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A Comprehensive Feasibility Study on the Properties of

LDPE-Ag Nanocomposites for Food Packaging


Applications

Nattinee Bumbudsanpharoke , Wooseok Lee, Seonghyuk Ko


Department of Packaging, Yonsei University, Wonju-si, Gangwon-do, Republic of Korea

The intense recent interest in active food packaging dioxide [4, 5]. Numerous efforts have been made to
with silver nanoparticles (AgNPs) is attributed to the improve the fundamental properties of LDPE for use in
extraordinary efficacies of the AgNPs against a broad-
spectrum of food-borne pathogens. A comprehensive
active food packaging as an advanced functional material.
study of silver nanocomposites was conducted to Various hybrid systems have been investigated by blend-
identify the effect of the AgNPs on the properties of ing organic or inorganic particles (i.e., montmorillonite,
low-density polyethylene (LDPE) for food packaging silica, calcium carbonate, and graphene) to LDPE matrix
applications. The investigation included the study of for enhancing the modulus strength and gas barrier
the optical, thermal, mechanical, and barrier proper-
ties, as well as antimicrobial activity against Gram- [6–10]. Essential oil (i.e., thyme, oregano, and clove) and
positive and Gram-negative bacteria. Upon addition of phenolic compound have also been incorporating with
AgNPs in LDPE, LDPE-AgNP composite films became LDPE to impart the antimicrobial and antioxidative activity
less transparent and more yellowish because of sur- [11–18].
face plasmon resonance vibrations of the AgNPs. The Recently, nano-enabled food packaging has become an
SEM, EDS, and TEM results revealed that spherical
AgNPs were distributed on both surface and interior of alternative way to preserve the quality of product by con-
the LDPE film. While these well-dispersed AgNPs trolling the surface microbial contamination [19, 20] or
enhanced the barrier properties of LDPE for both oxy- headspace gas and moisture of foods [21]. Among metal-
gen and water vapor, the incorporation of AgNPs based nanomaterials used in food packaging, silver nanopar-
impinged onto the thermal properties by reducing the ticles (AgNPs) have been receiving tremendous attention
thermal stability and the melting enthalpy of the LDPE
film. In addition, LDPE-AgNP composite film showed because of their extraordinary efficacy against various food-
effective antibacterial activity against Staphylococcus borne pathogens [22]. Although the antimicrobial mecha-
aureus and Escherichia coli. These findings suggest nism has not been clearly revealed yet, it is believed that
that the LDPE-AgNP composite film can be feasibly microbial inhibition comes from both the AgNPs themselves
used in food packaging to preserve the food quality
and from the discharged Ag ions [23, 24]. Because AgNPs
and extend the shelf-life of the product. POLYM. COM-
POS., 00:000–000, 2017. V
C 2017 Society of Plastics Engineers have a larger specific surface area than microscale silver
particles, the potential to release Ag ions is also greater
than that of their bulk or microcounter parts [25].
INTRODUCTION Most research performed on thermoplastic/AgNP com-
posites has focused on their antimicrobial properties and
Due to its good heat-sealability, chemical inertness, on migration studies, while mechanical and thermal prop-
and safety as food contact material, low-density polyeth- erties have been examined in a few studies. Becaro et al.
ylene (LDPE) is the simplest and the most widely used [26] used AgNPs with two distinct inorganic carriers to
plastic in the application of food packaging with various develop an antimicrobial LDPE-based film. From the
formats, that is, films, sheets, bottles, cups, tubes, and thermal analysis, they found that the crystallization of the
trays [1–3]. Conventional LDPE shows a good-moderate polymer chain is inhibited by the presence of nanopar-
moisture barrier while it has a low tensile strength and ticles during the polymer processing. Jokar et al. [27]
poor gas barrier property against oxygen and carbon reported that LDPE-AgNP composite film containing
more than 6.69 ppm of AgNPs exhibited good perfor-
Correspondence to: S. Ko; e-mail: s.ko@yonsei.ac.kr mance against Gram-positive and Gram-negative bacteria
Contract grant sponsor: Ministry of Food and Drug Safety (Korea); con- and yeast. However, the result showed that the high level
tract grant number: 15162MFDS031.
DOI 10.1002/pc.24325
of AgNPs degraded the mechanical properties of the
Published online in Wiley Online Library (wileyonlinelibrary.com). nanocomposite. In addition, Cushen et al. [28] studied the
C 2017 Society of Plastics Engineers
V migration behavior of AgNPs from plasticized polyvinyl

