Applied Clay Science 58 (2012) 79–87

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Applied Clay Science

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

Research paper

Development of MtCu 2+/LDPE nanocomposites with antimicrobial activity for

potential use in food packaging
J.E. Bruna ⁎, A. Peñaloza, A. Guarda, F. Rodríguez, M.J. Galotto
Center for the Development of Nanoscience and Nanotechnology (CEDENNA,), Food Packaging Laboratory (Laben-Chile), Department of Science and Food Technology, Faculty of Technology,
University of Santiago de Chile (USACH), Santiago, Chile

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

Article history: The antimicrobial efficiency of novel MtCu 2+/LDPE nanocomposites against Escherichia coli 0157:H7 n/t was
Received 23 June 2011 tested in the present work. Montmorillonite modified with copper (MtCu 2+) was obtained using cation ex-
Received in revised form 19 January 2012 change in solution and nanocomposite films were prepared by melt mixing in an extruder at 200 °C with dif-
Accepted 27 January 2012
ferent compositions. Characterization of MtCu2+ and MtCu 2+/LDPE nanocomposites was carried out using
Available online 19 February 2012
XRD, AA, TGA, DSC, and microbiological analysis. The clay polymer nanocomposites (CPN) were more stable
Keywords:
at higher temperatures, resulting from the incorporation of MtCu2+ in the polymer. The results indicate that
Montmorillonite the antibacterial effect of the CPN increases with the proportion of MtCu2+ added, obtaining a 94% reduction
Copper when 4% of MtCu2+ was added to the polymer.
Antimicrobial activity © 2012 Elsevier B.V. All rights reserved.
Copper modified clay
Polyethylene
Nanocomposites

1. Introduction polypropylene (Ciardelli et al., 2008), chitosan (Sanpo et al., 2009)

Food packaging has undergone a radical change in recent years,
from passive packaging, which acts as a simple container and/or insu-
lating barrier from the outside environment, to active packaging that
absorbs substances interacting with food, increasing the shelf life and
quality of products it protects (Risch, 2009).
Developments in active packaging have led to advances in many
areas, including delayed oxidation and controlled respiration rates, mi-
crobial growth, moisture migration, carbon dioxide absorbers/emitters,
odor absorbers, ethylene removers, and aroma emitters (Brody et al.,
2008).
Antimicrobial-active films represent an innovative concept in food
packaging, developed in response to consumer expectations for mi-
crobiologically safer food (Guiga et al., 2009). As a consequence,
there have been several studies using different antimicrobial agents
(Gutierrez et al., 2009).
There has been much interest in the use of metals because of their
antimicrobial effect. Among the metals that have been studied are
gold (Zhang et al., 2008), zinc (Kaczmarek et al., 2009), silver (Kim
et al., 2007), copper (Ren et al., 2009), manganese, molybdenum, titani-
um (Nomiya et al., 2009) and iron (Richards et al., 2009). Metals can
be incorporated in the form of solid metal nanoparticles or metal oxides
in different types of materials: polyethylene (Zhang et al., 2009),
⁎ Corresponding author. Tel.: + 56 2 7184520.
E-mail address: julio.bruna@usach.cl (J.E. Bruna).
and PVC (Rodolfo and Innocentini-Mei, 2010).
The antimicrobial mechanism of metals in some cases is the ability
to induce an electrical field on the microorganism membrane, chang-
ing the permeability of microbial cells; while in other cases, it is
through catalysis, affecting enzyme systems and the metabolism of
bacteria, thus killing the microorganism (Nan et al., 2008).
Copper has been of particular interest because, unlike other anti-
microbial metals, it presents a broad spectrum of action against bac-
teria and molds. The efficacy of copper depends on environmental
conditions, the concentration of copper ions and the type of microor-
ganisms (Cioffi et al., 2005). Given the effectiveness of copper against
pathogenic organisms associated with plant and animal diseases, it
has been widely used in the agricultural and livestock sectors as a
pesticide and growth promoter (Hu et al., 2010).
A critical factor responsible for the antimicrobial properties of
copper is the ability to easily accept or donate electrons, so that it
has a high level of catalytic oxidation and a high reduction potential
(Nan et al., 2008).
When copper is in the oxidation state Cu 2+, it is highly effective
against microbial cells due to interaction with nucleic acids, enzyme ac-
tive sites and components of the cell membrane that cause the death of
microbial cells (Lejon et al., 2010). Moreover, it has been shown that
copper has the ability to reduce the growth rate of E. coli as a microbial
agent by more than 99.99%, causing damage to cell walls and altering
bacterial cell contents (Nan et al., 2008).
Clay minerals have also been of great interest in packaging (Uddin,
2008) because they can be used to obtain clay polymer nanocomposites

