materials

Article
High Oxygen and Water-Vapor Transmission Rate and
In Vitro Cytotoxicity Assessment with
Illite-Polyethylene Packaging Films
Dong Min Seong 1 , Heysun Lee 1 , Jungbae Kim 2 and Jeong Ho Chang 1, *
1 Center for Convergence Bioceramic Materials, Korea Institute of Ceramic Engineering and
Technology (KICET), Chungbuk 28160, Korea; sdm6230@naver.com (D.M.S.); hslee@kicet.re.kr (H.L.)
2 Department of Chemical and Biological Engineering, Korea University, Seoul 02841, Korea;
jbkim3@korea.ac.kr
* Correspondence: jhchang@kicet.re.kr; Tel.: +82-43-913-1510




Received: 23 April 2020; Accepted: 19 May 2020; Published: 21 May 2020


Abstract: This work reports the preparation of a ceramic hybrid composite film with illite and
polyethylene (illite-PE), and the evaluation of the freshness-maintaining properties such as oxygen
transmission rate (OTR), water vapor transmission rate (WVTR), tensile strength, and in vitro
cytotoxicity. The particle size of the illite material was controlled to within 10 µm. The illite-PE
masterbatch and film were prepared using a twin-screw extruder and a blown film maker, respectively.
The dispersity and contents of illite material in each masterbatch and composite film were analyzed
using a scanning electron microscope (SEM) and thermogravimetric analyzer (TGA). In addition,
the OTR and WVTR of the illite-PE composite film were 8315 mL/m2 ·day, and 13.271 g/m2 ·day,
respectively. The in vitro cytotoxicity of the illite-PE composite film was evaluated using L929 cells,
and showed a cell viability of more than 92%. Furthermore, the freshness-maintaining property
was tested for a packaging application with bananas; it was found to be about 90%, as indicated by
changes in the color of the banana peel, after 12 days.

Keywords: illite; polyethylene; composite film; cytotoxicity; oxygen transmission rate; water-vapor
transmission rate

1. Introduction
Recently, freshness-maintaining technologies have been developed to extend the shelf lives of
foods or fruits without contamination [1–7]. In particular, fruits and vegetables produce unusual
smells due to breathing when stored in a package, or ripen more quickly due to the release of ethylene
gas, resulting in poor marketability [8]. To solve this problem, a laser processing technique was
used to create microperforations in polymer packaging films to improve freshness by enhancing
the oxygen permeability of fruits and vegetables [9,10]. However, microperforation technology has
some disadvantages. It can degrade the film’s tensile strength, making it more prone to tearing and
allowing the infiltration of external contaminants such as moisture to occur [11]. As another packaging
technique, many inorganic ceramic powders have been used in polymer packaging films to improve
their properties such as mechanical strength, gas permeability control, and thermal stability. Porous
ceramics such as silica and zeolite have been applied to packaging films to absorb carbon dioxide, ester,
and ethylene gas emitted due to the breathing of fruits and vegetables.
This study introduces a method of increasing the oxygen permeability by adding a ceramic
filler during the film manufacturing process to generate fine pores at the interface between the film
matrix and the filler. Illite materials, which have a plate-like structure, were used for this purpose.
According to previous studies, when a plate-like clay mineral is peeled off into nano units and added

Materials 2020, 13, 2382; doi:10.3390/ma13102382 www.mdpi.com/journal/materials

Materials 2020, 13, 2382 2 of 10

to a polymer film, the plate-shaped particles with a high aspect ratio complicate the permeation path
of gas or water, resulting in decreased oxygen permeability [12–14]. However, in this study, we used
microsized illite particles with a low aspect ratio to increase oxygen permeability. In addition, when
the illite material is mixed with polyethylene (PE) without any pretreatment, the interaction with the
polymer is reduced due to the low surface area. Moreover, as agglomeration occurs due to the nature
of the ceramic powder, it is not uniformly dispersed in the film, which results in decreased mechanical
strength. To address this problem, in this study, a jet mill was used to reduce the particle size of the
illite material down to 10 µm or less.
The illite–PE masterbatch was prepared using a twin-screw extruder, and then a illite–PE
composite film was manufactured with the blown method [15,16]. The contents and dispersity of
illite in the illite–PE masterbatch and film were characterized using a scanning electron microscope
(SEM), thermogravimetric analyzer (TGA), and Fourier transform infrared (FT-IR) spectrophotometer.
The oxygen and moisture permeability of the illite–PE film and control PE film were determined
by assessing the oxygen transmission (OTR) and water vapor transmission rates (WVTR) [17–21].
The in vitro cytotoxicity was evaluated using an MTT assay; L929 mouse fibroblast cells were
exposed to various concentrations of the extracts from illite and illite-PE composite film. In addition,
the freshness-maintaining property was demonstrated for a packaging application with bananas;
the color change of the peel was monitored for 12 days after packing with a control PE film and a
manufactured illite-PE composite film.

