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Nanoparticulas de Oxido de Zinc

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Nanoparticulas de Oxido de Zinc

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Composites Part B 172 (2019) 173–178

Contents lists available at ScienceDirect

Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Effective antimicrobial materials based on low-density polyethylene (LDPE)


with zinc oxide (ZnO) nanoparticles
Karina Rojas a, Daniel Canales a, b, Nicolas Amigo a, b, Lissette Montoille a, b, Alejandro Cament a, b,
Lina M. Rivas c, O. Gil-Castell b, d, e, Pablo Reyes b, f, Maria Teresa Ulloa c, A. Ribes-Greus b, d,
Paula A. Zapata a, b, *
a
Grupo Polímeros, Facultad de Química y Biología, Universidad de Santiago de Chile, USACH, Casilla 40, Correo 33, Santiago, Chile
b
Centro de Excelencia en Nanotecnología (CEN) Chile, Av. Mariano S� anchez Fontecilla 310, 701-D, Las Condes, Santiago, Chile
c
Programa de Microbiología y Micología, ICBM Facultad de Medicina Universidad de Chile, Avenida Independencia1 027, Comuna Independencia, Santiago, Chile
d
Instituto de Tecnología de Materiales (ITM), Universitat Polit�ecnica de Val�encia (UPV), Camino de Vera S/n, 46022, Valencia, Spain
e
Departament D’Enginyeria Química. Escola T�ecnica Superior D’Enginyeria. Universitat de Val�encia, Av. de La Universitat, S/n, 46100, Burjassot, Spain
f
Fundaci�on Leitat Chile, Av. Mariano S�anchez Fontecilla 310, 701-D, Las Condes, Santiago, Chile

A R T I C L E I N F O A B S T R A C T

Keywords: Effective antimicrobial polymeric nanocomposites were prepared with low density polyethylene (LDPE) and zinc
Antimicrobial packaging oxide nanoparticles by melt compounding. These nanoparticles (~17 nm) obtained by the sol–gel method, were
Polyethylene used both as-synthesized and modified organically with oleic acid (Mod-ZnO). Young’s modulus increased ~15
Zinc oxide nanoparticles
and 18% for LDPE/ZnO and LDPE/Mod-ZnO, respectively, compared to neat LDPE. When these composites were
Mechanical properties
irradiated with white light, they showed an increase with nanoparticle incorporation, and the antimicrobial
properties against E. coli were ~96–99%. The release of the Zn cations was related to the antimicrobial prop­
erties. These nanocomposites are attractive for use as food packaging without external irradiation.

1. Introduction activities both in vitro and in vivo. ZnO has a band gap of 3.37 eV at room
temperature and a large free-exciting binding energy of 60 meV. It also
Polyethylene (PE) is among the polymers used in food packaging due revealed antimicrobial properties against food borne pathogens and
to their low cost, high impact strength and reasonable chemical resis­ spoilage bacteria. Additionally, the ZnO is usually recognized as safe by
tance. The combination of nanoparticles and polymers is of great in­ the FDA under the conditions of its intended use, under prescribed limit
terest, giving an improvement of thermal and mechanical properties at properties [4–7].
low loading levels (<10 wt%). The preparation of nanocomposites using In the literature there are several studies dealing with the influence
small amounts of nanoparticles (<100 nm) may keep the easy process­ of the ZnO nanoparticles with diameters between 50 nm and 100 nm in
ability of polymer matrices by the traditional processing methods [1]. polyethylene on the final polymer properties. In our case we incorpo­
Some authors have studied metal nanoparticle incorporation into PE rated ZnO nanoparticles with diameters smaller than 20 nm.
in order to produce nanocomposites with antimicrobial properties for Li et al. [6] successfully prepared high density polyethylene
use in the packaging industry or in the medicine field by inhibiting the (HDPE)/nano-ZnO (50 nm) composite films and studied the influence of
growth of microorganisms [2]. Along this line, nanoparticles such as the modification and proportion (0.2, 0.5, 1 and 2 wt%) of γ-amino­
silver, copper, and titanium oxide have been considered for the prepa­ propyltriethoxy silane (ZnO-APS) nanoparticles on the antibacterial and
ration of PE-based nanocomposites [1,3]. The limitations of the mechanical characteristics of the films. As ZnO content increased, the
above-mentioned metal/oxide nanoparticles are related to their toxicity antibacterial rate was improved against Escherichia coli (E. coli) and
and external irradiation. Staphylococcus aureus (S. aureus) Also, the tensile strength of the
Zinc oxide (ZnO) nanoparticles are good and inexpensive semi­ HDPE/ZnO-APS composite films was enhanced compared to the original
conductors with good biocompatibility, chemical stability, and biocidal HDPE/ZnO composite due to the better dispersion of ZnO modified