0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2012.01.016
80 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87
(CPN) as an alternative to conventional technologies to improve poly-
meric properties. CPN exhibit better barrier properties, mechanical
strength and heat resistance than traditional polymers and convention-
al composites (Arora and Padua, 2010). In addition, clay minerals can
absorb antimicrobial agents. Malachova et al. (2009) studied the activ-
ities of antibacterial compounds, such as cetylpyridinium (CP), cetyltri-
methylammonium (CTA), silver ions and metallic silver, immobilized
on montmorillonite (Mt) against Escherichia coli and Enterococcus
faecium bacteria. Some authors have studied the mechanism of antibac-
terial action of clay minerals modified by incorporating copper (Tong et
al., 2005; Zhou et al., 2004).
The aim of the present study was to obtain a new material based
in low density polyethylene (LDPE) with antimicrobial activity, due
to the incorporation and blending of copper-modified montmorillon-
ite (MtCu 2+), in which Mt will enhance the distribution of copper in
the polymer matrix decreasing the copper agglomeration process.
2. Experimental
2.1. Materials
Low density polyethylene (LDPE) (MFI: 2 dg/min at 190 °C/2.16 Kg
and a density of 920 kg/m3 at 23 °C), Repsol (PE003), natural montmo-
rillonite, kindly supplied by Southern Clay Products, under the trade
name of Cloisite® Na+, Cupric sulfate pentahydrate (CuSO4 × 5H2O),
99.995% trace metals, Aldrich, Luria-Bertani (Muffler and Ulber, 2008)
medium for bacteria were used in this study, E. coli 0157:H7 n/t
obtained from the Public Health Institute, ISP (Santiago, Chile).
2.2. Modified clay mineral preparation
Mt was modified in a CuSO4 solution by ion exchange, mixed at
60 °C for 3 h with stirring. At the end of the reaction, the product was
centrifuged at 4000 rpm and the sediment was washed three times
with distilled water. The product was dried at 80 °C over night and
then ground to sizes lower than 325 mesh (b45 μm). The supernatant
was diluted properly and then the copper concentration was measured
using an atomic absorption spectrophotometer, obtaining the copper
percentage content in the modified montmorillonite (MtCu 2+).
2.3. CPN preparation
MtCu 2+/LDPE nanocomposites were prepared by melt mixing in a
twin screw DSM Xplore 15 mL micro compounder at 200 °C, for
15 min to obtain homogeneous mixtures, obtaining nanocomposite
blends with 1, 2, 3 and 4 wt.% of MtCu 2+. To produce the corresponding
films, a cast film line (Micro film device, DSM Xplore) was connected to
the laboratory scale compounder. The speed of collecting roller was ar-
ranged to obtain an average thickness of 50 μm and width of 300 mm
film. Thermal and mechanical characterizations, X-ray diffraction anal-
ysis and antimicrobial activity tests were performed on the films.
2.4. Characterization
2.4.1. X-ray diffraction
X-ray diffraction patterns of Mt, MtCu2+ and the CPN were recorded
at room temperature, on a Siemens D5000 diffractometer with Cu
λ = 1.54 Å. The scan rate was 1.2°/min, over a diffraction angle 2θ rang-
ing between 2.5 and 12°. The interlayer spaces were calculated by the
Bragg equation (Liao et al., 2010).
The samples were performed in powder form in the case of Mt and
MtCu 2+ and in 50-μm-thick film form in the case of CPN.
2.4.2. Differential scanning calorimetry
Thermal analysis experiments were performed using a Mettler To-
ledo differential scanning calorimeter (DSC) model DSC 822e. The
materials were scanned in non-isothermal conditions. Samples of
about 6 mg were heated from −20 to 200 °C at 10 °C/min and cooled
from 200 °C to − 20 °C at 10 °C/min, then heated again from −20 to
200 °C to obtain the melting point in the second heating and the crys-
tallization point in the cooling stage.
Crystallinity (wc) was calculated from the relationship between the
latent fusion heat of the samples analyzed (ΔHm) and the theoretical la-
o
tent fusion heat for LDPE with 100% crystallinity (ΔHm = 293 J/g) (Shah
et al., 2006), according to the equation used by Persico et al. (2009).
2.4.3. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed using a SDT
2960 DSC-TGA, TA Instruments, at 20 °C/min, between 0 and 800 °C,
in air.
2.4.4. Fourier Transform Infrared Spectroscopy
FTIR spectra were recorded on a Bruker IFS-66 spectrometer from
4000 to 400 cm − 1 with an average of 32 scans at 4 cm − 1 resolution.
The modified and unmodified clay minerals were mixed with KBr to
obtain pellets. LDPE and CPN films (50 micrometer thick) were di-
rectly measured in the spectrophotometer.
2.4.5. Opacity
Opacity of the CPN films was determined using a UV/Vis spectropho-
tometer UVmini-1240 (Shimadzu Corporation, Kyoto, Japan). The film
samples were cut into a rectangular piece (1.0×4.5 cm) and placed on
the sample compartment of a spectrophotometer. An empty compart-
ment was used as a reference in the measurement. The opacity of films
was calculated using Opacity=Abs600 /X (Tunc and Duman, 2010),
where: Abs600 =Absorbance at 600 nm; X =Film thickness (mm).
2.4.6. Surface color measurement
CPN film color was measured using a Cam-System 550 (Lovibond,
Amesbury, UK). The CIELAB scale was used, lightness (L) and chroma-
ticity parameters a (red-green) and b (yellow-blue) were measured. A
white standard color plate was used as the background for color mea-
surements D65 illuminant and 10° observer was used for analysis.
Each analysis was performed in five replicates and results reported
the average value. The total color change ΔE was calculated by ΔE =
[(ΔL*) 2 + (Δa*) 2 + (Δb*) 2] 1/2.
2.4.7. Mechanical properties
Tensile testing was performed at room temperature on a Zwick Roell
dynamometer, model M.BDO-FBO 5HT, according to ASTM D 882. Tests
were carried out at a cross-head speed of 50 mm/min until breaking.
2.4.8. Antimicrobial activity
The antimicrobial effects of CPN and MtCu 2+ were tested against
E. coli, selected as an example of gram-negative bacteria. E. coli 0157:
H7 n/t were obtained from the Public Health Institute, ISP (Santiago,
Chile). Antimicrobial capacity was determined using the E 2149 test of
the American Society for Testing and Materials (ASTM). The average ini-
tial microorganism concentrations were 109 CFU/mL. Serial dilutions in
buffer solution were carried out, and the microorganism suspensions
were plated on LBA. Colonies were quantified in the dilution 1 × 10− 6,
after incubation at 37 °C for 24 h. Results were expressed as the number
of colony forming units per mL. In turn, the percentage of inhibition of
different antimicrobial films was calculated with the equation estab-
lished in the standard test method ASTM E2149-01.
2.4.9. Scanning Electron Microscopy
SEM photographs were taken with a Zeiss EVO/MA10, at
4 × 10 − 5 Torr, 1 kV in inert atmosphere with 15,000× magnification.
The films were previously fractured under liquid nitrogen in prepara-
tion for cross-section analysis.
 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87 81