2. Materials and Methods

2.1. Chemical and Materials

PE with a density of 0.915 g/cm3 used to prepare the masterbatch was purchased from LG Chem.
in Seoul, Korea. The melting flow rate (MFR) of the PE measured using ASTM D1238 was 52.0 g/10 min
at 190 ◦ C and a load of 2.16 kg. The illite material was obtained from the Yongkoong Illite company in
Youngdong, Korea. It was pulverized prior to the production of the masterbatch, and the particle size
and specific surface area were confirmed using a particle size analyzer (Horiba, Kyoto, Japan) and
Brunauer–Emmett–Teller (Micromeritics, Norcross, GA, USA), respectively.

2.2. Preparation of Illite-PE Masterbatch

To control the illite content (30 wt.%) of the masterbatch, the feed rate of the pure low-density
PE pellets and the illite required in two feeders (Bautek, Pocheon, Korea) was measured prior to the
experiment. To produce the illite-PE masterbatch, illite and PE were introduced into a corotating
(Bautek, Pocheon, Korea), twin-screw extruder (Bautek, Pocheon, Korea) at a ratio of 30–70% under
a screw speed of 480 rpm at a temperature of 80–190 ◦ C. The extrudate from the screw was pelleted
using a pelletizer (Bautek, Pocheon, Korea) (speed 4.3 Hz), yielding the final masterbatch [22–25].

2.3. Preparation of Illite-PE Composite Film

To produce the illite–PE composite film, the illite–PE masterbatch was mixed with PE pellets at a
selected ratio using a blown film maker (Hankook E.M., Pyeongtaek, Korea) under screw speeds of
16.8 Hz at a temperature of 130 ◦ C. The final amount of the illite–PE composite film was adjusted to
1 wt.%–2 wt.%. The film thickness was about 0.05–0.06 mm. The surface morphology of the composite
film was observed by SEM (Tescan, Brno, Czech).

2.4. Assessments of Freshness-Maintaining Performance of Illite-PE Composite Film

Bananas of similar size and ripening stages were selected, packaged, and sealed one-by-one in
a control film and an illite-PE composite film, and the changes were observed with the naked eye
every four days. Observations continued until the 12th day, and the color differences between the
two films were compared by measuring the chromaticity of the banana before and after packing
Materials 2020, 13, 2382 3 of 10

using a colorimeter (Cortex Technology, Hadsund, Denmark). The chromaticity value is L*, a unit of
measurement of brightness in the CIE color system, which is generally used in the food industry. The L*
value ranged from 0 (black) to 100 (white). The storage conditions were maintained at a temperature
of 24 ◦ C and a humidity of 50 % RH [26].

2.5. In Vitro Cytotoxicity of Illite-PE Composite Film

To evaluate the biological stability of illite-PE packaging film, a cytotoxicity test was carried out
according to an elution test method (ISO 10993-5). The test solution was eagle minimum essential
medium (MEM) supplemented with 10% fetal bovine serum (FBS) (Welgene, Gyeongsan, Korea) and
2% penicillin (Gibco, Carlsbad, CA, USA) Sample (illite materials, illite-PE film) were eluted in the test
solution at 37 ◦ C for 24 h under continuous stirring. L929 mouse fibroblast cells (ATCC No. CCL-1)
were cultured in test solution in a humidified 5% CO2 incubator at 37 ◦ C for 24 h. L929 cells were
seeded into 96-well plates (104 cells/well) and incubated at 37 ◦ C for 24 h. Then, the cells were treated
with extracts of illite materials and the illite-PE composite film at various concentrations (12.5, 25, 50,
and 100%) and incubated in a cell incubator at 37 ◦ C. After incubation for 24 h, the cytotoxicity of each
extract was measured using a microplate reader (Tecan, Mannedorf, Switzerland) at a wavelength of
570 nm.

