Article

Journal of
Copyright © 2015 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 15, 2148–2156, 2015
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Polyethylene Films Containing Silver Nanoparticles for

Applications in Food Packaging: Characterization of
Physico-Chemical and Anti-Microbial Properties
Aline A. Becaro1 2 , Fernanda C. Puti1 2 , Daniel S. Correa1 2 , Elaine C. Paris2 ,
José M. Marconcini2 , and Marcos D. Ferreira1 2 ∗
1
Universidade Federal de São Carlos (UFSCar), Rodovia Washington Luís, km 235, São Carlos, SP, 13565-905, Brazil
2
EMBRAPA Instrumentação, Rua XV de Novembro, 1452, Caixa Postal 741, São Carlos, SP, 13560-970, Brazil

This paper reports the antibacterial effect and physico-chemical characterization of films containing
silver nanoparticles for use as food packaging. Two masterbatches (named PEN and PEC) con-
taining silver nanoparticles embedded in distinct carriers (silica and titanium dioxide) were mixed
with low-density polyethylene (LDPE) in different compositions and extruded to produce plain films.
These films were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD),
Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA) and Fourier Transform
Infrared Spectroscopy (FTIR). The morphology of the films showed the formation of agglomerates
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in PEN samples andIP: 94.203.164.177
TiO On:Thermal
2 in PEC samples. Mon, 12analyses
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indicated an increase in thermal
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stability of the PEC compositions. TheAmerican Scientific
antimicrobial efficacyPublishers
was determined by applying the test
strain for Escherichia coli and Staphylococcus aureus, according to the Japanese Industrial Stan-
dard Method (JIS Z 2801:2000). The films analyzed showed antimicrobial properties against the
tested microorganisms, presenting better activity against the S. aureus than E. Coli. These findings
suggest that LDPE films with silver nanoparticles are promising to provide a significant contribution
to the quality and safety of packaged food.
Keywords: Polyethylene, Silver, Nanoparticles, Antimicrobial, Food Package.

1. INTRODUCTION effect of nanoparticles when applied to polymers used for

Advances in nanotechnology have facilitated the
development of tools that supply the needs of society.
Nanotechnology refers to the application, production,
and processing of materials at the nanometer scale and
it has expanded its applications in physics, chemistry,
biology, engineering and technology, due to the appealing
properties of nanoscale structures.1 2 The applications
include materials designed for life care, environmental
monitoring, food safety, and defense.3
In the context of nanomaterials, metal nanoparticles
have dimensions smaller than 100 nm, presenting unique
physical, chemical and biological properties compared to
the particles in the micro scale. Such properties orig-
inate from its high surface area/volume ratio.4 Studies
reported in the literature show the strong reinforcing
∗
Author to whom correspondence should be addressed.
packaging.5–7 New polymeric materials containing inor-
ganic nanoparticles have also been proposed as food pack-
ing for food industry.8 Besides enhancing the physical
and mechanical properties of nanocomposites, some metal
nanoparticles present antimicrobial properties9 10 which
can also be used to improve food shelf-life.11
The use of nanoparticles within polymeric matrix to
produce food packaging has proven to be effective in pre-
serving food. For instance, antimicrobial films prepared
from LDPE resin containing TiO2 powders decorated with
silver nanoparticles have been reported.8 These master-
batches were mixed to pure LDPE resin into a single
screw extruder at 190  C in two heating zones, which
yielded films with little agglomeration well distributed in
the polymeric matrix. Some studies on the development
and use of food packaging containing silver nanoparticles
have shown a good distribution of silver nanoparticles in