3. Results and discussion

d=1,22 nm

3.1. Modified clay mineral

Relative Intensity (a. u.)

3.1.1. Quantification of Cu 2+ incorporated in the clay mineral
In order to quantify the amount of Cu 2+ incorporated in Mt, the b
effect of the initial concentration of copper on the extent of metal in-
corporation was evaluated. As shown in Fig. 1, the amount of Cu 2+ in-
corporated in Mt increases with the initial increase in copper salt
concentration. A maximum quantity of copper incorporation of 3.0% a d=1,12 nm

is attained when the concentration of CuSO4 × 5H2O is around 20%

w/w, maintaining the incorporation of copper at this level. This be-
havior could be due to the exchange sites being saturated, with no
possibility of adding more ions to reach the CEC, or caused by block-
age to the metal ions when the clay mineral is hydrated or partially
10
hydrated (Huang et al., 2004).
2 Theta (degrees)

3.1.2. X-ray diffraction Fig. 2. XRD patterns a) Mt and b) MtCu2+.

Fig. 2 shows the X-ray diffraction patterns of Mt and MtCu2+ in the
range of 2θ = 2–12°. These results demonstrate that Cu2+ was incorpo-
An additional absorption band around 3170 cm− 1, corresponding to
rated effectively into the interlayer of Mt, where the basal spacing
the Cu2+\OH stretching (Kloprogge et al., 2006), was identified by
(d001) of the clay mineral layers increased from 1.12 nm (2θ = 7.90°)
close examination of the FTIR spectrum of MtCu2+. This band which ap-
for Mt to 1.22 nm (2θ = 7.21°) for MtCu2+, due to Cu2+ ion exchange
pears to overlap with the water\OH stretching band (3410–3505 cm− 1)
by Na+. Similar values have been reported by Oueslati et al. (2009).
evidences the interaction of Cu2+\OH in the interlayer space clay
The increase in the clay mineral interlayer is due to the size differences
mineral.
of the hydrated forms of Cu2+ and Na+ ions (Tanaka et al., 2007), where
Moreover the band located at 1450 cm − 1, attributed to the pres-
copper species present in Mt are hexaaqua complexes form
ence of organic groups in the clay mineral, disappears due to the
([Cu(H2O)6] 2+). This has been reported by He et al. (2001) in studies
fact that those groups were removed in the washing procedure
about adsorption of different metals in Mt.
(Kloprogge et al., 2006).

