Food Packaging and Shelf Life 37 (2023) 101060

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Food Packaging and Shelf Life

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

Development of organic-inorganic hybrid antimicrobial materials by

mechanical force and application for active packaging
Weizhong Zhu a, b, Jiali Chen a, b, Qingfeng Dong a, b, c, Donglei Luan a, b, *, Ningping Tao a, b, c,
Shanggui Deng d, Li Wang a, b, c, Yi Hao a, b, Li Li a, b, c, *
a
College of Food Science and Technology, Shanghai Ocean University, Shanghai 201306, People’s Republic of China
b
Engineering Research Center of Food Thermal-Processing Technology, College of Food Science and Technology, Shanghai Ocean University, Shanghai 201306, People’s
Republic of China
c
Shanghai Engineering Research Center of Aquatic-Product Processing & Preservation, Shanghai 201306, People’s Republic of China
d
College of Food and Pharmacy, Zhejiang Ocean University, Zhoushan 316000, Zhejiang, People’s Republic of China

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

Keywords: The loading and delivery of nanomaterials have attracted considerable interest. In this study, the organic-
Cryogenic ball milling inorganic hybrid antimicrobial materials of clove essential oil (CEO) intercalated organic montmorillonite
Antimicrobial material (MMT) were prepared using a facile and novel cryogenic ball milling technology and characterized. Fourier
Active packaging film
transform infrared spectroscopy, powder X-ray diffraction, and transmission electron micrograph analysis
Sustained release
Abalone preservation
confirmed the successful preparation of the hybrid antimicrobial materials, and thermogravimetric analysis
further demonstrated the thermal stability. In a novel application, hybrid antimicrobial materials were extruded
with thermoplastic starch (TPS), polylactic acid (PLA), and poly (butylene adipate-co-terephthalate) (PBAT) to
prepare active packaging films. The film release experiments showed that the CEO in the film, containing hybrid
antimicrobial materials, was in a sustained release state, and its equilibrium release was higher than that of other
films. The prepared films were used to preserve fresh abalone （Haliotis discus hannai Ino）, physicochemical
changes and microbiological counts were determined. The results showed that the shelf life of fresh abalone
packed in films containing hybrid antimicrobial materials was extended by 3–5 days, indicating that cryogenic
ball milling is a simple and effective method for preparing organic-inorganic hybrid antimicrobial materials for
active packaging.

1. Introduction
Abalone is a valuable marine edible shellfish, known as the "soft gold
on the table", its meat is tender, tasty, and rich in nutrition. With the
change in lifestyle and the improvement of living standards, abalone is
becoming a larger and larger part of the personal diet structure (Dong,
Fang, Wang, Zhang, & Tao, 2017). However, fresh abalone meat is prone
to spoilage during the refrigeration process and needs to be preserved by
some methods to extend its shelf life.
Packaging systems help maintain food quality, integrity, and safety
while avoiding possible contamination in all food supply chains
(Rodrigues Arruda, Campos Bernardes, Robledo Fialho e Moraes, & de
Fátima Ferreira Soares, 2022). Growing public concern about food
safety has been observed due to the increasing occurrence of foodborne
illness outbreaks caused by pathogenic and spoilage microorganisms
(Zou, Tao, Ye, & Liu, 2019). To satisfy the demands of consumers and
restore their confidence in the safety of food products, the food industry
has been actively seeking natural alternatives with intense antimicrobial
and/or antioxidant properties (Bensid, El Abed, Houicher, Regenstein, &
Ozogul, 2020). Plant essential oils are promising natural antimicrobial
agents due to their safety, economy, and wide antimicrobial and anti­
oxidant properties (Sarıcaoglu & Turhan, 2020; Zaixiang et al., 2017).
However, its industrial application is limited due to its intense odor,
volatility, and instability under ambient conditions (Alves et al., 2014).
Consequently, the encapsulation of essential oils seems to be a solution
to facilitate their application as functional ingredients for food
packaging.
Organic hybrids based on nanolayer inorganic materials have
attracted tremendous interest due to their capacity to accommodate
various organic and inorganic fractions between layers and their

* Corresponding authors at: College of Food Science and Technology, Shanghai Ocean University, Shanghai 201306, People’s Republic of China
E-mail addresses: dlluan@shou.edu.cn (D. Luan), l-li@shou.edu.cn (L. Li).