2148 J. Nanosci. Nanotechnol. 2015, Vol. 15, No. 3 1533-4880/2015/15/2148/009 doi:10.1166/jnn.2015.9721

Becaro et al. Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging
LDPE12 and a decrease in the rate of microbial growth.13
Other studies have also reported shelf life extension of
food,14 besides the benefit of simple processing and feasi-
bility of becoming industrialized.9 However, studies com-
paring the performance of polymeric films containing
silver nanoparticles dispersed in distinct inorganic car-
riers are still limited. In this work, we produced and
characterized films of LDPE with different contents of
silver nanoparticles embedded in two distinct carriers:
silicon dioxide and titanium dioxide. Both films were
characterized by means of X-ray diffraction, infrared spec-
troscopy, electronic scanning microscopy, thermal analysis
and antimicrobial properties aiming at applications of this
material in food packaging.
2. MATERIALS AND METHODS
2.1. Materials
We employed two masterbatches based on Low-Density
Polyethylene, with distinct carriers containing silver
nanoparticles in their compositions. The first one, named
PEC, contains 15% of TiO2 carrier, while the second one,
named PEN, contains 5% of SiO2 carrier. The master-
batches and pure LDPE pellets (PB 608, obtained from
Quattor® ) were mixed in plastic bags for 3 minutes in dis- were performed using a thermogravimetric analyzer TGA-
tinct mass percentage according to Table I.
2.2. Film Preparation Delivered by Publishing Technology to: Adelaide Theological
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All the compositions displayed in Table I were extruded
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in films with thickness of 5 ± 08 m and width of 18 cm,
by using a plastic benchtop single screw extruder (AX
Plastic). These mixtures were added to the extruder with
three heating zones, set with the following parameters:
temperatures of 160  C (zone 1), 145  C (zone 2) and
130  C (zone 3), and screw speed of 35 rpm for all
materials. The extruded product was collected only after
the three zones reached equilibrium temperature and the
material was homogeneous (bubble and granules-free on
surface).
2.3. Characterization of the Films
2.3.1. Scanning Electron Microscopy SEM
Scanning Electron Microscopy (SEM) technique was used
to identify morphological features of the transversal film and FTIR spectra were recorded using the transmittance
Table I. Nomenclature and compositional ratio between the master-
batch the resin employed to produce the films.
Nomenclature Masterbatch:LDPE (mass percentage)
PEC 2.5 2.5:97.5
PEC 50 50:50
PEC 100 100:0
PEN 2.5 2.5:97.5
PEN 50 50:50
PEN 100 100:0
LDPE 0:100
J. Nanosci. Nanotechnol. 15, 2148–2156, 2015
profile as well as of the carriers containing silver. The
samples were prepared by cryogenic fracture, and the
images were obtained in backscattering mode, using a
FEI microscope, Inspect S50 model and 25 kV. Energy
dispersive X-ray Spectroscopy (EDX) measurements were
carried out to analyze the chemical composition of the
samples.
2.3.2. X-Ray Diffraction XRD
Shimadzu XRD–6000 system was used for X-ray diffrac-
tion measurements of the nanocomposite films. Polymeric
samples were placed into the X ray chamber under accel-
eration voltage of 30 kV, current of 30 mA and speed of
1  min−1 . The samples were scanned using 2 values from
5 to 80 degrees. The diffractograms were fitted using a
Gaussian profile curve. The extent of crystallinity (CI%)
was estimated on the basis of area under crystalline and
amorphous peaks after appropriate baseline correction and
application of a deconvolution technique and a Gaussian
line shape to the peaks.
2.3.3. Thermal Analysis
Thermogravimetric analysis (TGA) of the extruded films
Q500 (TA Instruments) in the temperature range from 10
to 800  C, using a heating rate of 10  C min−1 . The nitro-
gen and synthetic air flow were maintained at 40 mL min−1
−1
Library
and1260Oct
mL2015
min 06:57:44
, respectively.
Differential Scanning Calorimetry (DSC) curves were
obtained in a differential scanning calorimeter Q100 (TA-
Instruments). The experiments were performed in the tem-
perature range from 10 to 200  C, using a heating rate
of 10  C min−1 , under a nitrogen flow of 60 mL min−1 .
Thereafter, samples were cooled down to 10  C at a rate
of 10  C min−1 .
2.3.4. Infrared Spectroscopy FTIR
The films were analyzed by Fourier Transform Infrared
Spectroscopy (FTIR) using a Paragon 1000 Perkin–Elmer
Spectrophotometer. All measurements were obtained using
an average of 32 scans in the range from 4000 to 400 cm−1
with a resolution of 4 cm−1 . Samples of the films were
directly fixed on a support without further preparation,
method.
2.3.5. Microbiological Analysis
The antimicrobial activity of the films was evaluated using
the Japanese Industrial Standard (JIS) Z 2801:2000—
“Antimicrobial products”-Test for antimicrobial activity
and efficacy. The test strains used were Escherichia
coli (ATCC 8739) and Staphylococcus aureus (ATCC
6538). The microorganisms tested were prepared, grown
in a liquid culture, and standardized by dilution in
a nutritive broth, yielding a concentration of at least
2149
Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging Becaro et al.