3.1.3. Fourier Transform Infrared Spectroscopy (FTIR) 3.1.4. Thermogravimetrical analysis

The presence of copper in the interlayer space of the clay minerals
was confirmed by FTIR. Fig. 3 shows FTIR spectra of Mt and MtCu2+
(in the range 4000–500 cm− 1), in which the characteristic peaks of
this type of clay mineral can be observed. Therefore, a shift in the band
corresponding to the \OH stretching mode of the Al\OH or Si\OH of
Mt (Xie et al., 2010), from 3626 cm − 1 to 3631 cm-1 when Cu2+ was in-
corporated in the clay mineral. Kloprogge et al.(2006) obtained a shift in
the band between 5 and 20 cm − 1 with the addition of copper. This be-
havior is caused by eliminating structural groups from the clay mineral,
such as hydroxyl groups in Si\OH and Al\OH after cation exchange
with copper (Sarier et al., 2010). On the other hand, a minor effect of
copper was observed in the band associate with the bending in plane vi-
bration of the O\H from water at 1640 cm− 1(Sarier et al.,). So, this
band shifted to 1633 cm− 1 when the copper was added. However this
shift is not sufficient to establish that the addition of copper causes
changes in the hydrophilic nature of the clay mineral.
The thermal behavior of Mt and MtCu 2+ was evaluated by ther-
mogravimetrical analysis. Fig. 4 shows the two main weight losses:
the first, which occurs at 90 °C, corresponds to the dehydration of
water from the aluminosilicate layers (Hassanien and Abou-EI-
Sherbini, 2010) and (ii) the second, which occurs at 692 °C, corre-
sponds to the dehydroxylation typical of Mt. A new peak (iii) can be
observed in MtCu 2+ at 329 °C, which could be related to the water as-
sociated with the absorbed copper species (Ding and Frost, 2004;
Kloprogge et al., 2006). This weight loss is only appreciable at tem-
peratures higher than 500 °C.
3.1.5. Minimum inhibitory concentration
The growth of E. coli treated with different concentrations of
MtCu 2+ was evaluated (Fig. 5). Concentrations of 10 to 1000 ppm of
modified clay mineral were used to determine the minimum inhibito-
ry concentration (MIC). In this way, the MIC of MtCu 2+ was estimated

1,0
b
0,8
Absorbance

0,6 a
3626
0,4 1,0
b
Absorbance

3170
0,5 a
0,2
3631
0,0
4000 3800 3600 3400 3200 3000
0,0 \Wavenumber (cm-1)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)
Fig. 1. Variation of Cu2+ incorporate (wt.%) in Mt as function of the amount of
CuSO4 × H2O added. Fig. 3. FTIR spectra between 4000 cm− 1 and 400 cm− 1 of a) Mt and b) MtCu2+.
82 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87

a Table 1
Optical properties of pure LDPE and MtCu2+/LDPE nanocomposites.
100
0,00
MtCu2+/LDPE L* ΔE* Opacity

0/100 47.3 ± 0.3a 0.0 ± 0.0a 0.18 ± 0.10a

Weight Loss (%)

1/99 46.9 ± 0.5ab 0.5 ± 0.3b 0.65 ± 0.12b

95
-0,05 2/98 46.1 ± 0.6bc 1.5 ± 0.5c 1.29 ± 0.12c

DTG (%/°C)
3/97 44.9 ± 0.7d 2.5 ± 0.6d 1.71 ± 0.15d
4/ 96 43.9 ± 0.9e 3.4 ± 0.8e 2.87 ± 0.25e

90 -0,10 Each value is the mean of five replicates with the standard deviation. Some letters for
each colum are not significantly (p > 0,05) different by Fisher's multiples range test.

-0,15 (Hu et al., 2005) and 1024 ppm against E. coli K88 (Tong et al.,
85
2005). The results are quite positive compared to the MIC value
obtained using only copper nanoparticles (20–300 ppm) on E. coli
0 200 400 600 800 O157: H7 (Ruparelia et al., 2008).
Temperature (°C)

b 3.2. MtCu 2+/LDPE nanocomposites

0,00
100 3.2.1. Optical properties
-0,02
Table 1 shows the optical properties (color and opacity data) of
CPN and pure LDPE films. In general, the optical properties of the
Weight Loss (%)

-0,04
CPN films presented an increase on the opacity due to the presence
DTG (%/°C)

