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Polymer Testing 76 (2019) 73–81

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Effect of high pressure treatment on properties and nano–Ag migration of T


PLA-based food packaging film
Chunli Fana, Rui Cuia, Wangwei Lua, Haiyan Chena, Minglong Yuanb, Yuyue Qina,*
a
Institute of Yunnan Food Safety, Kunming University of Science and Technology, Kunming, 650550, China
b
Engineering Research Center of Biopolymer Functional Materials of Yunnan, Yunnan Minzu University, Kunming, 650500, China

A R T I C LE I N FO A B S T R A C T

Keywords: The effects of nano-Ag content, high pressure treatment, and migration time on nano-Ag migration and prop-
Polylactide erties of polylactide (PLA)/nano-Ag composite films were investigated. The PLA films incorporated with 1 wt%,
Nano-Ag 5 wt%, 10 wt%, 15 wt%, and 20 wt% nano-Ag were treated by 100, 200, 300, and 400 MPa high pressure for 10,
High pressure 20, and 30 min, respectively, and then soaked in isooctane food simulant at 40 °C for 49 days. The migration of
Migration
nano-Ag in the PLA nanocomposite films increased by the addition of nano-Ag, the pressure of high pressure
Nanocomposite film
treatment, and migration time. Thermal and mechanical properties showed that high pressure and migration
time would make the films rougher and increase the crystallization temperature of the PLA nanocomposite films.
Moreover, the addition of nano-Ag could improve the barrier properties of the PLA nanocomposite films.
However, the longer the migration time, the worse the barrier property. The results indicated that the migration
amount of nano-Ag and performance of the PLA/nano-Ag composite films were greatly affected by the migration
time.

1. Introduction trachomatis. Mechanical and barrier properties of the composite films


added nano-Ag have also been greatly improved [12,13]. At the same
In recent years, considerable research efforts have been devoted to time, however, the biosafety of nanoparticles has also attracted people's
biodegradable food packaging materials, with increasing attention to attention and research. Theoretical and experimental evidences have
issues such as shortage of petroleum resources, environmental protec- showed that the nano-components in composite packaging materials
tion and food safety [1–3]. Thence, polylactide (PLA) has become the have a tendency to migrate to food [14,15], which may pose safety
most active biodegradable biopolymer material in the world due to its hazards. At present, there have been few studies on the detection and
degradability, excellent biocompatibility and good transparency [4–6]. migration of harmful substances in nano-Ag food packaging at home
However, in actual production, the defects such as large brittleness, and abroad.
poor heat resistance and low barrier properties of PLA still greatly limit High pressure refers to a technology that pressurizes liquid or gas to
its application [7,8]. Therefore, a large number of PLA modification more than 100 Mpa. As the most promising high pressure treatment in
studies have been carried out in order to improve its various perfor- food processing and preservation technology, more and more attention
mance. has been paid [16,17], and it has been widely used in the processing
According to the existing reports, blending of PLA and metal na- and preservation of meat products, dairy products, fruits and vegetable
noparticles in films could impart its properties such as antibacterial products, aquatic products [18,19]. At present, the research hotspots of
property, mechanical strength, barrier properties, and thermodynamic high pressure technology mainly focus on the high-pressure steriliza-
properties [9]. At present, a variety of polymer-based nanocomposite tion effect of food microbes and food quality changes [20,21], but it is
materials have been applied in food packaging for fruits and vegetables, rarely used alone as a processing technology for food packaging ma-
meat products, and beverages [10,11]. Among all the metal nano- terials. In fact, a small number of studies have shown that high pressure
particles, the antibacterial property of nano-Ag is remarkable, and it has technology can be used to improve the internal structures, mechanical
strong inhibitory and killing effects on dozens of pathogenic micro- properties and barrier properties of packaging films [22,23], but studies
organisms such as Escherichia coli, Neisseria gonorrhoeae, and Chlamydia on the effects of component migration in film materials treated by high

*
Corresponding author.
E-mail addresses: fanchunli1995@163.com (C. Fan), cr1289158140@163.com (R. Cui), assmn89@163.com (W. Lu), seacome@163.com (H. Chen),
yml@vip.163.com (M. Yuan), rabbqy@163.com (Y. Qin).