1 × 105 cell mL−1 . A control sample was also employed. such as SiO2 and TiO2 are suitable matrix for the growth
The films were cut into samples with 5 × 5 cm and were of silver nanoparticles due to its high surface area and well
inoculated with the evaluated microorganisms, in triplicate. distributed pores, which can be adjusted between 2 and
Then, all samples were incubated at 37  C for E. coli and 20 nm.16
30  C for S. aureus in a 90% of relative humidity. After Furthermore, C element, present in EDS spectrum
24 hours of incubation, the colonies forming units (CFU) (Figs. 1(a)–(b), right side), is due to the polyethylene
were counted. The activity value was calculated from the composition. Cl peak observed in Figure 1(b) arises from
difference between the number of colony forming units AgCl compound, which was detected in the XRD analyses
(CFU) on the surface of samples containing silver nanopar- (Fig. 5(a)) of the PEC samples.
ticles with that measured on the control sample, according
to JIS Z 2801:2000.15 3.2. XRD
Figures 2(a) and (b) present the X-ray analysis
3. RESULTS AND DISCUSSION results for films containing PEC and PEN master-
3.1. SEM Analyses batches, respectively. The nanocomposites studied retained
SEM images of transversal profile of the fractured the orthorhombic crystalline structure characteristics of
films with PEN and PEC masterbatches are displayed polyethylene,17 18 presenting peaks in 2 values of 21.5
in Figures 1(a) and (b), respectively. It is observed in (110) and 23.9 (200).19 In addition, the obtained polyethy-
Figure 1(a) that the film contains Ag, Si, O and C lene structure is in agreement with orthorhombic phase
on according to the results obtained by EDX technique. according to JCPDS (Joint Committee on Powder Diffrac-
Figure 1(b) shows the formation of agglomerated parti- tion Standards) file number 053-1859 for all samples
cles of Ag, Cl, Ti, O and C. The circles indicate the Ag (Figs. 2(a) and (b)).
particles contained in a brighter area of SiO2 (Fig. 1(a)) Analysis of Figure 2(a) shows that for samples con-
and TiO2 (Fig. 1(b)), respectively. It is observed that silver taining major contents of PEC (PEC50 and PEC100)
nanoparticles are present in both materials, embedded in TiO2 peaks become visible, being determined by JCPDS
silica particles in the PEN films and titanium oxide in the file number 021-1276 as rutile structure. Accord-
PEC films. It is already known that mesoporous materials ing to literature20 a diffraction peak of rutile in 2 = 27, 4
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Figure 1. SEM images (left side) and EDS spectrum (right side) of films containing silver nanoparticles: PEN (a) and PEC (b).

2150 J. Nanosci. Nanotechnol. 15, 2148–2156, 2015

Becaro et al. Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging

(a) bands of pure LDPE, such as the band at 719 cm−1 , which
LDPE
AgCl corresponds to CH2 asymmetric angular deformation21 and
TiO2 the band at 1308 cm−1 that relates to wagging CH2 22 The
vibrations at 1465 cm−1 and 1377 cm−1 correspond to the
Intensity (Unid. Arb.)

−1
angular deformation of CH23 2 while the peaks at 2852 cm
−1
and 2920 cm are attributed to CH2 symmetric and asym-
metric stretching, respectively.20
PEC 100
FTIR spectrum displayed in Figure 3(a) corresponds
PEC 50 to the nanocomposite film containing particles of TiO2 .
According to literature20 two vibrations located at 425–
PEC 2,5 475 cm−1 and 600–625 cm−1 are related to rutile, which
in case of Figure 3(a) corresponds to peaks located at
LDPE 480 cm−1 and 645 cm−1 for samples PEC-100 and PEC-
10 20 30 40 50 60 70 80 50. Rutile bands were not observed in the sample PEC-2.5,
2θ/º probably because the high LDPE concentration masked the
lower PEC content.
(b) From Figure 3, one observes that the FTIR spectra of the
LDPE
nanocomposites are consistent with the standard infrared
spectrum of original LDPE. In Figure 3(b), which presents
the FTIR of the films containing SiO2 particles, one can
Intensity (Unid. Arb.)