POLYMER COMPOSITES—2017
chloride (PVC) nanocomposites for chicken meat. As a Characterization of LDPE-AgNP Composite Films
result, even in the worst-case scenario, the migration stud-
ICP-OES (Optima 8300 Perkin Elmer, Inc., Massachu-
ies showed the number of migrated AgNPs was lower
setts) was used to accurately measure the quantity of silver
than what the European Union (EU) legislation allows for
in the LDPE-AgNPs composite films. UV2Vis diffuse
general substances.
reflectance spectra (DRS) were recorded on a double-beam
The objective of this study is not only developing an
V-600 spectrophotometer (Jasco, Tokyo, Japan) with an
antimicrobial material but also improving the basic prop-
attached integrating sphere in the wavelength range of
erties of LDPE for achieving the superior food packaging
200–800 nm. A barium sulfate (BaSO4) pellet was used as
material. Since barrier properties are considered as key
a reference to measure the absorption of the LDPE-AgNPs
features of packaging for preserving the quality of food
composite films.
products [29, 30], to the best of our knowledge; however,
Optical properties of AgNP composite films were char-
no work has been reported on the barrier properties of
acterized with respect to CIE L*a*b* color values and
polyolefin-based nanocomposites containing AgNPs for
transparency. The CIE L*a*b* values were measured
application in food packaging. Therefore, this study is using a handheld color reader CR-10 (Konica Minolta,
devoted to preparation of LDPE-AgNP composite films Tokyo, Japan) and were recorded from three readings for
and thorough characterization of all properties including each sample. According to ASTM D1746, the transparency
optical, mechanical, thermal, and barrier properties as of the AgNP composite films was determined by measuring
well as antimicrobial activity of the nanocomposite the percent transmittance (%T) at 660 nm using a V-600
films. spectrophotometer (Jasco, Tokyo, Japan).
The surface morphology and cross section of the com-
EXPERIMENTAL posite films were observed with a field-emission scanning
electron microscope (FE-SEM, Quanta FEG 250, FEI
Ltd., Oregon) after sputtering platinum/palladium onto the
Materials specimen using a Cressington Sputter Coater 108 auto
A commercial grade LDPE, Lutene LB7500 (LG (Cressington Scientific Instruments, Watford, UK). Fur-
Chemical Co., Yeosu, Korea), with a melt flow index of ther elemental analysis was carried out with an energy-
7.5 g/10 min (ASTM D1238) and a density of 0.918 g/cm3 dispersive X-ray spectrometer (EDS, Ametek Inc., New
was used. The masterbatch of concentrated AgNP Jersey) equipped with FE-SEM.
(1,000 ppm) with LDPE (Hunion Co., Ltd., Kangwon, For transmission electron microscope (TEM) analysis,
Korea) was purchased and used as-received. the shape and size of impregnated AgNPs were examined
using a Tecnai G2 Spirit Twin (FEI Ltd.) operating at
120 kV. The sample was embedded in Caldofix resin, and
Preparation of LDPE-AgNP Composite Films blocks were subjected to cryo-ultrathin sectioning to
80 nm thickness on an EM FC7 Ultramicrotome (Leica,
The LDPE-AgNP composite films were prepared by Nussloch, Germany) at 2808C to obtain cross sections of
multi-layer extrusion with a T-die extruder (30 mm /, L/ the composite film. The ultrathin section was then trans-
D 5 30) (Hankook E.M Ltd., Incheon, Korea). The extru- ferred to 200 mesh carbon-coated copper grids prior to
sion temperatures were 190–2308C and the screw speed TEM observation.
was 40 rpm. In order to yield various concentrations of A nonisothermal crystallization study was conducted
AgNP composite films, pure LDPE and masterbatch were with differential scanning calorimetry (DSC Q20, TA
blended at the desired ratios and processed. Neat LDPE Instruments, Castle). About 5–6 mg of each samples was
film was also prepared in the same way for use as a refer- weighed and encapsulated in an aluminum pan. An empty
ence sample. Prior to processing, LDPE and AgNP mas- sealed pan was used as a reference. Under nitrogen atmo-
terbatch pellets were dried in a convection oven at 808C sphere, the samples were heated at a constant rate of
for 24 h, then mixed in a sealed plastic bag by manual 108C/min from 30 to 2508C (first heating scan) and held
tumbling before being fed into the extruder. Five different for 5 min to permit complete melting of the crystals in
compositions of LDPE-AgNP composite films were order to erase their previous thermal or morphological
obtained and their thickness was controlled at 60–70 lm. history. Subsequently, samples were cooled down to
To quantify the precise amount of Ag included in com- 2608C at a constant rate of 2108C/min (cooling scan) to
posite films, inductively coupled plasma optical emission study the crystallization behavior. Finally, the samples
spectrometry (ICP-OES) analysis was performed. As a were heated again up to 2508C (second heating scan) at
result, the concentration of Ag involved was confirmed as 108C/min to melt the crystals that had formed during the
0, 3, 36, 75, and 240 ppm; and the samples were named cooling scan and to find the melting temperature of each
according to their Ag contents as follows: LDPE, LDPE- sample. All DSC curves were normalized to the unit
AgNP 3 ppm, LDPE-AgNP 36 ppm, LDPE-AgNP 75 ppm, weight of the sample. The degree of crystallinity (Xc ) was
and LDPE-AgNP 240 ppm. then calculated using the specific heat required for