2.6. Instrumental Analysis

Illite pulverization was conducted at a feed rate of 0.43 kg/h and air pressure of 0.74 Mpa, using a
Nisshin SJ-500 (Nisshin, Tokyo, Japan). A particle size analysis was conducted using the wet method
of the LA-960 from HORIBA. The specific surface area was measured using a MicroStar® TriStar II
3020 (Micromeritics, Norcross, GA, USA); nitrogen was used for adsorption. For the XRD analysis,
Rigaku’s MiniFlex600 (Rigaku, Tokyo, Japan) was used to analyze the diffraction pattern in the range
of 5–90◦ at a rate of 10◦ /min [27]. A thermogravimetric analysis was performed from 25 to 700 ◦ C at a
rate of 10◦ /min in a nitrogen atmosphere using a Q600 TA instrument (TA instruments, New Castle,
DE, USA) [28]. FT-IR analysis was conducted using Jasco’s FT-IR 460 Plus equipment (Jasco, Easton,
PA, USA) with the attenuated total reflection method.
An SEM was used to scan the sample surface with a TESCAN MIRA3, which resulted in the
dispersibility of the illite contained in the polymer matrix of the masterbatch and film. The masterbatch
sample was cut parallel to the ejected direction and the surface was photographed at 5 kV after
being platinum-coated. The film sample was cut into a specimen size of 5 mm, and its surface
was photographed at 10 kV after platinum-coating the surface in the same manner as that for the
masterbatch. The tensile strength of the film was measured under a test speed of 500 mm/min in
accordance with the KS M 3001: 2001 standard using a DUT-3000CM (Daekyung, Bucheon, Korea).
To determine the moisture permeability of the film, the amount of moisture that penetrated an area
of 33.18 cm2 was measured five times under the conditions of 90% RH, 38 ◦ C temperature, and 60 min
test interval using a W3/031 (Labthink, Medford, MA, USA), in line with the ASTM E96 standards.
To determine the oxygen permeability of the film, the amount of oxygen permeating 1.131 cm2 of the
specimen for 30 min was measured with a masking technique at 23 ◦ C and 50% RH using a C230
(Labthink, Medford, MA, USA) in accordance with the ASTM D3985 standards. The chromaticity of the
banana was measured with a DSM III (Cortex Technology, Hadsund, Denmark) at three particular spots;
the measured values at these spots were averaged to produce the chromaticity value of the banana.

3. Results
Figure 1 shows the preparation process of the illite-PE masterbatch and film. Before the preparation
of the illite-PE masterbatch, the feed rate was set by measuring the weight of the illite and PE exited
through the feeder. The screw rate was adjusted to 480 rpm and extruded by mixing the illite and
PE through the feeder. The illite and PE were discharged through the feeder at a constant rate and
fed into the twin-screw extruder through the hopper. As the temperature of the extruder was higher
Materials 2020, 13, 2382 4 of 10

Materials 2020, 13, x FOR PEER REVIEW 4 of 10

than the melting point of PE, the extruder was mixed and extruded with the illite while the PE was
the PE was
molten. The molten. The
extrudate was extrudate wascooled
sufficiently sufficiently
in thecooled in the water-cooling
water-cooling zone and cut zone
with and cut withtoa
a pelletizer
pelletizer to obtain a masterbatch. The feed and screw rate of the sample should
obtain a masterbatch. The feed and screw rate of the sample should be set such that the samplebe set such that the
does
sample
not does notinaccumulate
accumulate the hopper.inThethepelletizer
hopper. Theratepelletizer
should beratesetshould
so that be
theset so that theare
extrudates extrudates are
not cut and
notproper
the cut and the proper
thickness thickness is The
is maintained. maintained.
preparedThe prepared masterbatch
masterbatch was fedfilm
was fed to a blown to amaker
blownwith
film
makerinwith
LDPE LDPE in
a constant a constant
ratio ratio
to prepare anto preparecomposite
illite-PE an illite-PE composite film.
film.

Figure 1. Schematic diagrams for preparation of (a) illite-PE masterbatch and (b) illite-PE film.
Figure 1. Schematic diagrams for preparation of (a) illite-PE masterbatch and (b) illite-PE film.
Figure 2a shows the XRD patterns of illite material, PE, illite-PE masterbatch, and illite-PE
Figure 2a shows the XRD patterns of illite material, PE, illite-PE masterbatch, and illite-PE
composite film. The XRD patterns of the illite material showed peaks at 8.8◦ , 17.7◦ , 19.8◦ , 26.6◦ ,
composite film. The XRD patterns of the illite material showed peaks at 8.8°, 17.7°, 19.8°, 26.6°, and
and 45.4◦ , while those of PE material showed peaks at 19.8◦ , 21.5◦ , and 23.9◦ . The illite-PE masterbatch
45.4°, while those of PE material showed peaks at 19.8°, 21.5°, and 23.9°. The illite-PE masterbatch
showed a broad peak at 21.5◦ , along with the peak of the illite material. In the illite-PE composite
showed a broad peak at 21.5°, along with the peak of the illite material. In the illite-PE composite
film, the illite peak became weak while the film exhibited strong peaks at 21.5◦ and 23.9◦ , which
film, the illite peak became weak while the film exhibited strong peaks at 21.5° and 23.9°, which were
were attributable to the increased content of PE. Stronger PE peaks were observed in the illite-PE film
attributable to the increased content of PE. Stronger PE peaks were observed in the illite-PE film (PE
(PE content of 98 wt.%) as compared to the illite-PE masterbatch (PE content of 70 wt.%). Figure 2b
content of 98 wt.%) as compared to the illite-PE masterbatch (PE content of 70 wt.%). Figure 2b shows
shows the FT-IR spectrum in the range of 4000–650 cm−1 for illite material, PE, illite-PE masterbatch,
the FT-IR spectrum in the range of 4000–650 cm for illite material, PE, illite-PE masterbatch, and
and illite-PE film. The spectrum of illite material showed a peak of 1000 cm−1 (Si-O-Si stretching
illite-PE film. The spectrum of illite material showed a peak of 1000 cm (Si-O-Si stretching
vibration) and 3600 cm−1 (H-O-H stretching vibration). In the spectrum of PE, 2920 cm−1 , 2850 cm−1
vibration) and 3600 cm (H-O-H stretching vibration). In the spectrum of PE, 2920−1cm , 2850 cm
(C-H stretching) peaks were observed [29]. In the illite-PE composite film, 1000 cm , 2900 cm−1 and
(C-H stretching) peaks were observed [29]. In the illite-PE composite film, 1000 cm , 2900 cm and
2850 cm−1 peaks appeared. As a result, it was shown that the peak of 1000 cm−1 weakens as the illite
2850 cm peaks appeared. As a result, it was shown that the peak of 1000 cm weakens as the
content in the polymer decreases.
illite content in the polymer decreases.
Materials 2020, 13, x FOR PEER REVIEW 5 of 10
Materials 2020, 13, x FOR PEER REVIEW 5 of 10
Materials 2020, 13, 2382 5 of 10