95
-0,06
of Mt. The increase on the opacity could be attributed to the presence
-0,08 of Mt as it is an inorganic material that is not dissolved in the polymer
90 matrix which causes a decrease in the transparency. Nevertheless the
-0,10
percentage of Mt incorporated is very low (less than 5%), the layers of
-0,12 Mt are smaller than wavelengths of the light, so, they do not deflect or
reflect the light (de Paiva et al., 2007). The increase on the opacity
85 -0,14
should not only be attributed to the presence of Mt but also to the
-0,16 copper that is intercalated in the clay mineral and thermally oxidized
0 200 400 600 800 to copper oxide during the extrusion process. This was also observed
Temperature (°C) by Labaki et al. (2005) in studies of copper compound calcinations in
presence of oxygen.
Fig. 4. TG and DTG curves of the thermal degradation of a) Mt and b) MtCu2+.
As it can be seen in Table 1 the presence of copper produces a de-
crease on the luminosity of the films (a decrease of L* parameter)
based on the concentration at which there was a 100% reduction of with a concomitant increases on ΔE value. It must be taken into ac-
bacteria (Michels et al., 2008), obtaining a MIC value of 100 ppm, count that ΔE of ±0.5 is able to be recognized by sensorial panel as
demonstrating that although copper is embedded in the clay mineral, a different color, being much more important when ΔE is higher
it does not lose its antibacterial activity. than ±2.0. It should be pointed out that ΔE is mainly affected by L*
This result agrees with a previous work in which the values decrease, meanwhile a* and b* values are not significantly modified
obtained were 150 ppm in assessing MtCu 2+ against A. hidrophyla (data not shown).

Fig. 5. Antimicrobial effect of MtCu2+ on Escherichia coli: a) without MtCu2+ b) 90 ppm MtCu2+ b) 100 ppm MtCu2+ ASTM E-2149 method.
 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87 83

3.2.2. X-ray diffraction Table 2

X-ray diffraction technique was used to reveal the kind of interac- DSC data of LDPE and MtCu2+/LDPE nanocomposites.

tion between the polymer and the clay mineral. Fig. 6 presents the MtCu2+/LDPE Tm (°C) ΔHm (J/g) Tc (°C) ΔHc (J/g) Crystallinity (%)
analysis of the pure LDPE and the CPN with different concentrations
0/100 111.8 63.1 96.7 90.1 21.5
(1, 2, 3 and 4% MtCu 2+). 1/99 111.8 54.5 95.1 79.0 18.8
All CPN showed a clear diffraction peak around 6.90–7.15 2θ angle, 2/98 109.5 53.4 97.2 85.3 18.6
which can only be associated to the interlayer distance (d001) of the 3/97 109.5 50.2 97.2 83.6 17.6
4/96 111.0 55.1 95.9 89.5 19.6
clay mineral incorporated in the polymer (Shah et al., 2006), because
the pure LDPE did not present this characteristic peak (Olewnik et al.,
2010).
On the other hand, it is observed that (Fig. 6), a shift of the
peak at 2θ angle values was smaller compared to the value 3.2.3. Differential scanning calorimeter
obtained from pure clay mineral, due to a certain degree of clay We studied the effect of adding different MtCu 2+ concentrations
intercalation into polymer matrix, as was observed in studies of on the thermal properties of the CPN in comparison to the effect of
Lee et al. (2010). pure LDPE. Table 2 shows that the melting temperature (Tm) for
The values of interlayer distances, d001 for the CPN were 1.26 nm pure LDPE and the different CPN remains practically unchanged.
(2θ = 6.96°), 1.24 nm (2θ = 7.12°), 1.24 nm (2θ = 7.14°) and This effect was also observed by Malucelli et al. (2007), who found
1.25 nm (2θ = 7.05°) with 1%, 2%, 3% and 4% of MtCu 2+, respectively, no significant differences in the melting temperature with the addi-
showing an increase in the interlayer of the clay mineral when com- tion of 3 wt.% Mt in LDPE. Similarly, Gao et al. (2010), found no
pared to the value obtained from the modified clay mineral change in the melting temperatures by adding different modified
(d001 = 1.22 nm), demonstrating that the clay mineral is intercalated clays in ionomers [poly (ethylene-co-acrylic acid)] neutralized by
into the polymer matrix. This was expected, because the apolar na- zinc salts.
ture of the LDPE and hydrophilic clay (Golebiewski and Galeski, On the other hand, the crystallization temperature (Tc) of pure
2007) does not allow for close interaction between them. Thus, the LDPE and the different CPN (Table 2) did not vary significantly, indi-
hydroxyl groups located at the edge of the clay mineral layers tend cating that the addition of modified clay mineral does not cause
to hinder the formation of intercalated or exfoliated CPN (Olewnik changes in LDPE crystalline structures. This is because MtCu 2+ can
et al., 2010). present a certain degree of polarity owing to the presence of copper
Moreover, it can be seen that the d001 variation of both CPN is not ions in the clay mineral that show less affinity for LDPE and therefore
significant, which confirms that the clay–polymer interaction is inde- do not affect the form of polymer crystallization. By contrast, when
pendent of the concentration added to the matrix. components with higher affinity to the polymer matrix are added,
the presence of small silicate layers induces the formation of nuclei,
and crystals can start growing at higher temperatures (Giannakas et
al., 2009), with significant variations beginning with the addition of
10% clay. It is worth noting that our study worked with quantities var-
e ies from 1% to 4%, which could explain why we did not observe vari-
d=1.25nm ations in the crystallization temperatures.
With regard to the results obtained from crystallinity (Table 2),
the CPN have lower values than pure LDPE, indicating a decrease in
crystallinity. This could be because modified clay mineral hinders
the movement of polymeric chains, slowing the growth of crystals.
A similar effect was reported by Olewnik et al. (2010), who estab-
d=1.24nm d lished that the addition of a small amount of Mt in PP represents an
increase in heat enthalpy, which they attributed to two factors: the
slowing of crystallization kinetics and obstruction of the crystalline
Relative Intensity (a.u.)

regions, caused by the dispersion of clay mineral in the polymer.