2 POLYMER COMPOSITES—2017 DOI 10.1002/pc


melting from the integration of the corresponding peak
according to the following equation:

DHm
Xc 5 0
3100 (1)
DHm

where DHm is the melting enthalpy obtained from the


0
DSC melting endotherms and DHm 5 293 J/g is the
melting enthalpy of 100% crystalline LDPE [31–33].
Thermogravimetric analysis (TGA) was performed
using a TGA 4000 thermogravimetric analyzer (Perki-
nElmer Co. Ltd., Massachusetts). The sample was heated FIG. 1. Digital photograph and UV–Vis spectra of the LDPE and
from 30 to 8008C at a rate of 108C/min under a nitrogen LDPE-AgNP composite films. [Color figure can be viewed at wileyonline-
flow rate of 20 mL/min. library.com]
Measurements of the tensile strength and elongation at
break of LDPE-AgNP composite films were performed was dispensed onto an agar plate and incubated at
according to the ASTM D882-02 by using a DTU- 35 6 18C and 90 6 5%RH. The antimicrobial activity is
900MHA tensile tester (Daekyung Tech Co., Incheon, evidenced by the reduction of microbial colonies. After
Korea) with a load cell of 10 kgf. Dumbbell-shaped test 24 h incubation, the colony-forming units (CFU) in a seri-
specimens were die-cut to 5-mm wide and 10-mm long ally diluted petri dish in which 30–300 colonies appear
(test region) and conditioned at 50% RH and 238C for 48 h were counted. Antibacterial activity was calculated to %
before the measurements. The specimen was stretched with reduction of the colonies using the following equation:
a constant crosshead speed of 10 mm/min at room tempera-  
ture and ambient relative humidity. Ten replicates were test- ðA 2BÞ
% Reduction5 3100 (2)
ed for each composite film and the average was reported. A
The oxygen transmission rate (OTR) of the LDPE-
AgNP composite films was measured with an OTR 8001 where A is the average number of viable cells from the
oxygen permeation analyzer (Systech Instruments Co. control sample after 24 h and B is the average number of
Ltd., Illinois) at 238C and 0% relative humidity, accord- viable cells from the test sample after 24 h.
ing to ASTM D3985.
The water vapor transmission rate (WVTR) was deter- Statistical Analysis
mined using a WVTR 7001 water vapor permeation ana- R
lyzer (Systech Instruments Co. Ltd., Illinois) at 388C and A statistical analysis was undertaken using the SPSSV
95% relative humidity, according to ASTM F1249. The program (SPSS Inc., Illinois). The results were interpreted
area of the test films was 50 cm2. The values obtained by one-way analysis of variance (ANOVA) with a confi-
for each sample after three replications were averaged. dence level of 95% (a 5 0.05) and further analyzed with