(a) (b)
(a) (b)

(a) XRD
Figure 2. (a) XRD and
and (b)
(b) FT-IR
FT-IR spectra of illite, iliite-PE masterbatch, and iliite-PE film.
Figure 2. (a) XRD and (b) FT-IR spectra of illite, iliite-PE masterbatch, and iliite-PE film.
Figure 33 shows
Figure shows the the SEM
SEM images
images and and TGA
TGA analyses
analyses ofof illite,
illite, illite-PE
illite-PE masterbatch
masterbatch and and illite-PE
illite-PE
composite
Figurefilm.
composite film. The SEM
The
3 shows SEM images
images
the SEM showand
show
images theTGA
the 33 μm of particle
particle
µmanalyses
of size
ofsize of illite-PE
of
illite, illite, dispersed
illite, dispersed in theand
in the
masterbatch PE matrix
PE matrix
illite-PEof
of
illite-PE
composite masterbatch,
illite-PE masterbatch,
film. The SEM and uniformly
andimages
uniformly dispersed
showdispersed inside
the 3 μm inside the PE
the PE
of particle matrix
sizematrix without
without
of illite, agglomeration
agglomeration
dispersed in illite-PE
in illite-
in the PE matrix of
composite filmfilm
[30].[30].
Aand
sudden drop in weight near ◦ C was due to the combustion of PE. The 50%
400the
PE composite
illite-PE masterbatch, A uniformly
sudden drop in weight
dispersed near
inside 400PE°Cmatrix
was due to theagglomeration
without combustion ofin PE. The
illite-
mass
50%
PE loss temperatures
mass
composite loss
film [30]. Aofsudden
temperaturesLDPE, of illite-PE
LDPE,
drop masterbatch
in illite-PE
weight near and°C
masterbatch
400 illite-PE
wasand composite
due illite-PE film were determined
composite
to the combustion film
of PE.were
The
to be 465 ◦ C, 477 ◦ C, and 473 ◦ C, respectively. The illite content in the film was calculated in the
determined
50% mass loss to betemperatures
465 °C, 477 °C, ofand 473 °C,
LDPE, respectively.
illite-PE The illite
masterbatch andcontent in the
illite-PE film wasfilm
composite calculated
were
section where it was stabilized ◦ C. The thermogravimetric analysis showed that the
in the section
determined towhere
be 465it°C,
was
477 °C,again
stabilized
and 473 after
again 500
°C,after 500 °C. The
respectively. Thethermogravimetric
illite content in theanalysis
film was showed
calculated that
illite
the
in the content
illite
section in
content the
where masterbatch
in the masterbatch
it was waswas
stabilized about
about
again 30%,
after while
30%,
500 °C.that
whileThe in
that the composite
in the composite
thermogravimetric filmanalysis
waswas
film about 1–2%.
about
showed 1–2%.
that
the illite content in the masterbatch was about 30%, while that in the composite film was about 1–2%.

20 μm 20 μm 50 μm
20 μm (a) 20 μm 50 μm
(a)
100 Illite
100 Illite
80

80
(%) (%)

60
Weight

60
Weight

40

40 Illite-PE MB

20
Illite-PE MB

20 LDPE
Illite-PE Film
0 LDPE
0 100 200 300 400 500Illite-PE
600 Film700
0
0 100 200 Temperature
300 400 (°C)
500 600 700
Temperature
(b) (°C)
Figure 3. (a) SEM images and (b) TGA (b)
analysis of illite, iliite-PE masterbatch, and iliite-PE film
Figure 3. (a) SEM images and (b) TGA analysis of illite, iliite-PE masterbatch, and iliite-PE
respectively.
Figure 3. (a) SEM images and (b) TGA analysis of illite, iliite-PE masterbatch, and iliite-PE film
film respectively.
respectively.
Materials 2020, 13, 2382 6 of 10
Materials 2020, 13, x FOR PEER REVIEW 6 of 10