This same effect was observed by Xia et al. in studies of Cu 0/LDPE
d=1.24nm nanocomposites (Xia et al., 2006) in which the values of crystallinity
c decreased from 87.84 J g − 1 to 76.23 J g − 1 and 71.64 J g − 1 for micro-
and nanoparticles of copper, indicating that the clay mineral blocked
heat flow through the polymer chain segments, with the layers acting
as a barrier preventing escape of volatile products of decomposing
material (Gao et al., 2010).
d=1.26nm No clear trend was observed in the crystallinity among different
b
CPN. There was perhaps a slight increase with increasing additions
of nanofiller because the silicate layers of modified Mt acted as a nu-
cleating agent and accelerated the growth of crystals, which has been
reported in other studies (Giannakas et al., 2009). Possibly, this effect
was not appreciated in this study because low concentrations were
used.
a
3.2.4. Thermogravimetric analysis
The thermal stability of LDPE and all CPN was studied by thermo-
4 8 12 16
gravimetric analysis (TGA). Fig. 7 shows an increase in degradation
2 Theta (degrees)
temperature when MtCu 2+ is incorporated into LDPE, in all cases, giv-
Fig. 6. XRD patterns of a) pure LDPE, b) 1%MtCu2+/LDPE, c) 2%MtCu2+/LDPE/, d) ing higher thermal stability to the polymer. This could be attributed
3%MtCu2+/LDPE and e) 4%MtCu2+/LDPE. to the presence of clay mineral, because it acts as a superior insulator
84 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87
120
pure LDPE
2+
100 1% MtCu /LDPE
2+
2% MtCu /LDPE
2+
3% MtCu /LDPE
Weight loss (% wt.)
2+
80 4% MtCu /LDPE
60
40
20
0
-20
200 400 600
Temperature (°C)
Fig. 7. TG curves of the thermal degradation of LDPE and its MtCu2+/LDPE nanocompo-
sites, with various levels of MtCu2+ nanoparticle content.
and mass transport barrier to the volatile products generated during
decomposition (Papaspyrides and Pavlidou, 2008).
This effect has been corroborated by Golebiewski and Galeski
(2007), where the addition of clay mineral in polypropylene in-
creased the degradation temperature from 350–380 °C to 420 °C. Al-
though the incorporation of Mt in the polymer matrix brings with it
an increase in thermal stability, the addition must be controlled, be-
cause that could cause catalysis in polymer degradation, due to exces-
sive incorporation (Zhao et al., 2005). Moreover, studies carried out
by Lomakin et al., using montmorillonite with polar compatibilizer
in LDPE, showed that the increase in the material degradation tem-
perature is due to an increase in activation energy (Lomakin et al.,
2008).
It has been reported that the addition of copper nanoparticles in
LDPE and LLDPE increases thermal stability due to their higher heat
capacity and thermal conductivity (0.39 kJ − 1 g − 1 compared to
0.18 kJ − 1 g − 1 LDPE) (Luyt et al., 2006) resulting in greater absorp-
tion of heat by the material, causing degradation of LDPE chains at
higher temperatures (Molefi et al., 2009). However, thermal stability
decreases when the copper content is greater than 5%, due to the
presence of metallic copper nanoparticles clusters, causes an increase
in energy diffusion (Luyt et al., 2006). Shen et al. (2008) indicate that
metal ions could accelerate the deterioration of some polymers, such
as SAN, in which the degradation mechanism is affected by the pres-
ence of CuSO4 when the material is in prolonged contact with a tem-
perature above 230 °C.
Finally, more detailed analysis of the TGA curves for the different
CPN shows that there is a slight inflection at 220 °C. This is because
some of the Cu 2+ is transformed into copper oxide in the presence
of heat and oxygen during the extrusion process, as reported by
Labaki et al. (2005).
3.2.5. Mechanical properties
MtCu 2+/LDPE nanocomposites were characterized by measure-
ments of tensile modulus (E), tensile strength (σb) and elongation
at break (εb), which showed the influence of MtCu 2+ on the proper-
ties studied (Table 3). The tensile modulus (Young's modulus) de-
creased with the incorporation of MtCu 2+, based on comparison to
pure LDPE. This differs from what was expected because the presence