https://doi.org/10.1016/j.fpsl.2023.101060
Received 25 August 2022; Received in revised form 3 March 2023; Accepted 10 March 2023
Available online 15 March 2023
2214-2894/© 2023 Elsevier Ltd. All rights reserved.
W. Zhu et al.
practical application as advanced functional materials (Taviot-Gueho
et al., 2018; Ye et al., 2020). These nanolayer organic-inorganic hybrid
materials exhibit extraordinary properties regarding high thermal sta­
bility, controllable and sustainable release of embedded materials, and
high biocompatibility (Rodrigues, Isoppo, Moro, & Rodembusch, 2022).
The solid-solid or solid-liquid grinding processes are usually accompa­
nied by the hybridization of organic and inorganic materials to produce
hybrid materials (Ayoub et al., 2019). Mechanical force milling, such as
ball milling, represents an ecological and economical alternative, which
opens new and unexplored routes for the preparation of advanced
functional materials (Gorrasi & Sorrentino, 2015).
The compatibility of polymer matrix with inorganic nanofillers has
been a long-studied subject. MMT has been well-used in the field of
material modification. It has been shown that the incorporation of
polymer chains into the MMT interlayer space after the addition of MMT
to the PLA/PBAT polymer system results in an intercalated morphology
(Freitas, Tonini Filho, Calvão, & Souza, 2017). Since the CEO has a
plasticizing effect on starch, which will undoubtedly improve the ther­
modynamic compatibility of the polymer with the nanofiller after ball
milling. Therefore, the TPS/PLA/PBAT system with the addition of
ball-milled nanofillers is feasible for the preparation of films.
The objective of the present study was to apply the cryogenic ball
milling technique to prepare antimicrobial materials for the develop­
ment of sustained-release packaging films. we prepared organic-
inorganic hybrid antimicrobial materials (BM-MMT-CEO) using a sim­
ple and effective cryogenic ball milling method. This is a novel method
of intercalating CEO into MMT compared with previously reported
methods. The proposed hybrid material obtained by the cryogenic ball
milling method based on the antimicrobial agent loaded on the layered
material exhibited antimicrobial, antioxidative, and excellent stability.
No other chemical reagents are involved in the preparation process,
which is an economic and ecological advantages. The thermoplastic
starch (TPS), polylactic acid (PLA), and poly (butylene adipate-co-
terephthalate) (PBAT) biodegradable materials were used as sub­
strates, and the BM-MMT-CEO obtained above were added. Then, the
degradable sustained-release antimicrobial packaging film was obtained
by blending and extrusion. The active packaging film has sustained-
release properties due to the addition of the BM-MMT-CEO. It can
continuously release antimicrobial substances for a long time, control
the reproduction and growth of microorganisms, release antioxidant
substances to prevent food oxidation, and effectively prolong the shelf
life of food.
2. Materials and methods
2.1. Materials
PLA (REVODE 721) was obtained from Hisun (Zhejiang, China),
exhibited a weight-average molecular weight (Mw) of 210 kDa and
polydispersity of 1.72. PBAT (Ecoflex F Blend C1200, BASF SE) was
supplied by Shengxiang (Shanghai, China) exhibited a weight average
molecular weight of 105 kDa and a polydispersity of 2.0. Corn starch
was supplied by Jinhui (Shandong, China), exhibited a weight average
molecular weight of 1174.5 kDa and a polydispersity of 9.06. Organic
montmorillonite (I.28E) was purchased from Nanocor (America). The
clove essential oil was purchased from Zhongxiang (Jiangxi, China).
Abalones were purchased from the local seafood market (Luchaogang
seafood market) in Shanghai, China. All the chemicals used in this study
were analytical-grade reagents. All experimental water was purified
using a Milli-Q Plus purification system (Millipore, Shanghai, China).
2.2. Synthesis of clay-based organic-inorganic hybrid antimicrobial
materials
The milling of MMT and CEO was performed using a cryogenic
planetary high-energy ball mill (MITR QM-QX-0.4 L). MMT (10.0 g)
2
Food Packaging and Shelf Life 37 (2023) 101060
dried at 105 ◦ C for 6 h and CEO (3.0 g) was added to the zirconia ball
mill containers. Zirconia balls of 1.5, 3 and 5 mm were used as the
milling media. The weight ratio of the balls to the powder was 40:1.
Next, the MMT/CEO mixture was ball-milled at 400 rpm for 1 h, which is
a stable low temperature environment of − 20 ◦ C. After grinding, clay-
based organic-inorganic hybrid antimicrobial materials were synthe­
sized. The composite obtained by manual grinding of a mixture of MMT
and CEO was denoted as MIX-MMT-CEO.
2.3. Preparation of antimicrobial active film
The film was prepared by melt-blending technology with slight
modifications (Shirai et al., 2013). TPS was prepared by mixing 77 wt %
starch with 23 wt % glycerol. The fixed weight contents of PLA, PBAT,
and TPS were 16, 64, and 20 wt %, respectively, while ADR4468, used as
a chain extender, was added at the rate of 1 % of the film substrate.
(TPS/PLA/PBAT). The BM-MMT-CEO was added at the rate of 6 % of the
film substrate. (TPS/PLA/PBAT) The mixture was then granulated using
a granulator (LSJ-20, Shanghai, China) at a heating temperature of
175 ◦ C. After extrusion and granulation, the masterbatch was cast into a
film through a single-screw extruder (LSJ-20, Shanghai, China) at
175 ◦ C and 100 rpm (Zhao et al., 2022). The final films without adding
other reagents, adding CEO, adding MIX-MMT-CEO, and adding
BM-MMT-CEO were marked as TPP, CEO-TPP, MIX-MMT-CEO-TPP, and
BM-MMT -CEO-TPP, respectively.
2.4. Characterization
2.4.1. Organic-inorganic hybrid antimicrobial materials characterization
2.4.1.1. FTIR. The prepared samples were subjected to FTIR spectros­
copy (Nicolet iS10, ThermoFisher, USA) in the transmission mode. Each
infrared spectrum was scanned 32 times with a range of 4000–400 cm− l.
2.4.1.2. XRD. The crystal structures of the samples were characterized
using a powder X-ray diffractometer (Bruker D8 ADVANCE, Billerica,
MA, USA) operated with Cu Kα radiation (λ = 1.5406 Å) at 40 mA and
40 kV. Moreover, complete PXRD patterns from the samples were ac­
quired in the range of 3–40◦ 2-theta, with a scan speed of 1 deg/minute
and a step size of 0.02◦ 2-theta (Fogelstrom, Malmstrom, Johansson, &
Hult, 2010). Jade 6 software was used for the analysis.
2.4.1.3. HRTEM. HRTEM was performed using an FEI Tecnai G2 F20
TEM. The samples were dispersed in methanol. The solution was then
ultrasonicated for 5 min. A small drop of the well-dispersed sample was
placed on an ultra-thin carbon film copper grid and then, visualized
using TEM (Guan & Zhong, 2019).
2.4.1.4. TGA. The samples were measured using a thermogravimetric
analysis instrument (TGA Q5000 V3.17 Build 265, New Castle, DE, USA)
under a nitrogen atmosphere at a heating rate of 10 ◦ C/min from 25 ◦ C
to 800 ◦ C (Cai et al., 2020).
2.4.2. Film characterization
Tensile strength (TS, MPa) and elongation-at-break (EAB, %) of
active films were measured using an XLW (PC) Intelligent Electronic
Tensile Testing Machine (Lab Think Instruments Co., Ltd., Jinan, China)
in accordance with ASTM D882–12 (ASTM, 2012).
The water vapor permeability (WVP, g/m20.24 h) of the films was
determined at 37 ◦ C and 90 % RH with a WVP tester (W-B-31E, Lab
stone, Guangdong, China) in accordance with ASTM E398–13 (2013)
(ASTM, 2013). The oxygen transmission rate (OTR, cm3/m20.24 h 0.0.1
MPa) of the film was measured using a differential pressure gas
permeation meter (PERME G2/132, Lab think, Jinan, China)
(Curtzwiler, Vorst, Palmer, & Brown, 2008).
W. Zhu et al. Food Packaging and Shelf Life 37 (2023) 101060