https://doi.org/10.1016/j.polymertesting.2019.03.005
Received 24 January 2019; Received in revised form 27 February 2019; Accepted 2 March 2019
Available online 14 March 2019
0142-9418/ © 2019 Elsevier Ltd. All rights reserved.
C. Fan, et al. Polymer Testing 76 (2019) 73–81

pressure are rare. analyzing five Ag standard solutions (0.1, 0.2, 0.3, 0.4, 0.5 μg/mL) di-
The safety of metal nanocomposite film materials for food packa- luted with 5% (V/V) HNO3 directly and by novAA400P atomic ab-
ging has been continuously concerned. Whether the metal nano- sorption spectrometry (Analytik Jena AG, Germany). The actual em-
particles in the composite films will migrate into the food, and whether bedding rate of nano-Ag in all composite films was calculated according
the amount of migration is a safe limit have been crucial points [24,25]. to the following formula (1):
In this study, PLA/nano-Ag composite films treated by high pressure 5000Q
were prepared and immersed in isooctane for 49 days. The food si- K=
0.1 × 1000 (1)
mulation fluid was used to simulate the real oily food packaging en-
vironment, and the migration amount of nano-Ag and the performance Where K is the actual embedding rate (%) of nano-Ag in composite
of composite film in different stages of soaking were tested. This will films, Q is the nano-Ag actual content diluted 50,000 times in the 0.1 g
facilitate the application of polylactide nanocomposites to food composite films.
packaging.
2.3.2. Determination of migration content of nano-Ag in the films
2. Materials and methods Isooctane was used as a food simulant to study the migration of
nano-Ag in composite films for fat food packaging. The films and the
2.1. Materials simulated liquid were in double-sided contact according to the stan-
dards of the European Food Safety Authority. Therefore, the films were
Polylactide (PLA) was a commercial material obtained from Unic cut into 4 cm × 4 cm and placed in glass bottles containing 25 mL of
Technology LTD. (Su Zhou, China). The molecular weight of PLA was isooctane, and the culture temperature was kept at 40 °C for 49 days
determined to be 4032 D by viscosity method, and chloroform was used [28,29]. The films were taken out every 7 days and the content of the
as a solvent. Nano-Ag was purchased from Nanjing Xianfeng Nano nano-Ag eluted in the simulated liquid was measured by novAA400P
Material Technology Co., Ltd. (Nanjing, China), with its diameter Atomic Absorption Spectrometry (AAS, Analytik Jena AG, Germany).
60–80 nm and purity of 99.9 wt%. Acetyl tributyl citrate (ATBC) was The amount of migration was expressed as mg/kg. Each group of ex-
used as a plasticizer. Dichloromethane and isooctane were used as periment was repeated three times and a blank control was performed.
solvents and food simulant respectively. All of which were supplied by The migration amount of nano-Ag in the films was calculated according
KrLab Scientific Co., Ltd. (Dongguan, China). In this experiment, the to the following formula (2):
nitric acid used was excellent grade and the other reagents were of C × V × 10−3
analytical grade. M=
0.1 × K × 10−3 (2)

2.2. Preparation of composite films and high pressure treatment Where M is migration amount (mg/kg) of nano-Ag in composite films, C
is the concentration (mg/ml) measured by the AAS, V is a fixed value of
2 g of pre-dried PLA and 0.2 g of ATBC were accurately weighed and 10 (ml), 0.1 (g) is the quality of the composite films weighed, K is the
dissolved in 50 ml of dichloromethane to form PLA/ATBC plasticized actual embedding rate (%) of nano-Ag in composite films.
modified system, and then 1 wt%, 5 wt%, 10 wt%, 15 wt%, and 20 wt%
nano-Ag was added to the system to form film-forming solution. The 2.4. Performance measurement
mixtures were stirred for 8 h with a magnetic stirrer, ultrasonically
degassed for 30 min, poured into polytetrafluoroethylene plates, and In order to understand the changes in the performance of the
finally subjected to a solvent evaporation method to obtain the PLA- composite films with nano-Ag migration, and the following indicators
based composite films with different nano-Ag content (1 wt%, 5 wt%, were measured by films immersed in isooctane simulating solution for
10 wt%, 15 wt%, or 20 wt% nano-Ag). 0, 14, 28, and 49 days at 40 °C.
Water was used as the pressure transfer mediator during high
pressure processing. The PLA nanocomposite films prepared above 2.4.1. Microscopic structure
were subjected to high pressure treatment at 100, 200, 300, or 400 MPa A NOVA Nano 450 field emission scanning electron microscope
for 10, 20, and 30 min (Freshertech-HPP 600 MPa, Baotou Kefa High (SEM, FEI company, American) was used to characterize the brittle
Pressure Technology Co., Ltd., Nei Menggu, China). The treated films fracture of the composite films. The composite films were placed in
were cleaned with ultrapure water and then placed in a desiccator at a liquid nitrogen to break them brittlely, and all the cross sections were
storage temperature of 23 ± 2 °C and a relative humidity of 50 ± 5%. subjected to gold plating treatment for 200 s in high vacuum environ-
Different PLA-based composite films were obtained. ment, and the thicknesses were about 20 nm. Morphology images of
brittle section of films were taken at a working voltage of 500 kV, and
2.3. Migration test the magnification was 10,000 times [30,31].