of clay mineral should have increased Young's modulus
(Papaspyrides and Pavlidou, 2008). This value would have increased
even more if compatibilizers had been used (Hwang et al., 2009),
due to presence of high-aspect-ratio stiff silicate layers in the polymer
Table 3
Mechanical properties of pure LDPE and LDPE nanocomposites.
MtCu2+/LDPE Tensile modulus Tensile strength Elongation at break
(N/mm²) (N/mm²) (%)
0/100 650 ± 28a 128.6 ± 6.6a 155.9 ± 35.9a
1/99 464 ± 39b 78.1 ± 11.6b 201.8 ± 74.1b
2/98 320 ± 11c 64.8 ± 4.0c 96.7 ± 7.2c
3/97 376 ± 17d 74.4 ± 4.5bd 152.5 ± 21.5ad
4/96 387 ± 56de 56.5 ± 4.7e 131.7 ± 25.9ade
Each value is the mean of ten replicates with the standard deviation. Some letters for
each colum are not significantly (p > 0,05) different by Fisher's multiples range test.
matrix, which resulted in more interaction with the polymer chains
(Mallick et al., 2010).
However, previous studies have reported that the addition of
small amounts of copper (≤4%) in a low linear density polyethylene
800
(LLDPE) matrix decreases the Young's modulus because of the weak
interaction between LLDPE and copper (Luyt et al., 2006). Studies of
micro- and nano-composites of LDPE/Cu 0 have shown that the higher
the copper particle content, the greater the agglomeration and the
lower is more serious the agglomeration and the worse the elonga-
tion at break and tensile strength of the composites (Tang et al.,
2011). Therefore, the variation in the tensile module in this study
may have been because of poor interaction between the polymer
and the modified clay owing to the presence of copper in the clay
mineral.
On the other hand, there were no significant changes in the tensile
modulus among the different CPN, which could have been because
variations among concentrations were from only 1 to 4%.
Finally the values of elongation at break decreased with the addi-
tion of modified clay mineral with copper because adding filler to the
polymer matrix reduces chain mobility, giving rise to a rapidly de-
creasing elongation at break (Molefi et al., 2010). This effect is due
to the type of interaction between the clay mineral and the matrix,
in which the clay reinforces the polymer (Ophir et al., 2010). This is
corroborated by previous studies that established that the effect on
the elongation at break is more significant in LDPE than in HDPE
(Olewnik et al., 2010). Even with LLDPE, the elongation at break is
higher because the polymer chains have enough room to orient them-
selves as a result of the structure of the material when force is applied
(Luyt et al., 2006).
So, presence of nanofiller inside the LDPE structure was not able to
produce changes on the mechanical properties. This can be attributed
to a lack of a good homogenization of MtCu 2+ in the polymer matrix
(Zhao et al., 2005), and to the use of a low concentration of
nanofiller(b5%), as it has been reported that to produce significant
changes on the mechanical properties, nanofiller should be added
with feed greater than 5 wt.%. (Weiss et al., 2006).
3.2.6. Scanning Electron Microscopy (SEM)
Scanning Electron Microscope (SEM) was used to check the solid
morphology of LDPE and the CPN on the upper surface and cross-
sections, as shown in Figs. 8 and 11 respectively.
As can be observed in the SEM images (Fig. 8), the upper surface of
the LDPE film is very soft and smooth. The surfaces of the nanocom-
posite films are different because the presence of particles modifies
the surface texture, changing the structure of the material and caus-
ing the more imperfect film that is observed (Zhu et al., 2011).
This could also be attributed to some of the nanoparticles that are
forming agglomerates. This effect was observed by Molefi et al.
(2009) working with copper nanoparticles in LDPE.
The fracture surface of LDPE (Fig. 9) is smooth and uniform with a
fairly smooth fracture, whereas with the addition of MtCu 2+ nano-
particles the fractue surfaces of nanocomposite films are rough. This
could be related to the mechanical properties given that previous
studies have shown that when there are obvious changes, such as
 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87 85

