when extruded foils were excessively bent on
take-up rolls. Cavitation plays also a very important
and positive role during material deformation.
 A small decrease of the elastic modulus and the yield
stress, while a notable increase of the ultimate strain
with increasing content of a-PHB were observed in ten-
sion. Modification of material properties was related to
the change of the deformation behavior and its micro-
mechanisms. Easily cavitating a-PHB inclusions initiate
numerous crazes in PLA matrix. These crazes become
diffused, frequently deflected, blunted and shortened
due to termination by other a-PHB inclusions. Cavita-
tion causes also some local shear yielding in surround-
ing PLA matrix. At higher content of a-PHB the dense
collections of diffused crazes merge to form deforma-
tion bands and eventually a macroscopic neck.
 Along with improved drawability at low deformation
rate also the impact properties, probed in tensile impact
test, are substantially improved in blends. Material
behavior changes from brittle to ductile at the concen-
tration of a-PHB around 10 wt.%. The thin-film tensile
impact resistance increases from about 50 kJ/m2 in
plain PLA to nearly 120 kJ/m2 in 80:20 PLA/a-PHB blend.
This demonstrated that a-PHB can be considered as an
effective impact modifier for PLA. The other important
feature is biodegradability which is retained in polylac-
tide toughened with a-PHB.
Acknowledgement
This research project has been partially supported by
the European Union European Regional Development
Fund, Contract No. POIG.01.03.01-00-018/08-00 (Margen).
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