Figure
Figure 4a4a shows
shows thethe oxygen
oxygen permeability
permeability andand moisture
moisture permeability
permeability ofof
thethe illite-PE
illite-PE composite
composite
film by oxygen transmission rate (OTR) and water vapor transmission
film by oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) [31]. The illite-PE rate (WVTR) [31]. The illite-
PE composite
composite film ahad
film had a permeability
permeability valuevalue of 8315
of 8315 mL/mmL/m 2
2 ·day,·day, while
while thethe oxygen
oxygen permeability
permeability value
value
of the illite-PE film was about 2 times higher (4090 mL/m 2 2·day) [32]. This was attributed to the
of the illite-PE film was about 2 times higher (4090 mL/m ·day) [32]. This was attributed to the
addition
addition of illite
of illite particles
particles between
between the PEthematrices,
PE matrices,
whichwhich
ensured ensured
a simplea path
simple path which
through through which
oxygen
oxygen
could could
easily easily
travel travelthe
through through
PE–illitetheparticle
PE–illite particle The
interface. interface.
moistureThepermeability
moisture permeability of the
of the illite-PE
illite-PE composite film was determined as the average of the
composite film was determined as the average of the five measured values. The results showedfive measured values. The results
showed
that that thepermeability
the moisture moisture permeability
was 5.35 g/m was 5.35for
2 ·day g/m 2·day for control PE and 13.27 g/m2·day for the
control PE and 13.27 g/m2 ·day for the illite-PE
illite-PE composite film. Figure 4b shows the tensile
composite film. Figure 4b shows the tensile strength of the film: 25.6 strength of the film:
Mpa for25.6
the Mpa for composite
illite-PE the illite-PE
composite film, which is higher than the value of 17.2 Mpa for the control
film, which is higher than the value of 17.2 Mpa for the control PE film. This is attributable PE film. This is attributable
to the
load distribution in the illite due to the interfacial stress between the polymer matrix and theand
to the load distribution in the illite due to the interfacial stress between the polymer matrix the
illite
illite particles [33]. In addition, the fact that the tensile strength was increased
particles [33]. In addition, the fact that the tensile strength was increased indirectly indicates that theindirectly indicates that
theparticles
illite illite particles were well-dispersed
were well-dispersed in thein the polymer
polymer matrix.matrix.

(a) (b)
10000 20 35
O W
T V
R T

30
8000
15
WVT (g/m •day)
OTR (mL/m •day)

25
Tensile strength (MPa)

6000
2
2

20
10

4000 15

5 10
2000
5

0 0
0
LDPE Illite-PE Film LDPE Illite-PE film

Figure 4. Comparison of (a) oxygen transmission rate (OTR) and water vapor transmission rate.
(WVTR), and (b) tensile strength of control LDPE and illite-PE film.
Figure 4. Comparison of (a) oxygen transmission rate (OTR) and water vapor transmission rate.
(WVTR), and (b) tensile strength of control LDPE and illite-PE film.
Figure 5 shows the in vitro cytotoxicity assessment for illite and illite-PE composite film using
MTT assay, where L929 mouse fibroblast cells were exposed to the various concentrations of the
Figure 5 shows the in vitro cytotoxicity assessment for illite and illite-PE composite film using
extracts from illite and illite-PE composite film. They were shown to be capable of metabolizing a dye
MTT assay, where L929 mouse fibroblast cells were exposed to the various concentrations of the
as 3-(4,5-dimethylthiozol-2-yl)-2,5-diphenyl tetrazolium bromide. Cell viability was calculated using
extracts from illite and illite-PE composite film. They were shown to be capable of metabolizing a dye
the following Equation (1).
as 3-(4,5-dimethylthiozol-2-yl)-2,5-diphenyl tetrazolium100 ×bromide.
OD570t Cell viability was calculated using
the following Equation (1). Cell viability (%) = (1)
OD570b
×
where OD570t and OD570b are the average Cell values
viability
of (%) =
absorbance of the blank solution. (1)
After 24 h of posttreatment, L929 mouse fibroblast cells showed excellent viabilities, i.e., 92.3%
andwhere
100%,OD 570t and OD570b are the average values of absorbance of the blank solution.
even up to a concentration of 50% illite and illite-PE composite film, respectively. These
After 24 h
results clearly showed of posttreatment,
the absenceL929 mouse
of any fibroblast
noticeable cells showed
toxicity excellent
of illite and viabilities,
illite-PE i.e., film.
composite 92.3%
and 100%, even up to a concentration of 50% illite and illite-PE composite film,
However, cell viability was decreased to 59% and 93% in the extract solution with a 100% concentration respectively. These
results clearly showed the absence of any noticeable toxicity of illite and illite-PE
of the illite and illite-PE composite film. This was attributed to the spontaneous MTT reduction which composite film.
However,
occurred cell dehydrogenase
because viability was decreased
enzymes whichto 59% wereand 93%
only in the
present extract
in viable solution
cells reducedwith a 100%
the yellow
concentration of the illite and illite-PE composite film. This was attributed
MTT to purple insoluble formazan crystals, which then accumulated inside the cell [34]. to the spontaneous MTT
reduction which occurred because dehydrogenase enzymes which were only present
Figure 6 shows the results of the evaluation of the freshness-maintaining function of the illite–PE in viable cells
reduced the
composite film.yellow MTT toinpurple
The changes insoluble
the state formazan
of bananas crystals,PE
in the control which thenthe
film and accumulated inside the
illite–PE composite
cell [34].
film were checked once every 4 days. The bananas packaged in the control PE film began to change
starting on the 4th day, and were severely changed in terms of decay and the color of the peel on the
12th day. The bananas packaged in the illite-PE composite film began to change starting on day 8,
and part of them turned black on day 12. The chromaticity of the banana was 46.6 and 46.5 for the
control and illite-PE composite film at the beginning, respectively, and 13.0 and 40.7 after 12 days.
Thus, the changes were 72.1% and 12.5% over 12 days, respectively. As a result, both visually and in
Materials 2020, 13, 2382 7 of 10