observe the presence of a low definition band around

1080 cm−1 , which can be attributed to Si O Si group.24
The bands corresponding 1100–900 cm−1 and 467 cm−1
can be attributed to the group Si O from silicon dioxide
PEN 100 particles.23 In this way, no contaminants were observed by
PEN 50 FTIR analysis, indicating a pure surface samples for both
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2,5 nanocomposite films.
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LDPE
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10 20 30 40 50 60 70 80 (a)
LDPE
2θ/°

Figure 2. X-ray diffraction of the composites containing: Ag/TiO2 (a); PEC 2, 5

Ag/SiO2 (b).
Transmittance

PEC 50
(110), as observed in Figure 2(a), differs from anatase,
which presents peaks in 2 = 25, 2 (101). AgCl peaks
2018 1304 1080
PEC 100
2341 1377
were observed in samples PEC50 e PEC100 (Fig. 2(a)),
645 480
according to JCPDS file number 031-1238. TiO2 and AgCl 2852 1465
2917 719
peaks were not found for PEC2, 5, due to the low concen- 4000 3500 3000 2500 2000 1500 1000 500
tration of these compounds in the sample, which are below Wavenumber/cm–1
the equipment detection limit. In Figure 2(b) only the (b)
polyethylene diffraction peaks are present in all samples.
This fact indicates that the Si element identified in these LDPE

samples by EDS analysis (Fig. 1(b)) could be in a non-

Transmittance

PEN 2,5
crystalline phase such as, amorphous SiO2 . Ag (Fig. 1(b))
was not observed in the XRD analysis due to low concen- PEN 50

tration of this element in the sample. PEN 100

2345 13031080 470

3.3. FTIR 1377 720
Figures 3(a) and (b) shows FTIR spectra of samples 2931 2851 1464

containing only LDPE and those containing silver 4000 3500 3000 2500 2000 1500 1000 500

nanoparticles dispersed in TiO2 and SiO2 in LDPE, respec- Wavenumber/cm–1

tively, according to nomenclature displayed Table I. The Figure 3. FTIR spectra of samples containing: Ag/TiO2 (a) and
spectrum of nanocomposite films presents characteristic Ag/SiO2 (b).

J. Nanosci. Nanotechnol. 15, 2148–2156, 2015 2151

Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging Becaro et al.

1.8 f
100 PEN 2.5
LDPE
100 1.6 a. 241 ºC
c a. 249 ºC 2

-d (Mass loss) / dT (%.°C)

b. 351 ºC

-d (Mass loss) / dT (%.ºC)

b. 321 ºC 1.4 80
80 c. 363 ºC c. 368 ºC
d e

Mass Loss (%)

1.2
d. 383 ºC
Mass loss (%)

d d. 376 ºC
60 c 1
60 e. 398 ºC 1.0 e. 393 ºC
f. 417 ºC g f. 415 ºC
ef 0.8
g g. 429 ºC 40 g. 442 ºC
40 0.6
h.472 ºC h. 473 ºC
b 1
i. 489 ºC 0.4 i. 492 ºC
20 b h i 20 hi
a 0.2
a
0 0.0 0 0
–0.2
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (ºC)

3.0 3.0
100 PEN 50 100 PEN 100
456 ºC
2.5 2.5
454 °C

- d (Mass loss) / dT (%.°C)

- d (Mass loss)/dT (%.°C)
80 80
2.0 2.0
Mass loss (%)

Mass loss (%)

60 60
1.5 1.5

40 1.0 40 1.0

20 0.5 20 0.5

0 0.0 0 0.0
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100 200 300 400 500 600 700 800
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Temperature (°C) Temperature (°C)

Figure 4. Thermogravimetric analysis (TGA) and Derivative Thermogravimetric Analysis (DTG) curves for samples studied in syntactic air from
10  C to 800  C.