The antibacterial activity of LDPE-AgNP composite Duncan’s post hoc test method. Data are represented as
films was evaluated according to the JIS method (JIS Z mean 6 standard deviation (SD). The p-value was less
2801:2000) against both Gram-negative and Gram- than 0.05, which indicates that the mean value of speci-
positive bacteria: Escherichia coli ATCC 8739 and Staph- mens is significantly different.
ylococcus aureus ATCC 6538P respectively. Briefly, each
test sample (50 mm 3 50 mm) was first sterilized with RESULTS AND DISCUSSION
UV light, and then 400 mL microbial inoculum in nutrient
broth (2.5–10 3 105 CFU/mL) was dropped onto both Characterization of the LDPE-AgNP Composite Film
control and composite samples. Each sample was covered
with 40 mm 3 40 mm sterilized Stomacher 400 Poly-bag To confirm the presence of AgNPs, UV–Vis spectros-
film followed by incubation at 35 6 18C and copy was used to characterize the SPR vibration of
90 6 5%RH for 24 h. After incubation, the tested sample AgNPs in the composite films. As shown in Fig. 1, UV–
and covered film were carefully washed with 10 mL of Vis absorption spectra of LDPE-AgNP composite films
nutrient broth in a sterilized stomacher pouch. For viable exhibit increasing absorption peaks with an increase of
cell enumeration, 1 mL from the washing was pipetted AgNP content at a wavelength of 425 nm, which is
and placed in a test tube containing 9 mL nutrient broth attributed to the SPR band of the AgNP [34, 35]. The
and mixed thoroughly. Then, 1 mL from this test tube inset in Fig. 1 demonstrates that AgNP inclusion in
was taken with a new pipette and placed in another test LDPE gradually alters the color of films. The AgNP com-
tube containing 9 mL of nutrient broth. These procedures posite films varied from pale yellow to dark yellow in
were repeated to prepare the 10-fold serial dilutions. Sub- color while the neat LDPE film was transparent without
sequently, a 400 mL aliquot of each microbial suspension any apparent color.

DOI 10.1002/pc POLYMER COMPOSITES—2017 3


TABLE 1. Effect of AgNP on the color and transparency of LDPE and LDPE-AgNP composite films.

Sample L* a* b* % transmittance

LDPE 55.2 6 0.06a 10.9 6 0.06a 6.5 6 0.06a 90.72 6 0.07a


LDPE-AgNP 3 ppm 54.9 6 0.06b 10.4 6 0.06b 8.9 6 0.21b 90.04 6 0.03b
LDPE-AgNP 36 ppm 54.3 6 0.10c 10.0 6 0.00c 11.7 6 0.20c 89.77 6 0.06c
LDPE-AgNP 75 ppm 53.3 6 0.06d 9.3 6 0.06d 16.7 6 0.27d 87.89 6 0.19d
LDPE-AgNP 240 ppm 51.6 6 0.10e 9.1 6 0.00e 23.2 6 0.10e 84.21 6 0.04e

Results are expressed as mean 6 SD for n 5 3. By Duncan’s multiple range tests, in the same column followed by different letters, are significant
difference (p < 0.05).

