Polymer Testing 36 (2014) 2023

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

Short communication: material behaviour

Orientation induced brittle Ductile transition

in a polyethylene/polyamide 6 blend
Francesco Paolo La Mantia a, *, Paolo Fontana a, Marco Morreale b,
Maria Chiara Mistretta a
a

Universit di Palermo, Dipartimento di Ingegneria Civile, Ambientale, Aerospaziale, dei Materiali, Viale delle Scienze,
90128 Palermo, Italy
b
Universit degli Studi di Enna Kore, Facolt di Ingegneria e Architettura, Cittadella Universitaria, 94100 Enna, Italy

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 27 January 2014
Accepted 13 March 2014

Polyamide/polyolen blends are of scientic and technological interest but, on the other
hand, the different chemical nature of the two components makes them incompatible,
resulting in unsatisfactory physical properties and making compatibilization necessary. In
particular, although the two components are ductile, the binary blends can show brittle
behaviour.
It is also known that the effect of the elongational ow (and then of the induced orientation) on polymer blends is a decrease of elongation at break with increase of the degree
of orientation.
In this work, the effect of orientation on the mechanical properties of a low density
polyethylene/polyamide 6 incompatible blend was investigated.
An unexpected, orientation-induced brittle/ductile transition has been found, and interpreted in terms of microstructural changes, involving the orientation of the matrix macromolecules and of the dispersed phase particles.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Polymer blends
Film blowing
Orientation
Mechanical properties

1. Introduction
Polyamide/polyolen blends are particularly interesting
and attractive from a scientic and industrial point of view.
The different chemical nature of the two components
makes these blends incompatible, with unsatisfactory
physical properties; this makes compatibilization techniques necessary in order to obtain the desired characteristics [18]. Ductility is one of the most penalized
properties because, although their two components are
very ductile, their binary blends can show brittle behaviour
depending on their composition. This is obviously due to
the poor adhesion between the two phases, acting as a

* Corresponding author.
E-mail address: francescopaolo.lamantia@unipa.it (F.P. La Mantia).
http://dx.doi.org/10.1016/j.polymertesting.2014.03.009
0142-9418/ 2014 Elsevier Ltd. All rights reserved.

material defect and giving rise to early breaking of the

samples.
Some papers are available dealing with the effect of the
elongational ow and then of the induced orientation in
polymer blends [9,10]. The observed effect is like in
semicrystalline polymers a decrease of elongation at
break with increase of the degree of orientation.
To our knowledge, no paper has dealt with the comparison between the ductility of the oriented polymer and
that of the isotropic state. The aim of this work is, therefore,
to make preliminarily investigation of the effect of the
orientation on the mechanical properties of a low density
polyethylene/polyamide 6 incompatible blend. This blend
is known to show signicantly different behaviour
depending on the polyolen and polyamide type used, as
well as their reciprocal amounts, the processing conditions
and the possible presence of additives [1113].

F.P. La Mantia et al. / Polymer Testing 36 (2014) 2023

An unexpected, orientation-induced brittle/ductile

transition has been found, and interpreted in terms of
microstructural changes [14].
2. Materials and methods
The polyamide 6 (PA6) used in this work, Radilon S35
100 NAT, was kindly supplied by Radicinova, Italy. It has an
intrinsic viscosity (measured in sulphuric acid) of 3.4 dl/g.
The low density polyethylene (LDPE) used was a lm
blowing grade (FC39, Versalis, Italy), melt ow
rate 0.26 g/10 min (at 190  C, 2.16 kg load). Neither
material contains any antioxidant or stabilizer.
Before processing, PA6 was dried for 10 h in a ventilated
oven at 90  C, followed by 16 h under vacuum at 120  C.
The blend (75wt% LDPE, 25wt% PA6) was then prepared
by premixing the materials in the solid state (with the help
of a tumble mixer), and then by feeding into an OMC (Italy)
corotating twin screw extruder, operating with a thermal
prole of 140/160/180/200/220/240  C and screw of speed
200 rpm.
The lm blowing operation was performed with a Brabender (Germany) single screw extruder (D 19 mm, L/
D 25), with a thermal prole of 180/200/220/240  C,
screw speed 60 rpm, by feeding it with granules of the
blends prepared with the twin-screw extruder. The single
screw extruder was equipped with a lm blowing head and
a lm blowing unit.
The blow-up ratio (BUR) was about 4 for all of the blown
samples, while the draw ratio (DR) was 5 and 10 (lm
thicknesses were 25 and 50 mm).
Scanning electron (SEM) micrographs were taken on
liquid nitrogen fractured samples, using a FEI (USA) Quanta
200F scanning electron microscope.
The micrographs were processed by Leica (Germany)
QWin analysis software to analyze the particle size distribution. At least 250 particles per sample were measured.
The particles diameters were averaged by using the
following Eqn. 1:

Pn
ni Di
D Pi n 1
i 1 ni

(1)

where Di is the diameter of the i-th particle, ni is the

number of particles having Di as diameter.
Mechanical characterization was carried out using
samples cut from the lms, in both the machine and
transverse directions. In order to evaluate the effect of the
orientation, tests were also carried out on isotropic samples
cut
from
compression-moulded
sheets
(10  90  w0.6 mm) using an Instron (USA) 3365 tensile
testing machine according to ISO 527-3. The grip separation was 50 mm and the crosshead speed was 50 mm/min.
The reproducibility was satisfactory (7%).
3. Results and discussion