3.4. Thermal Analysis Thermal behavior of PEC 2.5 approached LDPE with
The effects of silver nanoparticles content on the thermal nine steps of degradation, while PEC 50 and PEC 100 had
properties of the nanocomposite films were compared to eight steps, differently from PEN 50 and PEN 100, which
the neat LDPE, used as the matrix, under the same con- decomposed in a single stage. Addition of PEC master-
ditions. Figures 4 and 5 present the corresponding TGA batches in LDPE increased the degradation temperature
and derivative DTG curves for distinct compositions of of samples, as can be seen in Figure 5, although some
masterbatches/matrix. The composites LDPE and PEN catalytic activity could be expected in samples containing
2.5 decompose in multiple stages, while PEN 50 and high content of TiO2 27 However, the delay in the degrada-
PEN 100 decompose in a single stage as observed in tion of PEC samples may be due to the presence of TiO2
DTG curves. PEN 2.5 changes the decomposition behav- in the rutile structure, as shown in FTIR analysis, which
ior, with a distinct degradation profile. Figure 4 showed exhibits high thermal stability.28
that composites LDPE and PEN 2.5 had nine degrada- According to Figures 4 and 5, LDPE onset tempera-
tions steps evidenced by DTG peaks, and the “a” and “b” tures of decomposition (Tonset ) occurred around 430  C,
peaks can be related with volatile components. PEN 2.5 which agrees with results previously reported.29 30 PEC 2.5
anticipated the decomposition of the components, which and PEN 2.5 show Tonset close to 330  C, while Tonset of
shows that silver nanoparticles are capable of chang- PEN 100 and PEC 100 samples are 417  C and 451  C,
ing the films degradation profile, probably because silver respectively. These results may indicate that the thermal
metal donate electrons to polymer, catalyzing the oxidative stability variation of samples as a function of the master-
degradation.25 Such early stages of thermal degradation batch content is due to the distinct characteristics between
have been reported in the literature.26 However, PEN 50 the LDPE of the masterbatches and the LDPE used for
and PEN 100 had similar one-step-degradation with oxi- processing the films. Such distinct characteristics can be
dation temperature peak close to 455  C. originated from different LDPE synthesis.31 For the same

2152 J. Nanosci. Nanotechnol. 15, 2148–2156, 2015

Becaro et al. Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging

1.8
100 d PEC 2.5
100 LDPE c
1.6 a. 261 ºC 1.5
c a. 249 ºC

–d (Mass loss)/dT (%.°C)

-d (Mass loss) / dT (%.°C)
b. 321 ºC 1.4 b. 344 ºC
80 80
c. 363 ºC c. 358 ºC

Mass Loss (%)

1.2
Mass loss (%)

d d. 376 ºC d. 380 ºC
1.0 60 e 1.0
60 e. 398 ºC e. 407 ºC
f. 417 ºC 0.8 b f. 434 ºC
ef g
40 g g. 429 ºC 40 g. 447 ºC
0.6 f
h. 472 ºC h. 466 ºC 0.5
i. 489 ºC 0.4 h i. 485 ºC
20 b h i 20
0.2 a i
a
0 0.0 0 0.0

–0.2
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (°C)

c 1.8
PEC 100
100 PEC 50 100 d
1.6 a. 257 ºC
a. 250 ºC 2
e b. 349 ºC

–d (Mass loss)/dT (%.°C)

b. 342 ºC 1.4

–d (Mass loss)/dT (%.°C)

80 80 c. 366 ºC
d c. 372 ºC 1.2 f

Mass Loss (%)

d. 388 ºC
Mass loss (%)

d. 382 ºC
1.0 1
60 e. 423 ºC e. 397 ºC
60 g
f. 437 ºC 0.8 f. 410 ºC
e f g. 452 ºC g. 436 ºC
40 0.6
h. 492 ºC 40 h. 491 ºC 1
b g c
0.4 b
20 a h
h
0.2 20
a
0.0 0
0
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Temperature (ºC)

Figure 5. Thermogravimetric analysis (TGA) and Derivative Thermogravimetric Analysis (DTG) curves for samples studied in syntactic air from
10  C to 800  C.