* Corresponding author. Grupo Polímeros, Facultad de Química y Biología, Universidad de Santiago de Chile, USACH, Casilla 40, Correo 33, Santiago, Chile.
E-mail address: [email protected] (P.A. Zapata).

https://doi.org/10.1016/j.compositesb.2019.05.054
Received 25 January 2019; Received in revised form 1 April 2019; Accepted 5 May 2019
Available online 9 May 2019
1359-8368/© 2019 Elsevier Ltd. All rights reserved.
K. Rojas et al. Composites Part B 172 (2019) 173–178

nanoparticles. The tensile strength and toughness reached their nanoparticles were mixed with LDPE in an inert atmosphere (nitrogen)
maximum values at 0.5 wt% ZnO loading. At loadings greater than at 170 � C and a mixing speed of 110 rpm during 10 min. The materials
0.5 wt%, nanoparticle addition led to decreased mechanical properties. were moulded during 3 min in a hydraulic press (HP Industrial In­
Along this line, linear low-density polyethylene (LLDPE) and ZnO struments) at 50 bar and 170 � C, and then cooled to room temperature
(0–10% w/w) (d < 100 nm) nanocomposite films were produced by a under pressure with water circulation.
melt-mixing extrusion process. The prepared nanocomposite films of
LLDPE/ZnO revealed improved oxygen and UV barrier properties as
2.4. Characterisation of ZnO nanoparticles and LDPE/ZnO
well as better thermal properties compared to neat LLDPE films. The
nanocomposites
tensile strength of the nanocomposites increased with the ZnO concen­
tration. Although the antimicrobial properties were not assessed, the
2.4.1. ZnO nanoparticles and their organic modification characterisation
authors concluded that the LLDPE/ZnO nanocomposite films are good
The morphology and size of the nanoparticles was studied under a
candidates for being exploited as food packaging material, since they
Philips (The Netherlands) Tecnai 12 microscope at 80 kV. The X-ray
protect food from oxygen- and UV-induced lipid oxidation [2].
diffraction patterns of the ZnO nanopartilces were analysed on a
On the other hand, Emamifar et al. [8,9] assessed the antimicrobial
Siemens D5000 diffractometer using Ni-filtered Cu Kα radiation
activity of nanocomposites of low-density polyethylene (LDPE) and
(λ ¼ 0.154 nm). Fourier transform infrared (FTIR) studies of the ZnO and
Ag/ZnO nanoparticles (70 nm-10 wt%) against Lactobacillus plantarum
Mod-ZnO nanoparticles were made in a Bruker Vector 22 FTIR spec­
(L. plantarum). They found that the ZnO-based nanocomposites extended
trometer. The IR spectra were recorded in the 4000 to 500 cm 1 range at
the shelf life of fresh orange juice at 4 � C by 28 days without causing
room temperature.
adverse effects on the sensory properties. However, although the active
packaging materials containing Ag nanoparticles had greater activity in
increasing orange juice shelf life, they promoted undesirable effects on 2.5. LDPE/ZnO and LDPE/Mod-ZnO nanocomposite characterisation
the sensory quality of fresh juice.
In this work we studied the preparation of the PE/ZnO-based nano­ The thermal properties in terms of melting temperature and enthalpy
composites via melt compounding. The ZnO (~17 nm) nanoparticles of fusion of the LDPE and LDPE/ZnO nanocomposites were measured by
were obtained by the sol-gel method and were additionally surface- differential scanning calorimetry (DSC) (Mettler Toledo Modelo DSC1/
organic modified with oleic acid (Mod-ZnO). In this sense, the effect 500). For this purpose, a first heating segment from 25 � C to 180 � C was
of the presence of ZnO and Mod-ZnO on the thermal, mechanical, and applied at a rate of 10 � C/min to remove the thermal history. Then, a
antimicrobial properties of the nanocomposites was assessed in order to cooling segment to 25 � C at the same rate was applied. Finally, a second
evaluate its processing conditions, its final properties, and its antimi­ heating segment from 25 to 180 � C was applied, and the values of this