Table 1 shows the change in L* (lightness/darkness), The transparency of composite film was determined by
a* (redness/greenness), b* (yellowness/blueness) values, measuring the percent transmittance at a 660 nm wave-
and % transmittance of composite films. Neat LDPE film length. A lower transparency implies a greater opacity
is transparent and colorless; thus, it presents high lumi- [36]. It was found that the percent transmittance of the
nosity values (L*). However, as the AgNP concentrations LDPE-AgNP composite films decreases significantly from
increase from 0 to 240 ppm, the L* and a* values of the 90.72 to 84.21% with increasing AgNP concentration.
film decrease from 55.2 6 0.1 to 51.6 6 0.1 and from Bruna et al. [37] and Althues et al. [38] reported that the
10.9 6 0.05 to 9.1 6 0.1, respectively, whereas the b* presence of an inorganic material that is not dissolved in
value (an indicator of the tendency toward yellowness) the polymer matrix decreases the transparency of a poly-
increases from 6.5 6 0.05 to 23.2 6 0.55. A composite mer, resulting in increasing film opacity.
film in which the yellow tonality is perceptible to the Figure 2 displays the surface and cross-sectional SEM
naked eye is illustrated in Fig. 1. images of neat LDPE and LDPE-AgNP composite films.

FIG. 2. FE-SEM images of surface and cross-sections of neat LDPE and LDPE-AgNP composite films: (a)
neat LDPE; (b) LDPE-AgNP 3 ppm; (c) LDPE-AgNP 36 ppm; (d) LDPE-AgNP 75 ppm; and (e) LDPE-
AgNP 240 ppm. [Color figure can be viewed at wileyonlinelibrary.com]

4 POLYMER COMPOSITES—2017 DOI 10.1002/pc


thermal degradation temperature of the AgNP nanocom-
posites tends to be lower with increasing AgNP content.
Chan et al. [39] suggested, as a possible reason of this
behavior, that the addition of metal-based filler does not
improve but rather reduces the thermal stability of poly-
mer matrix. The uniform dispersion of metal nanopar-
ticles with high specific surface area in a polymer matrix
can destabilize the composite matrix and provide more
sites for thermal degradation upon heating. In addition,
Hidayah and Mariatti [40] and Luyt et al. [41] proposed
that the good thermal conductivity and high-heat capacity
of silver promote it to reach a high temperature more rap-
idly than the surrounding LDPE matrix. Consequently,
the adjacent LDPE matrix can acquires heat easily and is
stretched to its degradation point at an earlier stage (lower
temperature).
DSC analysis was carried out to study the effect of
incorporation of AgNPs on the crystallization behavior of
LDPE. Crystallinity is defined as a degree of structural
order in a polymer matrix [42]. As shown in Table 2, the
crystallinity of neat LDPE is about 54%, which is in
agreement with the general properties of LDPE [43], and
the crystallinity is obviously decreased by introducing
AgNPs to the LDPE matrix. Xia et al. [44] suggested that
metal nanoparticles can hinder the motion of LDPE chain
segments and retard crystal growth. In addition, Yeo
et al. [45] found that the AgNPs could act as impurities
in the polymer matrix and interfere with the crystalliza-
tion process of LDPE, causing the lower crystallinity.
This phenomenon is very consistent with the previous
studies in the literature where the AgNP content was var-
ied in other types of polyethylene [46–48]. The addition
of AgNPs has no effect on the melting point (Tm) of
FIG. 3. Representative TEM images of AgNPs from a LDPE-AgNP LDPE, ranging from 105.95 to 106.618C.
composite film at 240 ppm.

Mechanical Properties
The tiny white spots were found to be clusters of AgNPs,
which was confirmed by EDS analysis. The image of the The tensile strength and elongation at break of LDPE-
surface and cross-section of neat LDPE illustrates a clean AgNP films are illustrated in Fig. 5. The tensile strength
and homogeneous phase, while the presence of AgNP
clusters becomes more pronounced with increasing AgNP
content. It is also observed that AgNPs are distributed on
both the surface and the interior of the LDPE matrix.
For further microscopic investigation, TEM analysis
was performed to identify the shape and size of AgNPs in
composite films. Figure 3 presents representative TEM
images of LDPE-AgNP 240 ppm composite film. It was
observed that the AgNPs are mostly spherical and appear
to be in the range of 20–50 nm in diameter.