Fig. 1. (A)FTIR spectra of the different clays studied in all the range absorption: (a) CEO; (b) MMT; (c) BM-MMT; (d) MIX-MMT-CEO; (e) BM-MMT-CEO; (B) X-ray
diffraction pattern of the different clays studied. (C/D) TGA and DTG curves of the different samples studied. (E) Transmission Electron Microscope Image of the
different clays studied: (a/e) MMT, (b/f) BM-MMT, (c/g) MIX-MMT-CEO and (d/h) BM-MMT-CEO.

3
W. Zhu et al.
2.5. Release of active compounds into food simulants
The main component of the CEO was eugenol. Therefore, eugenol
was selected as the representative release. To evaluate the release of
CEO from TPS-PLA-PBAT films into food simulants, pure water, 3 %
acetic acid (v/v), 10 % ethanol (v/v), and 95 % ethanol (v/v) as simu­
lants of aqueous, acidic, alcoholic, and fatty foods, respectively. Film
samples (6 dm2/L) were placed in 500 mL Erlenmeyer flasks in contact
with 250 mL of each liquid simulant for immersion in the dark at 4 ◦ C.
Then 1 mL of the film sample extract was sampled at selected time in­
tervals, filtered through 0.22 µm nylon membrane filters, and analyzed
by HPLC to measure the eugenol concentration in the simulant (Oter­
o-Pazos et al., 2014).
To determine whether the release process complies with the
commonly used Fick’s second law, the release process of active com­
pounds in liquid food simulants can be fitted using the following Eq. (1):
MF,t
= ktn (1)
MF,∞
where MF, t is the concentration of the active compound released from
the food simulant at a given time t (s); MF, ∞ is the maximum released
concentration of the active compound in the simulant when equilibrium
is reached; and k is the rate constant incorporating the characteristics of
the simulant. α is the diffusion index, which provides information on the
kinetics of the release process. If the value of n is higher than 0.5, the
release process is an abnormal release, which does not conform to Fick’s
diffusion law; When the value of n is lower than 0.5, the release process
aligns with Fick’s diffusion law. Similarly, the release rate of eugenol
from the film into the food simulant was studied according to Eq. (2),
based on Fick’s second law.
[ ]
MF,t ∑∞ 8 (2n + 1)2 π
= 1− exp − Dt (2)
MF,∞ n=0
(2n + 1)2 π2 L2p
where t (s) is time, D (m2. s− 1) is the diffusion coefficient of the active
film, and Lp (m) is the thickness of the TPS-PLA-PBAT film. The initial
diffusion time for migration can be simplified according to Eq. (3). The
coefficient D is calculated according to the slope MF, t / MF, ∞ as a
function of t1/2.
MF,t 2 Dt 1
= ( )2 (3)
MF,∞ Lp π
The eugenol concentrations were quantified using an Agilent HPLC
1260 (Agilent 1260, Agilent, Santa Clara, CA, USA) equipped with a
diode array detector (G4212B) and an Agilent ZORBAX SB-C18 analyt­
ical column (4.6 mm × 250 mm, 5 µm). The calibration curve of the
eugenol standard was prepared using acetonitrile as the solvent, and the
concentration range of the standard was 5–250 µg/mL. The mobile
phase consisted of a mixture of Milli-Q water and acetonitrile (3:2, v/v)
at a 1 mL/min flow rate. The column temperature was 30 ◦ C, and the
analysis time was 10 min (Yang et al., 2019).
2.6. Storage test of abalone
The abalone was placed in sterile normal saline prepared in the
laboratory at approximately 4 ◦ C and pre-cooled for 1 h. The shell and
internal organs were removed with a knife and rinsed with sterile
normal saline at 4 ◦ C. The abalone meat was randomly divided into four
groups and sealed in packaging bags with four different films. After the
abalones were packed, they were stored in the refrigerator at 4 ± 1 ◦ C,
and the corresponding number of samples were taken at different pe­
riods (0, 3, 6, 9, 12, 15, 18d) to complete the test of each freshness index.
2.6.1. pH value
The pH of abalone meat was determined according to Huang et al.
4
Food Packaging and Shelf Life 37 (2023) 101060
(Huang, Wang et al., 2020) Briefly, 5 g of each sample was blended with
45 mL of distilled water in a homogenizer (FJ200-SH, Shanghai, China)
for 1 min, and the mixture was filtered through a qualitative filter paper.
Then, the pH of the filtrate was measured using a pH meter (PHSJ-4 F,
Shanghai, China) at 20 ◦ C.
2.6.2. Total volatile basic nitrogen (TVB-N)
The TVB-N of abalone meat was measured according to the method
described by Dai et al. using a Kjeltec System 1026 (Foss Tecator,
Sweden) (Dai, Cheng, Sun, Zhu, & Pu, 2016). 10 g of chopped fresh
abalone samples and 2 g of magnesium oxide distilled. In the presence of
an indicator (methyl red mixed with bromocresol green), the distillate
was collected in a solution of 10 mL 20 % boric acid and then titrated
with 0.1 N hydrochloric acid. The TVB-N value was expressed as the
number of milligrams of nitrogen per 100 g of fresh abalone sample (mg
N/100 g).
2.6.3. Microbiological analysis
Microbiological analysis followed the method described by Sirinet
et al. (Chaijan, Panpipat, Panya, Cheong, & Chaijan, 2020), with minor
modifications. The minced abalone meat (5 g) was transferred asepti­
cally to a sterile Stomacher bag containing 45 mL of sterile normal saline
(0.85 %) and homogenized for 1 min using a Stomacher blender (Bag
Mixer® 400, Inter-science, France). Normal saline was diluted to an
appropriate concentration and poured onto total count agar plates in a
continuous dilution. The total viable count (TVC) was determined using
plate count agar after incubation at 30 ◦ C for 72 h. All counts were
expressed as logarithms of the number of colony-forming units per gram
(log CFU/g).
2.6.4. Determination of thiobarbituric acid reactive substance (TBARS)
The method for determining the active substance of thiobarbituric
acid was based on Letricia et al. (Barbosa-Pereira et al., 2013), with
minor modifications. The abalone meat (5 g) was mixed with 25 mL of
7.5 % trichloroacetic acid (containing 0.1 % ethylene diamine tetra­
acetic acid solution), homogenized at 12000 r/min for 3 min using an
Ultra-Turrax. Ten milliliters of the filtrate were mixed with 10 mL of
thiobarbituric acid solution (0.02 mol/L), and heated in a water bath at
90 ◦ C for 40 min. After cooling to room temperature, the extract was
centrifuged at 8000g for 5 min. Chloroform (5 mL) was then added to
the extract. After stratification, the supernatant extract was used for
analysis, and the absorbance was measured at 532 nm and 600 nm using
an ultraviolet-visible spectrophotometer (Hitachi Ltd., Tokyo, Japan).
2.7. Statistical analysis
All tests were performed in triplicate, and the data were statistically
analyzed using SPSS Statistics 23. One-way analysis of variance
(ANOVA) and least significant difference (LSD) procedures were used
for sample comparison. Differences were considered statistically sig­
nificant at p < 0.05.
3. Results and discussion
3.1. Preparation and characterization of clay-based formulations
Fig. 1 A shows the FTIR data used to verify the intercalation of the
CEO into the MMT. Fig. 1A(d) and (e) show the FTIR spectra of MIX-
MMT-CEO and the FTIR spectra of BM-MMT-CEO, respectively. The
absorption peak at approximately 3618 cm− 1 arises from the stretching
vibration of OH of the hydroxide layers and co-intercalated water
molecules, which is a characteristic feature of MMT. The two samples
also exhibit absorption peaks at 2922 cm− 1 and 2851 cm− 1, whereas the
absorption peak intensity of BM-MMT-CEO is higher than that of other
groups, probably due to the intercalation of CEO into MMT, resulting in
the enhanced absorption peak of methylene. MIX-MMT-CEO shows an
W. Zhu et al. Food Packaging and Shelf Life 37 (2023) 101060