crobial properties without the need for ultraviolet treatment after segment were considered as representative. The crystallinity degree (Xc)
processing. was calculated according to Equation (1), where ΔHof is the enthalpy of
fusion of an ideal polyethylene with 100% crystallinity (289 J g 1 [11])
2. Experimental section and ΔHf is the melting enthalpy (J⋅g 1) of the polymer nanocomposite.
The values were normalized to the weight fraction of the matrix in the
2.1. Materials nanocomposite [3].
ΔHf *100
For the synthesis of the nanoparticles, sodium hydroxide (Merck Xc ¼ (1)
ΔH0f ð1 xÞ
KGaA, reagent grade, 99%), zinc chloride (Merck, reagent grade
80–100%) distilled water, and 2-propanol (Equilab, reagent grade The thermal stability of the nanocomposites was studied on a
99.8%) were used. The reagents used for organic nanoparticle modifi­ Mettler-Toledo TGA 851 thermogravimetric analyser (TGA). About 4 mg
cations were oleic acid (Sigma-Aldrich, 90%) and hexane as solvent (J.T. of samples were placed in 70 μL capacity perforated alumina crucibles.
Baker 99.8%). Low density polyethylene (LDPE), purchased from B.O. The samples were analysed from 25 to 600 � C at 10 � C⋅min 1 under an
packaging, was used as matrix. inert argon atmosphere at a flow rate of 50 mL min 1. All the experi­
ments were ran twice to verify the reproducibility of the results.
2.2. Synthesis of ZnO nanoparticles The distribution of the nanoparticles into the polymer matrix was
studied in a Zeiss Ultra 55 Field-Emission Scanning Electron Microscope
The ZnO nanoparticles were obtained by the sol–gel method reported (FE-SEM). The film nanocomposites were placed on the conductive tape
by Becheri et al. [10]. The precursor solution was obtained by adding and mounted on metal studs. Electron microscope images were taken at
5.5 g of ZnCl2 (to 200 mL of distilled water) at 90 � C in an oil bath. The 22 � C and 20 kV.
second solution was prepared with 5 M NaOH in distilled water and it The tensile properties were determined on an HP model D-500
was added dropwise to the first solution, stirring during 10 min at 90 � C. dynamometer. Dumbbell-shaped samples with a length of 30 mm and a
The suspension was washed with distilled water to reduce the NaCl width of 5 mm were cut from the compression-moulded films. The
concentration below 10 6 M, as verified with a silver nitrate (AgNO3) samples were evaluated at a rate of 50 mm/min at 20 � C. The experi­
solution. The particles were mixed with 2-propanol in an ultrasonic bath ments were run in quadruplicate to ensure representativity.
during 10 min at 20 � C. Next, the particles were centrifuged at 5000 The antimicrobial effect was analysed by a plate count method
RPM for 15 min and they were then washed three times with 2-propanol referred to ISO 20143 with E. coli ATCC 25922 as bacterial agent. The
at 60 � C. Finally, the particles were calcined at 250 � C during 5 h in order method used in this analysis was reported in a previous paper [1]. The
to obtain ZnO. The organic modification method for the ZnO nano­ percent reduction of the colonies was calculated by Equation (2), which
particles (Mod-ZnO) was described by our research group in a previous relates the number of colonies from the neat LDPE to the number of
report [3]. colonies from the LDPE/ZnO nanocomposites.
CFUneat polymer CFUnanocomposite
2.3. Preparation of LDPE nanocomposites with incorporation of %Reduction ¼ *100 (2)
CFUneat polymer
nanoparticles of ZnO and modified ZnO
The release of zinc ions (Zn2þ) from the nanocomposites was ana­
For the preparation of the composites a Brabender Plasti-Corder in­ lysed by means of inductively coupled plasma (ICP) spectrometry. The
ternal mixer was considered. In particular, 3, 5 and 8 wt% ZnO nanocomposite samples (1 � 2 � 0.01 cm) were soaked in 10 mL of

