Materials Letters 93 (2013) 14

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

HDPE/Cu-nanober nanocomposites with enhanced antibacterial and oxygen

barrier properties appropriate for food packaging applications
Dimitrios N. Bikiaris a,n, Kostas S. Triantafyllidis b
a
b

Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia, Greece
Laboratory of General and Inorganic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia, Greece

a r t i c l e i n f o

abstract

Article history:
Received 22 September 2012
Accepted 31 October 2012
Available online 10 November 2012

HDPE nanocomposites containing 0.5, 1, 2.5 and 5 wt% of copper nanobers (Cu-nanobers) were
prepared by the melt-mixing method and exhibited enhanced tensile strength, Youngs modulus, and
oxygen barrier as well as antibacterial properties. These improvements were attributed to the small
size of Cu-nanobers and their ne dispersion into the HDPE matrix.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
Polyethylene
Nanocomposites
Copper nanobers
Mechanical properties
Oxygen permeability
Antibacterial properties

1. Introduction
Polymer-based packaging materials should have good barrier
properties against oxygen and water vapor as well as antibacterial
properties in order to protect foods and beverages from undesirable changes of their physico-chemical and organoleptic properties, as well as their overall quality. Since these sensitive edible
products may undergo biological, chemical and physical deterioration during storage and distribution, appropriate multifunctional packaging materials should be used. Several oxidation and/
or hydrolysis reactions (due to the presence of oxygen and water
respectively) can occur within foods, which can be enhanced by
exposure to light, and can be accounted as the main reason for the
observed deterioration. Oxygen affects negatively the food properties during prolonged storage periods since it can cause oxidation of proteins and also can affect negatively avor and color.
Thus, the lower the oxygen permeability of packaging materials,
the higher the protection of product quality. Food deterioration
can be also caused from microbial growth on the food surface.
Packaging lms with antimicrobial properties can prevent such
deterioration [1,2]. The antibacterial lm can decrease the growth
rate and maximum growth of yeast, and extend the lag period
before mold growth can appear.
Researchers and packaging lm producers are employing
various types of packaging materials to be reactive, intelligent,

Corresponding author. Tel.: 30 2310 997812; fax: 30 2310 997667.

E-mail address: dbic@chem.auth.gr (D.N. Bikiaris).

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.10.128

or interactive [3]. The most well-known packaging materials

that meet these criteria are petrochemical based plastics such as
polypropylene (PP) and polyethylene (PE) which have been in use
by the food industry for over 50 years because of their availability
in large quantities at low cost and due to their favorable functional characteristics. These materials are not only safe, transparent, inexpensive and versatile, but are also exible and
compatible with foods and most household chemicals [4]. However, these materials are relatively high permeable by oxygen
compared to other materials like poly(ethylene terephthalate)
and poly(vinyl alcohol) [5]. The application of multi-layer plastics
or various types of laminates, which are made by bonding
together two or more different materials, i.e. plastic, paper or
foil, is the usual way to enhance the oxygen barrier properties of
packaging lms. However, a more sophisticated approach is
required when antibacterial properties should be also enhanced.
Antibacterial additives in packaging lms have been used
successfully for many years [6]. The application of antimicrobial
agents affects the mechanical properties of thin lms. Taking into
account all the above it seems that the appropriate material for
packaging applications should have good mechanical properties,
low oxygen permeability and high antibacterial properties.
These demands could be covered with the addition of appropriate
inorganic nanoparticles in a polymeric matrix. Such inorganic
nanoparticles are copper (Cu) and silver (Ag), which can serve as
antibacterial agents [7,8] and can also act as reinforcing nanollers of polymeric lms.
In the present study, high density polyethylene (HDPE) nanocomposites with Cu-nanobers were prepared by the melt-mixing

D.N. Bikiaris, K.S. Triantafyllidis / Materials Letters 93 (2013) 14

method. The aim was to prepare antibacterial plastic lms with

enhanced mechanical and oxygen barrier properties, appropriate
to be used as reactive packaging materials for food preservation.
Cu-nanobers are used for the rst time in such applications.