Fig. 8. SEM micrograph of upper surface of MtCu2+/LDPE nanocomposites with a) 0% MtCu2+, b) 1% MtCu2+, c) 2% MtCu2+, d) 3% MtCu2+, e) 4% MtCu2+.

the formation of microvoids due to the debonding of clay layers from 3.2.7. Antimicrobial activity
the matrix, they will coalesce into larger cracks, causing embrittle- The antimicrobial capacity of the CPN was established by comparing
ment and ultimately resulting in reduced toughness (Papaspyrides the initial number of CFU of E. coli (determined by a calibration curve) to
and Pavlidou, 2008). the final number of bacterial colonies after contact with the different

Fig. 9. SEM micrograph of the cross-sections of MtCu2+/LDPE nanocomposites with a) 0% MtCu2+, b) 1% MtCu2+, c) 2% MtCu2+, d) 3% MtCu2+, e) 4% MtCu2+.
86 J.E. Bruna et al. / Applied Clay Science 58 (2012) 79–87
Fig. 10. Logarithm of the number of colony-forming units (CFU) as a function of the concentration of MtCu2+ nanoparticles in the films. The photograph above shows LB plates on
Escherichia coli containing different concentrations of MMTCu2+: a) pure LDPE b) 1%MtCu2+/LDPE c) 2%MtCu2+/LDPE d) 3%MtCu2+/LDPE e) 4%MtCu2+/LDPE ASTM E-2149
method.
CPN. As expected, pure LDPE films did not show any antimicrobial activ-
ity (Fig. 10), while in the case of the CPN, antibacterial activity against
E. coli was observable after the addition of 2% MtCu2+ to the LDPE. Sig-
nificant reductions in bacteria were obtained with increasing MtCu2+
concentrations in the growth medium. High concentrations of copper
in the medium have demonstrated complete cytotoxicity against
E. coli (Raffi et al., 2010) because of the antimicrobial capacity of metal
ions, which is related to the number of the cations released in the solu-
tion (De Muynck et al., 2010). The antimicrobial capacity of copper
against E. coli is due to the ability to adhere to the cell wall by electrostatic
forces, imparting damage to the cell membrane. The cytoplasm is then de-
graded and disappears, leading finally to cell death (Raffi et al., 2010).
Although the polymer matrix is non-polar, the diffusion of the copper
atoms adsorbed on the surface is enhanced as the surface temperature in-
creases, which results in the atoms finding suitable positions to deposit
themselves and aggregate to form larger grains(Kong et al., 2010).
Regarding the percentages of reduction obtained (Table 4), adding
1% of MtCu 2+ does not obtain a significant reduction, which may be
improved by adding 2% of MtCu 2+. A maximum reduction value of
94% was obtained with the addition of 4% MtCu 2+.
Comparing these results to those reported by Hu and Xia (2006),
who obtained an inhibition value of 97.5% for Cu 2+/Na +Mt and
95.6% Cu 2+/Ca 2+Mt, tested against E. coli K88. The values obtained
in our study are quite close and could be considered very good. The
values reported by Hu et al. were obtained using modified clays di-
rectly, while in our study the nanofiller (MtCu 2+) was in the polymer
matrix, which could have slowed its diffusion and thus its antimicro-
bial activity during the period of contact with the bacterial strain.
4. Conclusions
In this work antimicrobial MtCu 2+/LDPE nanocomposites with
different concentrations of MtCu 2+ were prepared by using the
melt-blending technique in an extruder.
Table 4
Antimicrobial activity of pure LDPE and LDPE nanocomposites.
MtCu2+/LDPE Number of colonies UFC/ml × 10− 9 Reduction percent of
(in petri dish) bacteria (%)
1/ 99 527 ± 13 5.3 ± 0.1 1.4 ± 2.5
2/98 431 ± 13 4.3 ± 0.1 19.3 ± 2.5
3/97 263 ± 10 2.6 ± 0.0 50.8 ± 1.8
4/96 32 ± 15 0.3 ± 0.1 94.0 ± 2.8
The thermal properties of the CPN obtained were studied by DSC
and TGA. No variation in Tm or reduction in the crystallinity of LDPE
was found in the presence of nanoclays. The decomposition tempera-
ture of MtCu 2+/LDPE nanocomposites appears to increase with the
addition of modified clay content. This is due to the improved thermal
barrier effects of the clay in the CPN.
The XRD measurement indicated that the Mt layers were interca-
lated, and the SEM observation showed that the nanoparticles were
uniformly distributed in the CPN, except that some of them tended
to form agglomerates, due to the weak interaction between LDPE
and MtCu 2+.
The presence of a small amount of clay reduces the tensile modulus
and elongation-at-break compared to pure LDPE, which is more brittle.
The antimicrobial activity of MtCu 2+/LDPE nanocomposite films
against E. coli was very effective, obtaining the best results with 4%
of nanofiller, reaching a 94% reduction of colonies. In conclusion, the
MtCu 2+/LDPE nanocomposite could satisfy the mechanical property
requirements of food packaging.
Acknowledgements
The authors thank the Comisión Nacional de Investigación Científica
y Tecnológica, CONICYT, for financial support from the Programa Bicen-
tenario de Ciencia y Tecnología (Project PDA-22) and the Programa de
Financiamiento Basal para Centros Científicos y Tecnológicos de Exce-
lencia (Project FB0807). The authors are also grateful for support from
the Departamento de Investigaciones Científicas y Tecnológicas, Univer-
sidad de Santiago de Chile, DICYT-USACH (Project 051071BB). Finally,
the authors thank Juliano Denardin for carrying out the SEM.
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