21

Table 1
Mechanical properties of isotropic and anisotropic samples.
Tensile
strength [MPa]
Sheet
Film, machine direction, DR 5
Film, machine direction, DR 10
Film, transverse direction, DR 5

15
18
21
10

0.7
1
1
0.6

18
279
164
22






0.8
13
7
1

the mechanical properties are measured along both the

machine and the transverse direction.
The blown lm of the blend shows tensile strength and
elongation at break values which are between those of the
two component polymers, reported in Table 2. This is an
unexpected result since in the isotropic state (i.e.
compression molded sheets), the elongation at break of the
blend is well below the values of the two component
polymers prepared under the same conditions (Table 2).
The anisotropic samples (i.e. blown lms) of this
incompatible blend show an almost brittle behavior with
very low values of the elongation at break. This is well
expected on the basis of the incompatibility between the
two components: polyethylene is apolar while the polyamide is a polar polymer. This hypothesis is conrmed by
the SEM micrograph reported in Fig. 1.
The blend shows the typical morphology of incompatible blends, with very poor adhesion, presence of voids
between the two phases and dispersed particles of about
18 mm, with average diameter of about 2.8 mm.
The mechanical properties of the oriented lm show
unexpected features. Completely unexpected is the
behaviour of the elongation at break of these anisotropic
lms that become ductile after orientation. Indeed, a
decrease of the elongation at break with the orientation
should be expected [9,10]. The impressive difference between the isotropic and anisotropic sample measured in
the machine direction is well evidenced by two typical
stress-strain curves reported in Fig. 2. The elongation at
break of the isotropic compression moulded sheet is low,
and also lower in comparison to other previously published
results [15,16] for similar blends. This is of course the result
of this type of processing.
The SEM micrograph of an anisotropic sample (Fig. 3)
indicates that the dispersed particles of the polyamide
phase are deformed (relatively long cylinders and not
spherical particles) and preferentially oriented along the
machine direction since the elongational ow in this direction is much larger than that in the transverse direction,
as also revealed by the SEM micrograph. The calculated
average of the cross-section diameters of these cylinders is
about 0.63 mm. The contact area between the matrix and

Table 2
Mechanical properties of lm and sheet of the two components.
Tensile strength [MPa]

The values of tensile strength, TS, and elongation at

break, EB, of all the investigated samples are reported in
Table 1. The compression moulded sheets are unoriented,
isotropic samples, while lm is oriented and the values of






Elongation
at break [%]

PA6 (lm)
LDPE (lm)
PA6 (sheet)
LDPE (sheet)

40
17
30
15






2
0.8
2
1

Elongation at break [%]

210
410
40
480






10
21
3
28

22

F.P. La Mantia et al. / Polymer Testing 36 (2014) 2023

Fig. 1. SEM micrograph of the LDPE/PA6 isotropic sample.

the dispersed particles is then different between the

isotropic and the anisotropic samples. Actually, at a given
volume fraction, the average surface/volume ratio is, for the
spherical particles, about 1, while for the cylindrical particles it is about 6.15. The increase of the contact area can,
therefore, be considered responsible for the increased
ductility of the lm in the machine direction.
On the contrary, in the transverse direction, the samples
retain almost brittle behaviour. This incoherent behavior
can be interpreted considering the schematic representation in Fig. 4. The elongated macromolecules of the matrix
can be deformed like in the pure polymer, and the

Fig. 3. SEM micrograph of LDPE/PA6 lm, DR 5.

elongated PA6 particles having a relatively high area and

oriented in the same direction of the macromolecules of
the matrix - do not act as a defect, as they do in the isotropic
sample, because of the larger contact surface that mitigates
the effect of the poor adhesion. The effect of the defects is
mitigated because of the shape, dimensions and orientation of the dispersed particles.
On the contrary, in the transverse direction, the
dispersed particles magnify the effect of the defect since

Fig. 2. Stress-strain curves of isotropic and anisotropic samples.

F.P. La Mantia et al. / Polymer Testing 36 (2014) 2023

23

Fig. 4. Sketch of the stress-strain test of the anisotropic lm in the machine (a) and transverse (b) direction.

they are oriented in the opposite direction and the sample

is brittle.
Finally, on increasing the draw ratio, the elongation at
break decreases and this effect is expected and due to the
matrix macromolecules being more oriented.
A similar behaviour orientation induced brittle-toductile transition has been already reported for amorphous polymers [14].
The impressive change of the elongation at break and the
brittle-ductile transition is then only the effect of the processing, and in particular of the orientation achieved under
the elongational ow during the lm blowing operation.
4. Conclusions
The brittle behaviour of an incompatible polyethylene/
polyamide 6 blend is dramatically changed by the orientation acquired during the lm blowing operation. The elongation at break in the machine direction strongly increases
in comparison to the anisotropic value; however, it tends to
decrease with application of increased degrees of orientation. On the other hand, the sample remains brittle in the
transverse direction. The ductility has been interpreted in
terms of orientation of the matrix macromolecules and of
the dispersed phase particles, which give rise to a
morphology with reduced defects in the oriented direction.

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