Fig. 2. (X)State pictures of montmorillonite under different experimental conditions. (Y) SEM images and photographs of films. Film A: control; Film B: film with
added clove essential oil; Film C: film with manual grinding organic montmorillonite and clove essential oil; Film D: film with cryogenic ball milled organic-inorganic
hybrid antimicrobial materials.

absorption peak at approximately 1512 cm− 1 assigned to the stretching
vibrations of the C–– C bonds. This phenomenon may be due to the
adsorption of a small amount CEO on the MMT surface. In addition, the
peaks at 1364 cm− 1 and 1269 cm− 1/1238 cm− 1 correspond to the
bending vibration of the phenolic hydroxyl group and the C-O stretching
vibration of the aromatic ring, respectively. The above absorption peaks
were also found in the infrared absorption spectrum of BM-MMT-CEO,
but the intensity of the absorption peaks was evidently more intense
than that in the infrared absorption spectrum of MIX-MMT-CEO.
Compared with MIX-MMT-CEO, considerable amounts of carbon-
hydrogen bonds, carbon-carbon double bonds, carbon-oxygen bonds,
and hydroxyl groups were found in BM-MMT-CEO. It can be seen from
the FTIR spectra that the addition of CEO to MMT led to a significant
increase in the intensity of CH stretching peak at 2922 cm− 1, demon­
strating an increment in the content of ester groups arising from CEO
compounds (Rutakhli, Sabahi, & Riazi, 2019). All CEO peaks appeared
in the spectrum of CEO-intercalated MMT at the same wave number,
implying no alteration or interaction between MMT and CEO. In
conclusion, the FTIR results indicate the intercalation of the CEO into
MMT.
We further studied whether CEO successfully intercalated MMT
using powder X-ray diffraction (XRD). As shown in Fig. 1B, the struc­
tural characteristics of MMT-CEO prepared by the cryogenic ball milling
approach were compared to those synthesized by the manual grinding
method. The X-ray diffraction patterns of MMT (Fig. 1B(a)) show that
MMT exhibited a strong reflection at 2θ = 3.43◦ corresponding to a basal