terms of chromaticity, the bananas stored in illite-PE composite film had a lower degree of ripening
Materials
and decay 2020, 13, x FOR PEER
compared REVIEW
to those stored in the control PE film. 7 of 10

Figure 5. In vitro cytotoxicity of illite material and illite-PE film (negative control; high density.
polyethylene film, positive control; 0.1 % ZDEC polyurethane film).

Figure 6 shows the results of the evaluation of the freshness-maintaining function of the illite–
PE composite film. The changes in the state of bananas in the control PE film and the illite–PE
composite film were checked once every 4 days. The bananas packaged in the control PE film began
to change starting on the 4th day, and were severely changed in terms of decay and the color of the
peel on the 12th day. The bananas packaged in the illite-PE composite film began to change starting
on day 8, and part of them turned black on day 12. The chromaticity of the banana was 46.6 and 46.5
for the control and illite-PE composite film at the beginning, respectively, and 13.0 and 40.7 after 12
days.Figure
Thus, theInchanges were 72.1% illite
and 12.5% over 12 days, respectively. As a result, both visually
5. In vitro
Figure 5. vitro cytotoxicity
cytotoxicity of
of illite material
material and
and illite-PE
illite-PE film
film (negative
(negative control; high density.
control; high density.
and in terms of chromaticity,
polyethylene the bananas stored in illite-PEfilm).
composite film had a lower degree of
polyethylenefilm,
film,positive
positivecontrol;
control;0.1
0.1%%ZDEC
ZDECpolyurethane
polyurethane film).
ripening and decay compared to those stored in the control PE film.
Figure 6 shows the results of the evaluation of the freshness-maintaining function of the illite–
PE composite film. The changes in the state of bananas in the control PE film and the illite–PE
composite film were checked once every 4 days. The bananas packaged in the control PE film began
to change starting on the 4th day, and were severely changed in terms of decay and the color of the
peel on the 12th day. The bananas packaged in the illite-PE composite film began to change starting
on day 8, and part of them turned black on day 12. The chromaticity of the banana was 46.6 and 46.5
for the control and illite-PE composite film at the beginning, respectively, and 13.0 and 40.7 after 12
days. Thus, the changes were 72.1% and 12.5% over 12 days, respectively. As a result, both visually
and in terms of chromaticity, the bananas stored in illite-PE composite film had a lower degree of
ripening and decay compared to those stored in the control PE film.
Materials 2020, 13, x FOR PEER REVIEW 8 of 10
(a)

(a)

(b)
Figure 6. Comparison
Comparison of
of (a)
(a)freshness-maintenance
freshness-maintenanceproperty
propertyand
and(b)
(b) chromaticity
chromaticity changes
changes of of illite–
illite–PE
PE
filmfilm
andand control
control LDPE
LDPE fordays.
for 12 12 days.

4. Conclusions
Ceramic composite films containing PE polymer and illite minerals were prepared to increase
the freshness maintenance period of fruits and vegetables inside packaging materials. The illite
content in the illite-PE composite films adjusted using the masterbatch was 1.8%, according to TGA
Materials 2020, 13, 2382 8 of 10

4. Conclusions
Ceramic composite films containing PE polymer and illite minerals were prepared to increase the
freshness maintenance period of fruits and vegetables inside packaging materials. The illite content
in the illite-PE composite films adjusted using the masterbatch was 1.8%, according to TGA analysis.
The oxygen permeability value of the illite-PE composite film was 8315 mL/m2 ·day for the illite-PE
composite film, which was about 2 times higher than that of an ordinary PE film (4090 mL/m2 ·day).
The moisture permeability values of the film were 5.35 g/m2 ·day for ordinary films and 13.27 g/m2 ·day
for Illite-PE composite films. The tensile strength values were 25.6 Mpa for the illite-PE composite
film, which was higher than those of the control film (17.2 Mpa). In the storage experiment of the
banana, the ripening difference between the control film and illite-PE composite film was observed
from the 4th day of the experiment. On the 12th day, there was a noticeable decrease in the extent
of the decay and color change of the bananas packaged in the illite-PE composite film compared to
those packaged in the control film. In view of these results, because the oxygen permeability increased
when the composite film containing illite was used as a packaging material, it is expected to reduce the
oxygen concentration inside the package by breathing or increase the shelf life of vegetables and fruits
that release aging-expediting gases.