reason, a difference can be observed in the residual percent- 50) had intermediate values for m, suggesting a suitable
age (Table II). However, the difference in thermal stability homogenization of the polymeric system, also observed in
among the samples does not compromise the film process- DSC analyzes. The residues left after the polymeric films
ing, once the extrusion temperature did not exceed 200  C. degradation (at temperatures above 600) increased with
In contrast, the addition of the masterbatch PEC slightly the addition of both masterbatches (PEN and PEC), which
increased the films thermal stability, mainly caused by two may be also be from LDPE.30
factors: (i) a higher content of TiO2 nanoparticles pro- Figure 6 shows DSC curves used to calculate the
vides a higher heat diffusion inside the composite,32 which melting temperature (Tm ) and melting enthalpies (Hm ),
delays material burning and (ii) possible occurrence of displayed in Table III. All analyzed films showed endother-
grafting reaction between the two polymers (LDPE) com- mic peaks strictly related to melting of the polymer matrix,
posing the masterbatch and the matrix.33 since degradation temperature for the samples starts only
The mass loss (m) of the samples ranged from 90.92 to at higher temperatures (leading to mass loss, as seen in
99.81 (Table II). The intermediate compositions (2.5 and Fig. 6). The melting temperature (Tm ) of the neat LDPE
was 104  C. On the other hand, PEC 100 films showed
Table II. Thermogravimetric analysis (TGA) data of the films.
melting temperature at 120  C (higher than LDPE films),
Samples Tonset ( C) Tpeak ( C) r (%) m (%) the same value found in Ref. [34]. As expected, PEC 50
showed intermediate Tm between LDPE and PEC 100,
LDPE 428.14 463 3.69 96.27
while PEC 2.5 presented Tm close to pure LDPE films.
PEN 2.5 328.72 365 0.28 99.81
PEN 50 428.97 456 0.70 99.22 The PEC 50 films presented broader endothermic reac-
PEN 100 417.42 454 1.52 98.37 tion with three peaks (Fig. 6). The first temperature peak,
PEC 2.5 335.63 369 0.72 99.25 at 102  C, is corresponding to the endothermic peak films
PEC 50 442.04 462 6.65 93.35 of LDPE (Tpeak 104  C). The second and third peak, at 118
PEC 100 451.88 466 9.89 90.92
and 122  C, respectively, corresponds to both peaks at 121

J. Nanosci. Nanotechnol. 15, 2148–2156, 2015 2153

Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging Becaro et al.

(a) Table IV. Crystallinity of films.

2
PEN 2.5
Samples XRD method Xc (%)
0 PEN 50
Neat LDPE 50.0
–2 PEN 100 PEN 2.5 51.0
Heat Flow

LDPE
PEN 50 49.0
–4 PEN 100 44.0
PEC 2.5 42.0
–6 PEC 50 56.0
ENDO

PEC 100 63.0

–8

–10 be caused by a strong interaction between the masterbatch

104 ºC
and the matrix polymer to form a homogenous mixture.37
50 75 100 125 150 175
The crystallinity peak of samples PEC and PEN was
Temperature (°C) determined by DSC analyses by cooling the samples at
(b) 4 10  C/min.
PEC 2.5 In Table IV are depicted the crystallinity degrees (Xc ) of
2
all the samples, which were calculated from XDR difrac-
0 PEC 50 tograms. In principle, the addition of silica to the poly-
PEC 100 meric matrix would result in increased crystallinity of the
–2
Heat Flow

final product, since silica particles may act as nuclei for

LDPE
–4 crystal growth of LDPE.6 However, the addition of mas-
terbatch PEN to the LDPE matrix does not cause signif-
ENDO

–6
icant changes in LDPE crystalline structures, as observed
–8 in previous works.38 PEC 2.5 composite showed a crys-
–10 tallinity reduction from 50.0 to 42.0% compared with neat
LDPE. The crystallization inhibition effect occurs during
50 75 100 125 150 175
the polymer processing due the nanoparticles presence in
Temperature (°C)
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films: (a) PEN e (b) PEC. 3.5. Antimicrobial Activity of Films
Containing Silver Nanoparticles
and 123  C, observed in PEC 100 films. Three melting The antimicrobial tests, according to the JIS Z 2801:2000
peaks for LDPE were already reported,35 which is possi- Japanese Industrial Standard, showed that the obtained
bly caused by the existence of several crystalline struc- polyethylene nanocomposites containing silver nanopar-
tures with distinct morphologies caused by the presence ticles exhibited intense antimicrobial properties against
of different materials in its composition. It is observed in the tested microorganisms. The antimicrobial properties
Figure 6(a) a displacement of the intermediate composi- of nanoparticles are enhanced39 40 by its larger sur-
tion curves for both materials, which is more noticeable to face area/volume ratio. The antimicrobial activity of Ag
PEC samples, confirming the homogenization of the sys- nanoparticles41 42 arises from its ability to produce pits on
tem. This fact is in agreement with TGA results (Fig. 5), the bacteria cell membranes, thus causing non-repairable
suggesting homogenization. damage.8 According to literature43 the antibacterial activ-
The melting enthalpies (Hm ) of the films were affected ity occurs when the metallic silver nanoparticles (non-
when compared to pure LDPE film, which was also oxidized ones) bound to oxygen and then act as catalyst to
observed in Ref. [36]. The decrease in enthalpy of PEN oxidation. The oxygen absorbed onto the silver atom sur-
samples and PEC 2.5, when compared to pure LDPE, can face will readily react with the sulfhydryl (–S H) groups
surrounding the surface of bacteria or viruses, causing the
Table III. Differential Scanning Calorimetry (DSC) curves data for
samples. sulfur atoms to form an R S S R bond, and therefore
blocking respiration and causing the bacteria to die.
Samples Tm ( C) Hm (J g−1 ) The nanocomposite films present stronger antimicrobial
activity against the S. aureus than E.Coli, for all nanocom-
Neat LDPE 1046 1054
PEN 2.5 1044 917
posites studied, as displayed in Table V. These results are in
PEN 50 1045 796 agreement with literature,44 where a better inhibitory effect
PEN 100 1050 895 on Gram-positive S. aureus than Gram-negative E. coli
PEC 2.5 1055 723 yeast was observed. The antimicrobial action is related to
PEC 50 10985 9772 differences between gram-positive and gram-negative bac-
PEC 100 12261 1068
teria membranes due to the thickness of the peptidoglycan