5
W. Zhu et al.
spacing of 25.93 Å. A similar result has been reported by Tomohiko et al.
(Okada, Watanabea, & Ogawa, 2004). The interlayer spacing of the
BM-MMT (D-value=26.43 Å) was slightly wider than that of the MMT
from Fig. 1B(b), representing an increase of approximately 0.5 Å, and
the peak intensity was reduced, consistent with results reported by
Rabah where montmorillonite formed an amorphous structure through
ball milling, and the crystallinity decreased (Hamzaoui, Muslim, Gues­
sasma, Bennabi, & Guillin, 2015). The PXRD pattern of MIX-MMT-CEO
synthesized by the manual grinding method is similar to that of MMT,
and the calculated interlayer spacing considering the d001 base reflec­
tion was 26.04 Å. For the BM-MMT-CEO prepared via the cryogenic ball
milling approach, a significant shift in the basal spacing and full width at
half maxima was observed, as shown in Fig. 1B(d). The corresponding
interlayer spacings calculated for the (001) basal reflections were
36.64 Å. The shift in the basal spacing suggests successful intercalation
of the CEO within the interlayer space. The 001 basal reflection of
BM-MMT-CEO was increased by adding CEO, as demonstrated by the
decrease in the 2θ angles of the CEO-containing clays (Fig. 1B). As a
result, the interlayer spacing of BM-MMT-CEO calculated by the Bragg
equation increased, indicating that the increase in basal spacing resulted
from the intercalation of CEO in the interlayer spaces of the clays,
confirming that the CEO was encapsulated in the clays.
To observe the changes in the overall structural disorder of the MMT
mineral layer, TEM analysis was performed on some samples before and
after cryogenic ball milling. As shown in Fig. 1E, MMT exhibited the
typical stacked lamellar structure (Fig. 1E a/e). The separation and
exfoliation of the MMT layer were observed (Fig. 1E b/f) when MMT was
ball-milled at a low temperature. The TEM images of MIX-MMT-CEO
(Fig. 1E c/g) show that the MMT structure is not exfoliated or
destroyed; instead, unordered aggregates are formed. However, the
layer separated and exfoliated of the MMT was observed in the TEM
images of the organic-inorganic hybrid antimicrobial materials (Fig. 1E
d/h) prepared from CEO and MMT under cryogenic ball milling
(Ramadan, Esawi, & Gawad, 2010). It could be because the cryogenic
ball milling caused the CEO to be embedded between the MMT layers.
Furthermore, the interlayer distances observed along the 001 plane di­
rections about the four samples were 2.59, 2.64, 2.60, and 3.67 nm,
respectively. This result corresponds to the (001) basal reflection values
obtained from the XRD measurements, and it was attributed to the fact
that cryogenic ball milling promoted the successful intercalation of CEO
into the interlayer structure of MMT.
The TGA and DTG thermograms of CEO, MMT, BM-MMT, MIX-MMT-
CEO, and BM-MMT-CEO are shown in Fig. 1C and D. The thermal
decomposition of clay is carried out in four stages: the first stage is from
room temperature to approximately 100 ◦ C, which corresponds to the
loss of physically adsorbed water molecules; in the second stage, the loss
of interlayer water in the temperature range 100–250 ◦ C; in the third
stage, 250–700 ◦ C, simultaneous loss of water from both MMT and the
minor components (opal CT); and in the fourth stage, 350–700 ◦ C,
corresponding to the dihydroxylation of the OH group of the clay
structure (Dellisanti et al., 2018).
First, we observed that the CEO begins to volatilize at approximately
60 ◦ C, and all volatilization is completed at approximately 200 ◦ C. As
shown in Fig. 1C(e), this may be due to weight loss caused by the volatile
components in CEO, such as eugenol, eugenol acetate, and β-car­
yophyllene. In addition, the DTA data (Fig. 1D) showed that the
decomposition of clay occurred at elevated temperatures. However, the
decomposition temperature of the CEO intercalated into the MMT layer
structure by cryogenic ball milling was higher than that of the CEO
adsorbed to the surface of MMT by manual grinding. The intense
decomposition temperatures are 182 ◦ C (CEO), 334 ◦ C (MMT), 334 ◦ C
(BM-MMT), 262 ◦ C (MIX-MMT-CEO), and 327 ◦ C (BM-MMT-CEO)