Author Contributions: Conceptualization, J.H.C.; methodology, J.H.C. and J.K.; formal analysis, D.M.S. and
H.L.; investigation, D.M.S and H.L.; writing—original draft preparation D.M.S. and J.H.C.; writing—review and
editing, J.H.C.; project administration, J.H.C.; funding acquisition, J.H.C. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by a grant from the R&D program funded by the Ministry of Trade, Industry
and Energy (MOTIE, Korea), part of the Industry Core Technology Development Program funded by the Korea
Evaluation Institute of Industrial Technology (KEIT) [10063291] and also supported by Korea Institute of Ceramic
Engineering and Technology (KICET, Korea).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Ahmed, I.; Lin, H.; Zou, L.; Brody, A.L.; Xing, L.Z.; Qazi, I.M.; Pavase, T.R.; Lv, L. A comprehensive review on
the application of active packaging technologies to muscle foods. Food Control 2017, 82, 163–178. [CrossRef]
2. Caleb, O.J.; Opara, U.L.; Witthuhn, C. Modified atmosphere packaging of pomegranate fruit and arils:
A review. Food Bioprocess Technol. 2011, 5, 15–30. [CrossRef]
3. Han, J.H. A Review of food packaging technologies and innovations. Innov. Food Packag. 2014, 3–12.
[CrossRef]
4. Ghaani, M.; Cozzolino, C.A.; Castelli, G.; Farris, S. An overview of the intelligent packaging technologies in
the food sector. Trends Food Sci. Technol. 2016, 51, 1–11. [CrossRef]
5. Poyatos-Racionero, E.; Ros-Lis, J.V.; Vivancos, J.-L.; Martínez-Máñez, R. Recent advances on intelligent
packaging as tools to reduce food waste. J. Clean. Prod. 2018, 172, 3398–3409. [CrossRef]
6. Biji, K.B.; Ravishankar, C.N.; Mohan, C.O.; Gopal, T.K.S. Smart packaging systems for food applications:
A review. J. Food Sci. Technol. 2015, 52, 6125–6135. [CrossRef] [PubMed]
7. Brockgreitens, J.; Abbas, A. Responsive food packaging: Recent progress and technological prospects.
Compr. Rev. Food Sci. Food Saf. 2015, 15, 3–15. [CrossRef]
8. Pech, J.; Bouzayen, M.; Latché, A. Climacteric fruit ripening: Ethylene-dependent and independent regulation
of ripening pathways in melon fruit. Plant Sci. 2008, 175, 114–120. [CrossRef]
9. Gonzalez, J.; Ferrer, A.; Oria, R.; Salvador, M.L. Determination of O2 and CO2 transmission rates through
microperforated films for modified atmosphere packaging of fresh fruits and vegetables. J. Food Eng. 2008,
86, 194–201. [CrossRef]
10. Kartal, S.; Aday, M.S.; Caner, C. Use of microperforated films and oxygen scavengers to maintain storage
stability of fresh strawberries. Postharvest Boil. Technol. 2012, 71, 32–40. [CrossRef]
11. Wang, Z.-Y.; Du, Z.; Chan, J.K.Y.; Teoh, S.H.; Thian, E.S.; Hong, M. Direct laser microperforation of
bioresponsive surface-patterned films with through-hole arrays for vascular tissue-engineering application.
ACS Biomater. Sci. Eng. 2015, 1, 1239–1249. [CrossRef]
Materials 2020, 13, 2382 9 of 10