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K. Rojas et al. Composites Part B 172 (2019) 173–178

deionized water with continuous stirring. The measurements were


studied after immersion for 1, 4, 8, 12, 15, and 28 days.

3. Results and discussion

3.1. ZnO nanoparticle characterisation

The yield of the reactions of ZnO nanoparticles was 88.9%. The ZnO
nanoparticles show irregular spherical shapes with an average size of ca.
17 � 3.2 nm, as determined from the TEM images shown in Fig. 1.
The crystalline phase of the ZnO nanoparticles was studied by X-ray
diffraction (XRD), whose resultant spectra are displayed in Fig. 2.
Several peaks are seen in a 30� –80� range, and the crystallographic
planes coincide with those reported by other authors. ZnO NPs exhibited
strong diffraction peaks at 32� (100), 34� (002), 36� (101), 47� (102),
57� (110), 63� (103), 66� (200), 68� (112), and 69� (201), associated
with the hexagonal wurtzite structure of ZnO [12–14].
The chemical structure of the nanoparticles was further assessed by
FTIR, with the characteristic spectra of ZnO, oleic acid, and Mod-ZnO
displayed in Fig. 3. The modification of the nanoparticles will improve
the interaction between the matrix and ZnO nanoparticles. ZnO shows a
signal from 450 cm 1 to 600 cm 1, correlating to the vibrations of the Fig. 2. XRD pattern spectrum of zinc oxide nanoparticles.
Zn–O bond of the nanoparticle. The second signal, between 719 cm 1
and 899 cm 1, corresponds to the stretching and deformation vibrations
of Zn–O. Finally, the band from 3452 cm 1 to 3493 cm 1 corresponds to
the vibration of the O–H bond [15].
The spectrum of the Mod-ZnO shows that the nanoparticles were
modified after the treatment with oleic acid as suggested by the signals
associated with the vibration at 2854 and 2925 cm 1 of CH2 from the
alkyl carbon chain of oleic acid. The peak at 1590 cm 1 is due to the
presence of carboxylate groups, and the peaks at 1550 cm 1 and
1430 cm 1 correspond to the presence of COO [3], caused by the
carboxylic acid group of oleic acid reacting with surface hydroxyl groups
from the ZnO nanoparticles.

3.2. Characterisation of LDPE nanocomposites with ZnO incorporation

3.2.1. Dispersion and thermal analysis of LDPE/ZnO nanocomposites


The dispersion of the ZnO nanoparticles into the LDPE matrix was
assessed by means of field-emission scanning electron microscopy (FE-
SEM), from the study of the surface of the film with a high accelerating
voltage. The FE-SEM micrographs of the LDPE/ZnO and LDPE/Mod-ZnO
nanocomposites are displayed in Figs. 4 and 5, respectively. In general,
the ZnO nanoparticles in the LDPE matrix were homogeneously
distributed, except for some zones with agglomeration, which increased
with the amount of nanoparticles. A better dispersion was found when
Mod-ZnO nanoparticles were incorporated into LDPE, because the sur­
Fig. 3. Infrared spectrum of oleic acid, ZnO, and ZnO nanoparticles modified
face modification is an efficient route for improving nanoparticle
with oleic acid (Mod-ZnO).
dispersion in the matrix. The better dispersion of Mod-ZnO is due to the
presence of the oleic acid cues. Therefore, the nanoparticle modification
temperature (Tm) and degree of crystallinity (Xc) of LDPE and LDPE/ZnO
could increase the interaction between the modified nanoparticles and
nanocomposites are gathered in Table 1. The assessment of the Tm and Xc
the polymer, therefore improving the distribution of ZnO.
results showed that the thermal behaviour remained almost constant
Regarding the thermal analysis, the characteristic melting

Fig. 1. Image of TEM analysis of zinc oxide nanoparticles.