(Fig. 1D), which shows that the CEO is embedded in the MMT because of
strong host-guest interactions in the BM-MMT-CEO, including hydrogen
bonding and electrostatic attraction between the montmorillonite layer
and CEO. This shows the ability of CEOs to improve their thermal
6
Food Packaging and Shelf Life 37 (2023) 101060
Table 1
Barrier and mechanical properties of films.
Sample TS MPa EAB % OTR cm3/m20.24 h WVP (g/
0.0.1 MPa m20.24 h)
A 7.93 305.63 847.57 ± 0.77a 683.36
± 0.40a ± 19.32a ± 10.56a
B 8.27 307.53 808.24 ± 5.49 ab
693.43
± 0.10a ± 79.88a ± 18.04a
C 8.62 307.33 764.26 ± 17.28b 669.40
± 0.66a ± 50.25a ± 19.03a
D 8.69 304.80 697.83 ± 6.75c 620.83
± 0.67a ± 41.15a ± 34.65b
A: TPP; B: CEO/TPP; C: MIX-MMT-CEO/TPP; D: BM-MMT-CEO/TPP. Significant
difference (p < 0.05) among the values within the same column is indicated by
different superscripts (a–c).
stability. In addition, as shown in Fig. 1C, approximately 15 % of CEO in
the BM-MMT-CEO obtained by cryogenic ball milling are embedded in
the interlayer structure of MMT. Therefore, the novel high-efficiency
cryogenic ball milling technology enables intercalated CEO to have
higher thermal stability.
We compared the states of untreated MMT, MIX-MMT-CEO, ball-
milled clove essential oil-montmorillonite mixture at room temperature
and BM-MMT-CEO (Fig. 2X), and found that the MIX-MMT-CEO and
ambient temperature ball-milled mixture were agglomerated together,
difficult to disperse, and mostly stuck to the container walls, which were
no longer suitable for the preparation of active films, while the BM-
MMT-CEO obtained by cryogenic ball milling was in the powder form
with uniform particles. Cryogenic ball milling allows more essential oil
to enter the interlayer space, thereby increasing the loading rate while
maintaining the particle shape. This indicates that low temperature
provides a good intercalation environment for clove essential oil.
Therefore, cryogenic ball milling can be considered a simple and effec­
tive method for preparing organic-inorganic hybrid antimicrobial
materials.
3.2. Characterization of films
The mechanical and optical properties of the TPS/PLA/PBAT (TPP)
films are listed in Table 1. The TS and EAB of Film A were 7.93 MPa and
305.63 %, respectively. By adding BM-MMT-CEO, the TS of the film
gradually increased from 7.93 MPa to 8.63 MPa, and the EAB of the film
showed a trend of first rising and then decreasing. The melt rheology
affects the mechanical properties of the film, the formation of copolymer
monomers in the polymer, and the improved homogeneity of the melt
due to the homogeneous dispersion of the montmorillonite, resulting in
improved mechanical properties of the film (Rana, Cho, Woo, Lee, &
Choe, 1999; Rana et al., 2000). In addition, the presence of active
compounds and MMT enhances the mobility of the PLA-PBAT polymer
chain and reduces intermolecular forces, improving the flexibility of the
PLA-PBAT film.
The OTR and WVP values for each film are listed in Table 1. It can be
observed that the oxygen permeability of TPP-based films gradually
decreases from 847.57 cm3/m20.24 h 0.0.1 MPa to 697.83 cm3/
m20.24 h 0.0.1 MPa with the addition of active compounds and MMT.
This phenomenon can be explained by the increases in chain mobility in
the TPP matrix caused by the plasticization effect of the CEO. The active
ingredient in clove essential oil contains a large number of hydroxyl
groups, which can form hydrogen bonds with thermoplastic starch after
melt blending to obtain a better plasticization effect, and after blending
with PLA and PBAT to cast the film, resulting in an increase in film
tensile strength (Surendren, Mohanty, Liu, & Misra, 2022). The film
oxygen transmission rate will then decrease when the thermoplastic
starch forms a tighter structure with PLA and PBAT, and the presence of
the CEO clogged the intermolecular voids of the film (Huang, Han et al.,
2020). In the films (Film C and D) added with MMT, porous structure of
W. Zhu et al. Food Packaging and Shelf Life 37 (2023) 101060

Fig. 3. Release of eugenol from active TPS-PLA-PBAT films into food simulant: (a) water; (b) 3 % acetic acid; (c) 10 % ethanol; (d) 95 % ethanol.