12. Alexandre, M.; Dubois, P. Polymer-layered silicate nanocomposites: Preparation, properties and uses of a
new class of materials. Mater. Sci. Eng. R Rep. 2000, 28, 1–63. [CrossRef]
13. Rhim, J.-W.; Hong, S.-I.; Ha, C.-S. Tensile, water vapor barrier and antimicrobial properties of PLA/nanoclay
composite films. LWT-Food Sci. Technol. 2009, 42, 612–617. [CrossRef]
14. Fasihi, M.; Abolghasemi, M.R. Oxygen barrier and mechanical properties of masterbatch-based PA6/nanoclay
composite films. J. Appl. Polym. Sci. 2012, 125, E2–E8. [CrossRef]
15. Pokharel, P.; Lee, D.S. High performance polyurethane nanocomposite films prepared from a masterbatch of
graphene oxide in polyether polyol. Chem. Eng. J. 2014, 253, 356–365. [CrossRef]
16. Adak, B.; Joshi, M.; Butola, B.S. Polyurethane/clay nanocomposites with improved helium gas barrier
and mechanical properties: Direct versus master-batch melt mixing route. J. Appl. Polym. Sci. 2018, 135,
46422–46426. [CrossRef]
17. Hong, S.-I.; Rhim, J.-W. Preparation and properties of melt-intercalated linear low density polyethylene/clay
nanocomposite films prepared by blow extrusion. LWT-Food Sci. Technol. 2012, 48, 43–51. [CrossRef]
18. Rosa, D.S.; Neto, I.C.; Calil, M.R.; Pedroso, A.G.; Fonseca, C.P.; Neves, S. Evaluation of the thermal and
mechanical properties of poly(ε-caprolactone), low-density polyethylene, and their blends. J. Appl. Polym.
Sci. 2004, 91, 3909–3914. [CrossRef]
19. Hasegawa, N.; Okamoto, H.; Kato, M.; Usuki, A. Preparation and mechanical properties of polypropylene-clay
hybrids based on modified polypropylene and organophilic clay. J. Appl. Polym. Sci. 2000, 78, 1918–1922.
[CrossRef]
20. Mangaraj, S.; Goswami, T.K.; Panda, D.K. Modeling of gas transmission properties of polymeric films used
for MA packaging of fruits. J. Food Sci. Technol. 2014, 52, 5456–5469. [CrossRef]
21. Wang, Y.; Easteal, A.J.; Chen, X.D. Ethylene and oxygen permeability through polyethylene packaging films.
Packag. Technol. Sci. 1998, 11, 169–178. [CrossRef]
22. Li, Y.; Chen, G.-H. HDPE/expanded graphite nanocomposites prepared via masterbatch process. Polym. Eng.
Sci. 2007, 47, 882–888. [CrossRef]
23. Gomes, E.V.D.; Visconte, L.L.Y.; Pacheco, E.B.A.V. Morphological, thermal and mechanical properties of
polypropylene and vermiculite blends. Int. J. Polym. Mater. 2008, 57, 957–968. [CrossRef]
24. Elleithy, R.; Ali, I.; Ali, M.A.; Al-Zahrani, S.M.; Al-Zahrani, S.M. High density polyethylene/micro calcium
carbonate composites: A study of the morphological, thermal, and viscoelastic properties. J. Appl. Polym. Sci.
2010, 117, 2413–2421. [CrossRef]
25. Raji, M.; Essabir, H.; Essassi, E.M.; Rodrigue, D.; Bouhfid, R.; Qaiss, A.E.K. Morphological, thermal,
mechanical, and rheological properties of high density polyethylene reinforced with illite clay. Polym. Compos.
2016, 39, 1522–1533. [CrossRef]
26. Gomes, J.F.S.; Vieira, R.R.; De Oliveira, I.A.A.; Leta, F.R. Influence of illumination on the characterization of
banana ripening. J. Food Eng. 2014, 120, 215–222. [CrossRef]
27. Villanueva, M.; Cabedo, L.; Gimenez, E.; Lagaron, J.; Coates, P.; Kelly, A. Study of the dispersion of nanoclays
in a LDPE matrix using microscopy and in-process ultrasonic monitoring. Polym. Test. 2009, 28, 277–287.
[CrossRef]
28. Xia, X.; Cai, S.; Xie, C. Preparation, structure and thermal stability of Cu/LDPE nanocomposites. Mater. Chem.
Phys. 2006, 95, 122–129. [CrossRef]
29. Gulmine, J.; Janissek, P.; Heise, H.; Akcelrud, L. Polyethylene characterization by FTIR. Polym. Test. 2002, 21,
557–563. [CrossRef]
30. Prashantha, K. Multi-walled carbon nanotube filled polypropylene nanocomposites based on masterbatch
route: Improvement of dispersion and mechanical properties through PP-g-MA addition. Express Polym.
Lett. 2008, 2, 735–745. [CrossRef]
31. McHugh, T.H.; Krochta, J.M. Sorbitol- vs glycerol-plasticized whey protein edible films: Integrated oxygen
permeability and tensile property evaluation. J. Agric. Food Chem. 1994, 42, 841–845. [CrossRef]
32. Shi, Q.P.; Li, D.L.; Xu, W.C. LDPE/EVA Modified film prepared by melt blend method and study of its
mechanical performances and barrier property. Mater. Sci. Forum 2011, 689, 321–327. [CrossRef]
Materials 2020, 13, 2382 10 of 10

33. Liang, J.-Z. Estimation of tensile strength of inorganic plate-like particulate reinforced polymer composites.
Polym. Eng. Sci. 2012, 53, 1823–1827. [CrossRef]
34. López-García, J.; Lehocký, M.; Humpolíček, P.; Saha, P. HaCaT Keratinocytes response on antimicrobial
atelocollagen substrates: Extent of cytotoxicity, cell viability and proliferation. J. Funct. Biomater. 2014, 5,
43–57. [CrossRef]

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