2. Experimental
Materials: High density polyethylene (HDPE) appropriate for
blown lm production was supplied by Total Petrochemicals
(Feluy, Belgium) under the trade name Lumicenes mPE M5510
EP and is a second generation metallocene HDPE. It has a melt
ow rate (MFR) of 0.28 g/10 min at 2.19 kg/190 1C, density of
0.955 g/cm3 and Tm of 133 1C. Copper nanobers were synthesized via a slightly modied method from that described by
Cho and Huh [9], the reduction of a copperamine complex
in an aqueous-non polar bilayer system with molar composition
of CTAB/TMEDA/H2O/Cyclohexane. For the preparation of
Cu-nanobers the reaction time was 12 h instead of 24 h proposed by Cho and Huh [9].
Nanocomposites preparation and characterization: HDPE nanocomposites containing 0.5, 1, 2.5 and 5 wt% of Cu-nanobers were
prepared by melt-mixing in a HaakeBuchler Reomixer (model
600) at 220 1C and 30 rpm for 15 min. Prior to melt-mixing the
nanoparticles were dried by heating in a vacuum oven at 130 1C
for 24 h. The two components were physically premixed before
being fed into the reomixer. In order to achieve a better dispersion of the nanoparticles in HDPE, a RETSCH planetary ball mill
model S100, was used. The HDPE akes along with the proper
amount of nanoparticles were fed into a C type stainless steel
grinding jar with a capacity of 25 ml. Five steel spheres were also
added as a grinding medium. The milling was set at 500 rpm for a
period of 3 h.
Materials characterization was performed using scanning
electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS) and mechanical properties measurements were
conducted on an Instron 3344 dynamometer, in accordance with
ASTM D638 using a crosshead speed of 5 mm/min (detailed
description of methods and characterization data is provided in
our previous paper) [10].
Oxygen permeability: Oxygen permeability was studied on
relatively thin lms (5075 mm) of HDPE/Cu-nanober samples
prepared by an Otto Weber, Type PW 30 hydraulic press at a
temperature of 22073 1C. Permeability rates of O2 through these
lms were measured using a Davenport Apparatus (London) [11].
Antibacterial behavior: Antibacterial behavior of nanocomposites was studied according to the method proposed be Bahloul
et al. [12]. A mixture of three kinds of bacterial strains, that is,

Eschericia coli DHSa, Pseudomonas uorescens BS3 and Staphylococcus aureus strain, was used in this work. The organisms were
grown on nutrient agar plates. About 3 mm2 of each nanocomposite lm specimen was placed in a petri dish and 100 ml of the
bacterial suspension which contained 1.2  105 colony forming
units (CFU) per ml was added onto the lm surface. Petri dishes
were incubated at 37 1C for 24 h and the number of colonies was
counted. Triple parallel experiments were carried out for each
sample.

3. Results and discussion

Characterization of nanocomposites: The SEM images (Fig. 1a)
veried the successful formation of pure Cu-nanobers, as also
evidenced by the EDS analysis (Fig. 1b), in accordance with the
previously reported method. From SEM micrographs it can
be seen that these Cu-nanobers have an average diameter
200400 nm and length in the range of 1525 mm.
The SEM images of the prepared nanocomposites (Fig. 2)
showed clearly that the Cu-nanobers were well dispersed inside
the polymer matrix. Aggregates were not formed at any nanober
content. This is an advantage since in most cases, especially when
multi-walled carbon nanotubes (MWCNTs) are used, aggregates
are always formed in such types of polymer nanocomposites [13].
From preliminary experiments it was found that the ball milling
procedure applied, before melt mixing, improved substantially

Fig. 2. SEM images of HDPE/Cu-nanober nanocomposites containing 2.5 wt% Cunanobers.

Fig. 1. a) SEM image of Cu-nanobers and b) EDS analysis of Cu-nanobers.

D.N. Bikiaris, K.S. Triantafyllidis / Materials Letters 93 (2013) 14

where TR is the gas transmission rate (ml cm/m2 day atm), p is the
rate of pressure change in the capillary pipe (cmHg/day), V is the
total free volume in the sample cell (5 ml), A is the surface of the
sample (23.77 cm2), T is the temperature at which the experiment
is carried out in Kelvin, and P is the pressure difference at the
beginning of the experiment in cmHg which can be considered as
76 cmHg. Transmission rates can easily be converted to gas
permeability using the following equation:
P TR  l

where l is the lm thickness.

As can be seen in Fig. 3, the neat HDPE has an oxygen
permeability of 8.1 ml cm/m2 day atm. In the case of nanocomposites the permeability was reduced to a signicant extent
by increasing the Cu-nanobers content. At low Cu-nanobers
content (0.5 and 1 wt%) the oxygen permeability was 7.9 and
7.6 ml cm/m2 day atm, which is very close to that of neat HDPE.
However, in nanocomposites containing 2.5 and 5 wt% of
Cu-nanobers there is a reduction to 4.9 and 3.6 ml cm/m2 day atm respectively. It seems that the presence of Cu-nanobers
creates a more tortuous path that the oxygen molecules must go
through within the nanocomposite lm.
Antibacterial properties: In the literature there are some papers
studying the antibacterial effect of copper nanoparticles when
they are added to several polymers [7,17,18]. However, there is no
report concerning the use of copper nanobers. The screening of
the antibacterial activity of the nanocomposites prepared in this

Oxygen Permeability (ml.cm/m2.day.atm)

9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

Cu-nanofibers content (wt%)

Fig. 3. Oxygen permeability of HDPE and its nanocomposites containing different
Cu-nanobers contents.