MMT (Fig. 2Y) leads to the growth of oxygen transmission paths; thus,
Table 2
its oxygen transmission rate decreases. The tortuous path has a greater
Diffusivity and diffusivity exponent of eugenol in films contact to different
effect on the oxygen permeability of the film than the multi-phase mo­
simulants.
lecular gap, and the oxygen permeability of Film D is lower than that of
Film B with the addition of essential oils. Similar results were obtained Sample Simulant n k R2 D (m2.s¡1)

for the water vapor transmission rates of the films. CEO-TPP water 0.12592 0.49193 0.90772 7.41 × 10− 14
3 % acetic 0.12073 0.49507 0.94692 1.7 × 10− 13
acid
13
10 % 0.10738 0.54683 0.94164 1.9 × 10−
3.3. Release of active compound into food simulants ethanol
12
95 % 0.00873 0.94522 0.99986 1.4 × 10−
Fig. 3 shows the release behavior of eugenol from TPP films using ethanol
different types of liquid food simulants. The eugenol concentration in MIX-MMT- water 0.13722 0.46553 0.85871 8.7 × 10− 14
CEO-TPP 3 % acetic 0.17566 0.3644 0.98543 7.25 × 10− 14
the four liquid food simulants increased sharply and slowly reached
acid
equilibrium. In general, the release values (V) of active compounds 10 % 0.14354 0.43862 0.97245 9.47 × 10− 14

obtained at similar temperatures and times followed the order: V95% ethanol
13
ethanol > V3% acetic acid > V10% ethanol > Vwater. However, for TPP films, 95 % 0.07481 0.67919 0.84281 1.84 × 10−
ethanol
V95% ethanol > V10% ethanol > V3% acetic acid > Vwater. These results may be
BM-MMT- water 0.16976 0.38775 0.94111 6.3 × 10− 14
attributed to the nonpolar nature of eugenol. Furthermore, the release of CEO-TPP 3 % acetic 0.10862 0.54122 0.94996 1.57 × 10− 13
eugenol may be related to the degree of dissolution of TPP substrates and acid
organic montmorillonite in the different food simulants. Thus, changes 10 % 0.12727 0.49304 0.91602 1.11 × 10− 13

in the food matrix can significantly affect the release of active com­ ethanol
12
95 % 0.02852 0.85715 0.99587 1.01 × 10−
pounds from the films. However, based on the data released in 95 %
ethanol
ethanol, a certain amount of eugenol was lost during the film prepara­
tion process. In addition, as a controlled-release carrier, montmorillonite
has a large specific surface area and good selective adsorption, which release behavior of eugenol from packaging substrates (Hu et al., 2017).
reduces the loss of the active ingredients. The determination and diffusion coefficients of the model are shown in
In this study, the Peppas model (Eq. (1)) was used to evaluate the Table 2. All n-values were < 0.5, indicating that the eugenol release

7
W. Zhu et al. Food Packaging and Shelf Life 37 (2023) 101060

Fig. 4. (A/B/C/D) Changes of biochemical indexes and (E) Physical map of fresh abalone stored at 4 ◦ C for 18 days. (A: control; B: CEO-TPP; C: MIX-MMT-CEO-TPP;
D: BM-MMT-CEO-TPP) A significant difference (p < 0.05) among the values within the same column is indicated by different superscripts (a–d).

process was consistent with Fick diffusion (Chen et al., 2021). The dif­
ference in the D values clearly shows the release behavior of eugenol in
the four food simulants. It can be observed in Figure 6 that both the
content and rate of eugenol released from Film D are greater than those
released from Film B and C. These results suggest that eugenol
pre-embedded in MMT tends to yield low diffusion coefficients. The
main reason for this is that the adsorption properties of MMT hinder the
contact between eugenol and food simulants. The active substances
adsorbed by MMT have different degrees of sustainedrelease depending
on the polarity of the medium (Zheng et al., 2022). Eugenol is the