2.3.1. Determination of the embedding rate of nano-Ag in composite films 2.4.2. Thermal performance
Each composite film weighing 0.1 g and 8 mL of concentrated nitric The thermal properties of the composite films (glass transition
acid were added into open polytetrafluoroethylene (TFM) microwave temperature-Tg, crystallization temperature-Tc, melting temperature-
digestion tanks, and put in the EHD-24 electric heating acid-driven Tm, and crystallinity-Xc) were measured by differential scanning ca-
apparatus (Beijing Eastern Airlines Keyi Instrument Co., Ltd., Beijing, lorimeter (DSC 214, Netzsch, Selb, Germany). 10 mg of the composite
China). After 30 min of pre-dissolution at 120 °C, the digestion tanks film were accurately weighed. Then, sealed in an aluminum crucible
were removed and the lids were tightened. Then, put the tanks into the and heated in a nitrogen atmosphere [32,33]. The second heating
microwave digestion device and set up a three-step heating program. curves were taken as the research object, and the Xc of the samples were
First, the microwave heating temperature was raised to 120 °C in 8 min calculated by the following formula (3):
for 5 min, then, the temperature was raised to 150 °C in 5 min for 5 min,
ΔHm − ΔHc
finally, the temperature was raised to 180 °C in 10 min for 20 min Xc = × 100
ΔHm0 × w (3)
[26,27]. The solutions in the digestion tanks were evaporated to 1 ml
remaining at 150 °C by acid-driven apparatus, and diluted to 50,000 Where Xc is the crystallinity (%) of the composite films, ΔHm is the
times with ultrapure water to be tested. For the determination of nano- melting enthalpy (J/g) of the samples, ΔHc is the cold crystallization
Ag in films, linearity and correlation coefficients were obtained by enthalpy (J/g) of the composite films, ΔH0m is the melting enthalpy

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C. Fan, et al. Polymer Testing 76 (2019) 73–81

(93.7 J/g) when the pure PLA is completely crystallized, w is the mass in the films and pressure conditions, the migration of nano-Ag in all
fraction of PLA in the composite films. films increased with the migration time. The film containing 20% nano-
Ag and treated by 200 Mpa for 30 min had the largest migration volume
2.4.3. Mechanical property at 49 days, which was as high as 28 mg/kg at the end of the test. The
The mechanical properties (tensile strength - TS, modulus of elas- migration rate was also growing during the 49-day storage period. It
ticity - EM, and elongation at break - ε) of the composite films were was slower in the early stage of storage, but after 35 days, the migration
measured by a texture analyzer (Stable Micro System company, rate began to increase sharply until the end of the storage period. The
England). The samples were cut into rectangles of 15 mm × 100 mm possible reason was that under the heterogeneous degradation of
and the thickness was measured by spiral micrometer. Firstly, the dis- composites, the nano-Ag which was not embedded in the polylactide
tances between the two clamps were measured. Then, both ends of the matrix and the nano-Ag exposed on the cut surface of the composite
films were clamped. Lastly, the moving speed was set to 50 mm/min films migrated into the simulated liquid first in the early stage of sto-
[34,35]. rage [38,39]. Then, the homogeneous degradation of the films began to
occur under the action of the simulated liquid, and the nano-Ag em-
2.4.4. Water vapor permeability (WVP) bedded inside the composites began to migrate out [38,39]. Finally, at
The barrier properties of the composite films were characterized by 40 °C for long-term storage, with the degradation of PLA crystalline
the rate of water vapor transmission by the rubber film and the sealing zone, the amount of carboxyl-terminated groups increased, and the
tape. The film samples were sealed on 25 mm × 40 mm weighing bot- degradation rate was accelerated, resulting in autocatalytic phenomena
tles, which were filled with 12 g of anhydrous silica gel. The weighing [39,40]. Consequently, the dense structure of PLA/nano-Ag composite
bottles were placed in a desiccator equipped with saturated sodium films were severely damaged, and a large number of holes in the films
chloride and measured every hour [36,37]. Tests were lasted for 12 h, accelerated the migration of nanoparticles, which was consistent with
and the WVP of the samples was calculated according to formula (4): existing research results [41,42].
Observing figure, it can be found that under the same high pressure
ΔB×N
WVP = treatment conditions, the migration amount of nano-Ag increased with
Δ T× A× ΔP (4)
the initial addition amount of nano-Ag in the films, and in the pre-
Where ΔB is the change in weight of the weighing bottle (g), N is the storage period (storage time < 7 days), migration amount had little
average thickness of the samples (in mm), ΔP is the difference between difference. Probably because the first dissolved nanoparticles were at-
the water vapor pressure inside and outside the composites (KPa), ΔT is tached to the surface of the composite films and the external cross
the measured time (h), A is the test area (m2). sections, and their content was not much different. In addition, by
comparing the curves, it can be concluded that the migration amount
3. Results and discussion increased as the pressure and the treatment time increased. For ex-
ample, the migration of film containing 20% nano-Ag increased from
3.1. Migration test 7.2 mg/kg (100 Mpa, 10 min) to 18.5 mg/kg (400 Mpa, 10 min), and
the migration of film containing 20% nano-Ag increased from 20.8 mg/
In this migration test, isooctane was used to simulate the packaging kg (200 Mpa, 10 min) to 29.5 mg/kg (200 Mpa, 30 min). This result was
environment of fatty food to evaluate the suitability and safety of PLA/ contrary to the conclusion that the high pressure treatment could re-
nano-Ag composite films. Figs. 1–3 displayed the migration of nano-Ag duce the migration of nanoparticles by increasing the crystallinity of
in the composite films with different initial nano-Ag content, different the composite film in the study [43]. Damaging effect on the structures
conditions of high pressure treatment within 49 days. It can be seen of composites caused by long-term high-temperature immersion in oily
from the figure that at 40 °C, regardless of the initial content of nano-Ag