120000

100000

80000

CFU

the dispersion of nanotubes. However, as can be seen also from

the SEM images, in all HDPE/Cu-nanobers composites the length
of nanobers was slightly reduced. This is due to the shear stress
that is applied inside the head of the mixer, thus resulting in the
breaking of the nanotubes.
In order to evaluate the reinforcing effect of Cu-nanobers to
the HDPE matrix, mechanical properties were measured by the
stressstrain experiments. The tensile strength at break of the
neat HDPE was about 28.4 MPa and Youngs modulus was about
652 MPa. After the addition of Cu-nanobers, the tensile strength
was slightly increased up to 30.8 MPa and 31.7 MPa for the
samples containing 2.5 and 5 wt% Cu-nanobers respectively.
Youngs modulus was increased to 805 MPa and 936 MPa for
the same samples, correspondingly. This is an indication of the
reinforcement effect of Cu-nanobers on HDPE. However, elongation at break slightly deteriorated from about 800% in neat HDPE
to 600% and 370% respectively in nanocomposites containing
2.5 and 5 wt% Cu-nanobers, which was expected due to the stiff
nature of the inorganic additive that cannot be extended.
Oxygen permeability: It is well known that the gas barrier
properties of a polymer matrix can be enhanced by the addition of
inorganic nanoparticles [11,14,15]. This is because inorganic
nanoparticles are impermeable to gases, at least compared
to polymers and organic macromolecules, and their presence
constitutes a solid barrier in the path of the gas molecules
throughout the polymer bulk phase. Thus, gases are forced to
follow a more tortuous path as they diffuse through the material.
The more tortuous the path, the longer it takes for the gas to pass
through the material resulting macroscopically in a reduced permeability. Consequently, nanocomposites prepared by layered materials or other inorganic nanoadditives with relatively high aspect
ratio have been extensively studied for their gas barrier properties
[15,16]. Thus, the permeability rates of O2 through thin lms of
HDPE and its nanocomposites were measured in order to evaluate
the effect of Cu-nanobers. The gas transmission rates (TR) through
each lm were calculated using the following equation:


273pV  24  104
1
TR
ATP

60000

40000

20000

Cu-nanofibers (wt%)
Fig. 4. Growth of bacterial colonies forming units (CFU) in nanocomposites
containing different amounts of Cu-nanobers during incubation time of 24 h.

work was performed by monitoring the colonies increase in petri

dishes. It was observed that the antibacterial effect after 24 h for the
HDPE and HDPE/Cu-nanobers nanocomposites containing up to
1 wt% Cu-nanobers was relatively weak, whereas the antibacterial
effect increased remarkably for the nanocomposites containing
2.5 and 5 wt% Cu-nanobers (Fig. 4). These results clearly show
that the higher the Cu-nanobers loading, the lower the number of
CFU; i.e., the stronger the antibacterial effect. This was expected
since Cu-nanobers due to their small size and relatively high
external area, as well as their ne dispersion into HDPE matrix,
could interact closely with the bacterial membranes leading to
inhibition of their growth. The same behavior was reported also
for copper or silver nanoparticles [19]. It has been proposed that the
bacterial DNA loses its replication ability once the bacteria have
been treated with copper nanoparticles [20]. In another study it was
reported that when copper or silver nanoparticles come in contact
with the bacteria they destroy the cell walls of the bacteria, showing
coppers antibacterial activity [21].

4. Conclusions
HDPE/Cu-nanober nanocomposites exhibited enhanced mechanical, oxygen barrier and antibacterial properties. The improvement of

D.N. Bikiaris, K.S. Triantafyllidis / Materials Letters 93 (2013) 14

these properties depends on the Cu-nanober loading with the

2.5 and 5 wt% showing the best performance. The particular materials
could be appropriate for food packaging applications [19].

Acknowledgments
This research was co-funded by European Union-European
Regional Development Fund and Greek Ministry of Education/
EYDE-ETAK through program ESPA 20072013/EPAN II/Action
SYNERGASIA (Project 09SYN-42-831)
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