8
W. Zhu et al.
primary substance of the CEO, and the release behavior of eugenol can
characterize the release process of the CEO from the film.
3.4. Preservation and characterization of abalone
3.4.1. pH value
It is generally believed that changes in the freshness of aquatic
products are related to changes in pH (Silva-Pereira, Teixeira,
Pereira-Junior, & Stefani, 2015). As shown in Fig. 4(A), the pH of
abalone first decreased and then increased at a chilling temperature of
4 ◦ C. The pH of fresh abalone muscle was approximately 6.56. The pH
value of the abalone muscle in the control, CEO-TPP, and
MIX-MMT-CEO-TPP groups reached the lowest value on days 9 and 12,
respectively, while the pH value of the abalone muscle in the
BM-MMT-CEO-TPP group reached the minimum value on day 15, and it
was at a low level during the pH value rising stage. This pH value hys­
teresis phenomenon can be considered the slower spoilage rate of aba­
lones in the experimental group than in the other groups.
3.4.2. Microbiological analysis
Changes in the microbial communities are shown in Fig. 4(B). The
initial bacterial count in abalone muscle was 2.51 log CFU/g, consistent
with previously reported results (Hao et al., 2017). As recommended by
the International Committee on Microbiological Specifications for Foods
(ICMSF), the permissible limit for the total viable count (TVC) in fresh
meat is 7 log CFU/g. Initially, the TVC of all abalone samples increased
with the storage time. However, the TVC of abalone in control,
CEO-TPP, and MIX-MMT-CEO-TPP groups exceeded the limit on day 15,
whereas that of the BM-MMT-CEO-TPP group outperformed the limit on
day 18. It is indicating that the antimicrobial effect of the
BM-MMT-CEO-TPP film was better than that of the other three groups of
films.
3.4.3. TVB-N analysis
TVB-N refers to alkaline nitrogen-containing volatile substances such
as ammonia and amines produced by the decomposition of protein in
animal food due to the action of endogenous enzymes or bacteria in the
muscle and is widely used as an indicator for evaluating the freshness of
aquatic products. The TVB-N of all samples showed a gradually
increasing trend during abalone preservation (Fig. 4(C)), and the value
increased significantly after the 9th day (p < 0.05). The China hygienic
standard limit for TVBN in fresh shellfish aquatic products was set at
15 mg N/100 g. In this study, the TVB-N values of abalone in the control
group, CEO-TPP, and MIX-MMT-CEO-TPP groups exceeded their pre­
scribed freshness indicators on day 15, whereas the fresh abalone with
the film added organic-inorganic hybrid antimicrobial materials reached
16.27 mg N/100 g on day 18. This trend is consistent with that observed
in the TVC of chilled abalones. Therefore, we believe that the active
substances released by the film had inhibitory effects on endogenous
enzymes and microorganisms.
3.4.4. Determination of TBARS
Malondialdehyde (MDA) is the final lipid oxidation product as
determined by the TBARS value (Byun, Bae, Cooksey, & Whiteside,
2010; Yang et al., 2019). From Fig. 4(D), it can be observed that the
TBARS value of fresh abalone was 0.37 ± 0.01 mg MDA/kg, and there
was no significant difference in TBARS value between the control and
treatment groups during the early storage period. The TBARS value of
the control group was significantly higher than that of the treatment
group over the storage period (p < 0.05), but the increased rate in the
TBARS value of the treatment group was lower. This result is consistent
with the release of active components from the CEO into the abalone
during storage. Because the added organic-inorganic hybrid antimicro­
bial materials have thermal stability and sustained release properties,
and the main components of the loaded CEO, such as phenols, have
antioxidant properties, the films of the BM-MMT-CEO-TPP group have
9
Food Packaging and Shelf Life 37 (2023) 101060
excellent antioxidant properties. Therefore, the TBARS value was always
low throughout the storage process.
As observed in Fig. 4(E), the abalone samples in groups A, B, and C
spoiled at 15 days, and greenish skirts were observed, while the abalone
in group D showed spoilage at 18 days. From a macroscopic point of
view, we can also assume that active films with the BM-MMT-CEO are
more effective in preserving fresh abalone.
4. Conclusions
In this study, we introduced the preparation of clove essential oil-
montmorillonite organic-inorganic hybrid antimicrobial materials by
the cryogenic ball milling technique. X-ray powder diffraction and
transmission electron microscopy images showed an increase in the
interlayer spacing of MMT, indicating the successful CEO intercalation.
Thermogravimetric analysis showed that the prepared organic-
inorganic hybrid antimicrobial materials were thermally stable. Func­
tionalized active packaging films were prepared by blending organic-
inorganic hybrid antimicrobial materials with TPS/PLA/PBAT. The
active compound release experiment showed that the prepared active
packaging film had the sustained-release effect. An abalone preservation
experiment successfully verified this conclusion. Overall, the efficient
and straightforward cryogenic ball milling technology provides a novel
idea for the research and development of film materials.
CRediT authorship contribution statement
Weizhong Zhu: Conceptualization, Methodology, Investigation,
Writing - original draft. Jiali Chen: Conceptualization, Methodology,
Investigation. Qingfeng Dong: Conceptualization, Writing - review &
editing. Donglei Luan: Conceptualization, Writing - review & editing.
Ningping Tao: Conceptualization, Writing -review & editing. Shanggui
Deng: Conceptualization, Writing - review & editing. Li Wang:
Conceptualization, Methodology, Investigation, Writing - review &
editing. Yi Hao: Conceptualization, Methodology, Investigation. Li Li:
Conceptualization, Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The data that has been used is confidential.
Acknowledgments
This work was supported by the National Key R&D Program of China
(grant numbers 2020YFD0900905).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.fpsl.2023.101060.
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