Thermal Analysis
Figure 4 is a TGA thermogram showing the percent of
weight loss of the composite film as a function of AgNP
content. The temperatures at which 10 and 50% weight
loss occur are listed in Table 2; these temperatures are FIG. 4. TGA curve of LDPE and LDPE-AgNP composite films. [Color
indicators of thermal stability. It is noticeable that the figure can be viewed at wileyonlinelibrary.com]

DOI 10.1002/pc POLYMER COMPOSITES—2017 5


TABLE 2. TGA data and melting temperatures, melting enthalpy, and crystallinity levels determined by DSC.

Sample T10% (8C) T50% (8C) Tm (8C) Enthalpy (J/g) Crystallinity (%)

LDPE 449.0 487.1 106.25 157.20 53.65


LDPE-AgNP 3 ppm 444.3 483.3 106.61 148.41 50.65
LDPE-AgNP 36 ppm 438.6 480.6 105.95 140.65 48.00
LDPE-AgNP 75 ppm 428.0 473.6 106.26 138.17 47.16
LDPE-AgNP 240 ppm 414.6 463.3 105.99 128.21 43.76

T10%: temperature (8C) at 10% weight loss and T50%: temperature (8C) at 50% weight loss.

of the neat LDPE was determined to be approximately LDPE matrix as shown in Table 2. Indeed, this behavior
19.8 N/mm2; and as the amount of AgNPs increased, it can be explained by the concept of crystallinity. As crystal-
tends to improve slightly. However, the trend is not statis- linity increases, modulus, yield point, and stiffness increase,
tically significant (p > 0.05) implying that the tensile while the elongation decreases. In contrast, lower crystallin-
strength of the film is typically not sensitive to incorpora- ity enables the material to be less brittle, more stretchable,
tion of small amounts of AgNPs. It has been reported and finally to be tougher with greater elongation [50–52].
that, to obtain tangible and significant results, the filler
content must usually be in the range of 5–20 wt% for
Barrier Properties
spherical fillers and 2–7 wt% for higher aspect-ratio fill-
ers (e.g., layered silicate and carbon nanotubes) [49]. Sev- The dispersion of inorganic nanoparticles into a homo-
eral research groups have attempted to study the geneous polymer film alters the barrier properties of the
reinforcing behavior of the nanofiller in polyolefin. Gen- bulk polymer. Figure 6 illustrates the OTR and WVTR of
erally, the tensile strength of the polymer increases with neat LDPE versus LDPE-AgNP composite films. As the
the increase in crystallinity. However, in a weak matrix concentration of AgNPs in the LDPE increased to
(i.e., LDPE and low crystalline), the filler plays an impor- 240 ppm, both permeabilities gradually decreased indicat-
tant role in the load absorption, and consequently reinfor- ing that the barrier properties were enhanced. More exact-
ces the matrix. The extent of load transfer depends on the ly, the OTR is reduced by 28.3%, from 2,735 to
specific surface area and adhesion strength at the interface 1,994 mL/m2/day, while the WVTR shows a relatively
of the filler [50]. Jeziorska et al. [47] suggested that lower decrease of 14.4%, from 6.27 to 5.48 g/m2/day. It
although the crystallinity of polyethylene is reduced by is generally known that the polymer crystallinity and the
incorporating nanofillers, an improvement in the tensile tortuosity are considered to be impediments to mass trans-
modulus can be observed because of the contribution of port. However, other parameters such as polarity, structur-
filler rigidity and good interfacial adhesion between the al compactness, free volume, filler type, and the interface
polymer matrix and the nanofiller. between the filler and the polymer matrix also play a sig-
On the contrary, the elongation at break of the LDPE- nificant role in the final barrier properties [7, 53–56]. It
AgNP composites seems to increase upon increasing the has been reported that well-dispersed nanoparticles can
AgNP content. This is due to the loss of crystallinity of the not only restrict the polymer chain motion but also extend
the mean path length for gas diffusion by filling in inter-
stitial voids between polymer chains [57, 58]. A study by
Vladimirov et al. [59] indicated that spherically shaped
silica nanoparticles can maximize the path length and
affect the gas diffusion through the material, resulting in