2154 J. Nanosci. Nanotechnol. 15, 2148–2156, 2015

Becaro et al. Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging

Table V. Comparison of the antimicrobial activities of silver nanocomposites.

S. aureus E. coli
Inoculum for the Concentration after Inoculum for the Concentration after
calculation basis 24 h (CFU/mL) Reduction (%) calculation basis 24 h (CFU/mL) Reduction (%)

LDPE 19 × 104 19 × 104 0 14 × 107 14 × 107 0

PEN 2.5 19 × 104 37 × 104 0 14 × 107 16 × 107 0
PEN 50 19 × 104 < 10 99999 14 × 107 11 × 106 92
PEN 100 19 × 104 < 10 99999 14 × 107 52 × 104 996
PEC 2.5 19 × 104 < 10 99999 14 × 107 73 × 104 994
PEC 50 19 × 104 < 10 99999 14 × 107 42 × 105 97
PEC 100 19 × 104 < 10 99999 14 × 107 37 × 103 9997

layer. Gram-positive bacteria exhibit peptidoglycan layer References and Notes

of about 30 nm, while Gram negative exhibit much thinner
peptidoglycan layer, although they present an outer mem-
brane not found in Gram-positive bacteria.45
Data in Table V display the efficacy in the reduction
percentage of microorganisms for both PEC and PEN
samples, except for PEN 2,5 composite, probably due to
the low silver content. In general, PEC presented a slight
superior antimicrobial performance compared to the PEN
samples, probably due to the AgCl presence in former
sample (see Fig. 2), once this compound presents efficient
antimicrobial properties.46 47 Furthermore, TiO2 used as
silver carrier in PEC samples is highly oxidative and it is
capable to degrade organic compounds, such as bacterial
membranes,48 and this effect can be
Delivered byamplified in presence
Publishing Technology to: Adelaide Theological Library
39 49
of Ag nanoparticles. IP: 94.203.164.177
Our results On: Mon, 12
show that both mas-
terbatches (PEC and PEN) are good Copyright:
candidates American
for pro- Scientific
ducing antibacterial food packaging based on LDPE/Ag
nanoparticles, aiming at improving product shelf life.
4. CONCLUSIONS
Distinct LDPE films containing two distinct masterbatches
with silver nanoparticles have been produced and char-
acterized by distinct techniques, including DSC, XRD,
TGA, FTIR, SEM and antimicrobial activity. The degree
of crystallinity according to XRD analysis proved the
high dispersion of silver nanoparticles embedded in SiO2
and TiO2 carriers. The crystallinity difference between the
compositions does not greatly affect the film formation.
Both PEC and PEN composites presented good antimi-
crobial properties, for Escherichia coli and Staphylococ-
cus aureus, according to the Japanese Industrial Standard
Method. Specifically in terms of antimicrobial properties,
PEC showed to be slightly more efficient due to presence
of AgCl and TiO2 . Our results demonstrate the possibility
of using nanocomposites based on low-density polyethy-
lene and silver nanoparticles dispersed on distinct carriers
to produce films for food packaging since antimicrobial
activity is highly demanded to increase food shelf life.
Acknowledgments: The authors are grateful to CNPq,
FAPESP, CAPES, MCTI, FINEP and Embrapa from Brazil
for financial support.
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Received: 17 October 2013. Accepted: 26 February 2014.

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