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K. Rojas et al. Composites Part B 172 (2019) 173–178

Fig. 4. Scanning electron microscopy images of a) LDPE; b) LDPE/ZnO; and c) LDPE/ZnO-Mod nanocomposites with 5 wt% nanoparticle incorporation.

Fig. 5. Scanning electron micrographs of a) LDPE, b) LDPE/ZnO, and c) LDPE/Mod-ZnO nanocomposites with 8 wt% nanoparticle incorporation.

with the ZnO incorporation into the LDPE matrix. Similar results have point of view, the surface of some nanoparticles can interact with rad­
been reported when different nanoparticles like clay, silica, silver, or icals coming from the polymer’s degradation, and this mechanism had
TiO2 were incorporated into LDPE. This behaviour may be correlated been explained when spherical nanoparticles were incorporated into the
with the minimum volume fraction of the nanoparticles incorporated polymer. On the other hand, the physical models established the lower
into the composite [1,2,16]. Also, the similar thermal properties of the diffusivity due to the presence of nanoparticles, which may decrease the
matrix and composites would suggest analogous processing conditions out-diffusion of volatile compounds from the decomposition.
as that of LDPE at a hypothetical industrial-scale production of these
nanocomposites. 3.2.2. Mechanical properties of the LDPE/ZnO nanocomposites
The effect of the ZnO nanoparticle incorporation on the thermal The mechanical properties of the neat LDPE and the nanocomposites
stability of LDPE/ZnO and LDPE/Mod-ZnO nanocomposites were stud­ were assessed by tensile tests, whose results are shown in Table 2.
ied by thermogravimetric analysis (TGA) in an inert atmosphere. The Young’s modulus increased approximately 18% and 15% for the LDPE/
results in terms of the temperature for 10% mass loss (T10) and the peak ZnO and LDPE/Mod-ZnO nanocomposites, respectively, compared to
of each degradation stage obtained from the derivative TGA curve (Tmax) neat LDPE. The elastic limit of the LDPE/ZnO and LDPE/Mod-ZnO
are given in Table 1. All the materials displayed at Tmax related to the remained constant compared to neat LDPE. The elongation at rupture
thermal degradation of LDPE at 480 � C. With the nanoparticle incor­ decreased ~15% and 11% for LDPE/ZnO and LDPE/Mod-ZnO, respec­
poration, the nanocomposites showed analogous Tmax values. The T10 tively, compared to neat LDPE.
increased 9 � C for LDPE/ZnO with 8 wt% of ZnO compared to LDPE, Comparing our results with other literature reports, Ahmed et al. [2],
regardless of the nanoparticle modifications. These results suggest that obtained PE/ZnO nanocomposites with 10 wt% of ZnO (d < 100 nm).
the nanoparticles may provide a better insulator and mass transport They found an increase of only approximately 12% of Young’s modulus
barrier for the volatile products generated during their decomposition in and a 63% decrease of elongation at break. They explained this behav­
the LDPE [2,17–19]. Palza et al. [19] described several models related to iour as due to ZnO nanoparticles incorporated into the LLDPE matrix
the increased thermal stability of polymer nanocomposites, which can having toughening and reinforcing effects, thereby restricting the mo­
be caused by either chemical or physical processes. From the chemical lecular motion of LLDPE polymer chains. On the other hand, Li et al. [6]
prepared HDPE/ZnO nanocomposites by melt-blending. In order to
Table 1
Thermal properties of the LDPE and LDPE/ZnO nanocomposites. Table 2
Sample ZnO wt.% Tm � C Xc % T10 � C Tmax � C
Mechanical properties of neat LDPE and LDPE/ZnO nanocomposites.
Sample ZnO (wt.%) E (MPa) σy (MPa) ε (%)
LDPE – 113 24 450 479
LDPE/ZnO 3 112 24 449 480 LDPE – 220 � 7 9.1 � 0.4 59.0 � 8.0
5 112 25 455 479 LDPE/ZnO 3 240 � 7 9.9 � 0.3 53.0 � 2.2
8 112 24 459 482 5 255 � 5 8.8 � 0.2 51.0 � 3.1
LDPE/Mod-ZnO 3 113 25 455 480 8 261 � 8 9.2 � 0.2 50.0 � 4.1
5 113 26 452 479 LDPE/Mod-ZnO 3 230 � 3 8.9 � 1.0 51.0 � 3.0
8 112 25 458 481 5 250 � 6 8.9 � 0.1 53.6 � 1.0
8 256 � 8 9.3 � 0.1 52.2 � 1.2
Tm: melting temperature; Xc: crystallinity degree, T10: decomposition tempera­
ture at 10% weight loss, Tmax: temperature for maximum weight loss rate. E: Young’s modulus; σy: elastic limit; ε: elongation at rupture.