FIG. 5. Tensile strength and elongation at break of LDPE and LDPE-


AgNP composite films. The results are expressed as mean 6 SD for
n 5 10. According to Duncan’s multiple range tests, the same column
followed by the different letter are significant difference (p < 0.05).
[Color figure can be viewed at wileyonlinelibrary.com] FIG. 6. OTR and WVTR of LDPE and LDPE-AgNP composite films.

6 POLYMER COMPOSITES—2017 DOI 10.1002/pc


FIG. 7. The quantitative antimicrobial activity of LDPE and LDPE-AgNP composite films. [Color figure
can be viewed at wileyonlinelibrary.com]

a reduced permeability. Bikiaris and Triantafyllidis [60], outer membrane of bacteria, causing structural changes,
Yoksan and Chirachanchai [61], and Sanchez-Valdes [62] degradation, and finally cell death [24, 25].
reported that metal nanoparticles are impermeable materi-
al to gases and moisture. Therefore, incorporating metal CONCLUSIONS
nanoparticles, such as copper or silver into a polymer
matrix can retard the traveling of gas and water vapor LDPE films containing with different concentrations
molecules through the polymer bulk phase because of the (3, 36, 74, and 240 ppm) of AgNPs have been prepared
increased diffusion path length. In this present study, and extensively characterized by distinct techniques,
consequently, it is believed that the oxygen and moisture including UV–Vis DRS, color measurement and % trans-
barrier is promoted because of the fact that well-dispersed mittance, FE-SEM, EDS, TEM, TGA, DSC, mechanical,
spherical AgNPs were incorporated into the interstitial and barrier properties as well as antimicrobial activity.
space between LDPE polymer chains, thereby delaying The presence of AgNPs in the composite film was initial-
mass diffusion. The increase of tensile strength supports ly confirmed by SPR from UV–Vis absorbance, while the
the good interfacial affinity between the polymer matrix SEM, EDS, and TEM revealed that spherical AgNPs
and the nanoparticles. were uniformly located on both the surface and the interi-
or of the LDPE film. Although the composite film with
the AgNP inclusion has a lower thermal resistance and
Antimicrobial Analysis crystallinity as shown by the results of TGA and DSC,
The antibacterial activity of the LDPE-AgNP nano- the reduced crystallinity does not greatly affect the tensile
composite films against S. aureus and E. coli bacteria strength and barrier properties. In turn, incorporation of
was determined based on the JIS Z 2801:2000 method, AgNPs significantly improved the barrier properties of
and the results are depicted in Fig. 7. The nanocomposite LDPE as shown by the reduction of OTR and WVTR.
films incorporating various concentrations of AgNPs were This could be caused by the increased diffusion path
proven to be effective in killing bacteria. Even when the length. In addition, LDPE-AgNP composite films exhibited
AgNP content was only 3 ppm, the nanocomposite film strong antimicrobial activity against Gram-negative and
exhibited antimicrobial activity with over 99% reduction Gram-positive food-borne pathogens. The comprehensive
against both Gram-negative and Gram-positive bacteria. study of LDPE-AgNP composite film demonstrated here
Indeed, the mechanism of the bactericidal effects of offers practical insights into the active food packaging
AgNP is partially known. Generally, in the presence of material, which has high potential to preserve the food
oxygen and water, the Ag ions discharged from the sur- quality and extend the shelf-life of the product.
face of elemental AgNPs play a vital role of the antimi-
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DOI 10.1002/pc POLYMER COMPOSITES—2017 9

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