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K. Rojas et al. Composites Part B 172 (2019) 173–178

increase the interaction between ZnO (d � 50 nm) and polymer, the cells, (iii) permeation of nanoparticles (ZnO) into the cell membrane,
nanoparticles were modified with ϒ-aminopropyltriethoxy silane and (iv) the formation of reactive oxygen species (ROS) as explained
(ZnO-APS). With increased nanoparticle amounts above 1.5 wt%, the before [7,14]. Zn2þ ions obtained from the hydrolysis of ZnO nano­
mechanical properties were not significantly enhanced. HDPE/ZnO-APS particles generate toxicity in the medium containing the microorgan­
nanocomposites with 2 wt% ZnO-APS increased the tensile strength isms. The solubility of ZnO depends on concentration and time. With
~12% compared to that of neat HDPE. The authors correlated this respect to the second mechanism proposed, the interaction electrostatic
observation with the feasible aggregation of nanoparticles, which leads forces between ZnO and bacterial cell membranes is due to the fact that
to a decrease in the interaction between the nanoparticles and the HDPE. ZnO nanoparticles have a positive charge, (zeta potential: þ24 mV)
The results proposed in the present study revealed improved me­ [21], and the cell has a negative charge due to the excess of carboxylic
chanical properties compared to other literature reports when using groups. This causes a strong interaction between the nanoparticles and
nanoparticles, and this may be ascribed to the smaller particle diameter the bacterial surface, and consequently damage to the cell membrane of
(d � 17 nm), which increased the contact area between the nanoparticle the bacteria. After the contact between ZnO and the bacteria, there is a
and LDPE for a given weight percentage. Also, the decrease of the perturbation of the cell wall, causing the penetration of nanoparticles
elongation at rupture of the nanocomposites was similar to that found in into the bacterial cells [22].
the literature. These results may be due to the fact that modified Finally, it should be noted that such small nanoparticles have greater
nanoparticles increased slightly the interaction between the polymer surface area leading to a high inhibition of bacteria due to easy pene­
and the nanoparticles, as shown by FE-SEM images. tration into the bacterial cell membrane [23]. In general, the results
confirm that the toxicity of ZnO nanoparticles could take place in the
3.2.3. Antimicrobial properties of LDPE and LDPE/ZnO nanocomposites dark and it is not just affected by ROS production [24].
The antimicrobial properties of the polymers against E. coli are given
in Table 3. The polymers were irradiated with UV light and the results 3.2.4. Ion release from LDPE matrix
were compared to those after white light irradiation. The results of the ICP analysis of zinc cation release in an aqueous
All the LDPE/ZnO nanocomposites after UV irradiation were effec­ environment during 28 days are shown in Fig. 6, for the LDPE/ZnO and
tive against E. coli ~99.99%, regardless of the nanoparticle concentra­ LDPE/Mod-ZnO composites. The cations released increase with the
tion and surface modification. Given the semiconducting behaviour of amount of nanoparticles. After 20 days of immersion of the LDPE/ZnO
ZnO, the incident radiation with photon energy higher than the value of and LDPE/Mod-ZnO nanocomposites, the cation release took place
its band gap (~3.3 eV) causes the movement of electrons from the regardless of the nanoparticle modification. The cation release results
valence band to the conduction band of the nanoparticle, promoting the obtained were related to the antimicrobial properties, but we do not
formation known as an electron hole (hþ) in the valence band and a free discard the presence of reactive oxygen species (ROS) on the surface.
electron (e ) in the conduction band. The electron hole (hþ) reacts with In particular, for LDPE/ZnO and LDPE/Mod-ZnO with 8 wt%, on the
H2O molecules giving �OH and Hþ. Furthermore, O2 molecules are first 5 days Zinc ion release increased, causing a quick release from the
charged generated superoxide radicals (O2 _ ), it react with Hþ to LDPE matrix. After that, the zinc ion release increased slowly. The initial
generate (HO�2). These species generating hydrogen peroxide anions release of zinc ions is due to particles on the specimen’s surface.
(HO2 ). Thus, the hydrogen peroxide anion reacts with hydrogen ions to Amorphous layers near the surface are able to accommodate more water
produce H2O2. It was reported that the H2O2 can penetrate the cells, molecules, resulting in greater ion release. A similar behaviour was
causing their peroxidation and then their death [20]. obtained from silver nanoparticles [1].
The antimicrobial properties of the LDPE/ZnO and LDPE/Mod-ZnO
nanocomposites irradiated with white light show increased effective­ 4. Conclusions
ness with the nanoparticle incorporation, and high antimicrobial prop­
erties ~99% against E. coli were achieved. At low ZnO incorporation ZnO nanoparticles with diameter of ~17 nm were successfully ob­
(3 wt%), the modification of the nanoparticles had an effect on the tained, modified, and incorporated in a low-density polyethylene
antimicrobial properties, as revealed by the bacterial reduction of (LDPE) matrix by means of industrial machinery, and good dispersion of
~82.26%. This behaviour may be correlated with the enhanced the nanoparticles was achieved.
dispersion of modified ZnO nanoparticles into the LDPE matrix. At The thermal behaviour of nanocomposites scarcely differs from that
higher nanoparticle concentrations (5 and 8 wt%), the antimicrobial
properties were independent of the modification.
The antimicrobial mechanism of ZnO nanoparticles is unclear, and it
is being studied in order to understand the behaviour of ZnO. However,
the antimicrobial properties of ZnO nanoparticles is attributed to
different mechanisms. Based on the experimental evidence, the anti­
microbial activity of ZnO nanoparticles has been related to four mech­
anisms, such as (i) the release of zinc cations from the surface of
nanoparticles, (ii) interaction between nanoparticles and microbial

Table 3
Reduction percentage of E. coli by LDPE/ZnO and LDPE/Mod-ZnO nano­
composites under UVA and white light.
Sample ZnO (wt.%) Bacterial reduction (%)

UV light White light

LDPE/ZnO 3 99.99 33.87


5 99.99 91.94
8 99.99 99.90
LDPE/Mod-ZnO 3 99.99 82.26
5 99.99 89.03
Fig. 6. [Znþ2] release from LDPE/ZnO and LDPE/Mod-ZnO with 5 and 8 wt%
8 99.99 99.16
of as a function of time after 28 days.

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K. Rojas et al. Composites Part B 172 (2019) 173–178

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Acknowledgements synthesized by microemulsion route. Int Lett Chem Phys Astron 2013;19:26–36.
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tiveness of the Chilean Economic Development Agency (CORFO) under nanocomposites. Polym Compos 2013;34:1878–83. https://doi.org/10.1002/
Grant 13CEI2-21839 is gratefully acknowledged. pc.22594.
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