Fig. 1. Migration of nano-Ag from PLA nanocomposite films treated by (a) 100 MPa, (b) 200 MPa, (c) 300 MPa, and (d) 400 MPa for 10 min.

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Fig. 2. Migration of nano-Ag from PLA nanocomposite films treated by (a) 100 MPa, (b) 200 MPa, (c) 300 MPa, and (d) 400 MPa for 20 min.

food simulating liquid far exceeded the positive effect of high pressure micropores appeared on the cross section of the composite films, which
treatment on the tight alignment of molecular chains, and it may be the became more and more rough. According to the literature, this may be
explain for this result. related to electrostatic binding between nanoparticles. When a large
number of nanoparticles were embedded in the polylactide matrix,
some particles would aggregate together to form clusters due to elec-
3.2. Microscopic structure trostatic bonding, which would gradually enlarge the micropores [44].
Electron micrograph of different soaking time displayed that as the
Figs. 4 and 5 showed the microstructure of brittle fracture section of migration time increased, more and more longitudinal folds appeared
different nano-Ag proportions of composite films which were treated by in the microscopic cross section of the composite films, which became
200 and 400 Mpa for 20 min and soaked in food simulating liquid for 0, uneven. The large amount of such wrinkles provided more channels for
14, 28 and 49 days. Through horizontal comparison, it can be found the continuous migration of nano-Ag and the entry of the simulated
that as the content of nano-Ag increased, a large number of clusters and

Fig. 3. Migration of nano-Ag from PLA nanocomposite films treated by (a) 100 MPa, (b) 200 MPa, (c) 300 MPa, and (d) 400 MPa for 30 min.

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Fig. 4. Microstructure changes of the composite during migration.

liquid into the composite films, which led to loose internal structure of order to study the changes in thermal properties of composite films with
PLA and decrease in crystallinity [45]. different nano-Ag content during migration. Fig. 6 showed DSC ther-
In addition, comparing with the composite films treated by pressure mogram of the composite films under argon atmosphere over tem-
of 200 and 400 Mpa, it can be found that at 400 Mpa, the clusters of the perature range of 40–200 °C. Table 1 listed the thermal performance
brittle section reduced, but the wrinkling phenomenon was more ob- parameters of the different composite films from the different migration
vious, and a large number of depressions and holes gradually appeared. stages summarized in Fig. 6. Based on Table 1, it displayed that the
This indicated that the high pressure treatment blocked the electrostatic composite films after high pressure treatment had no significant change
binding effect between the nanoparticles, allowing them to be uni- in Tm with the increase of nano-Ag and migration time, and the Tg of
formly dispersed inside the PLA [46]. However, at the same time, the the composite films increased with increasing migration time, in-
high pressure treatment would make the microscopic section uneven. It dependent of the nano-Ag content. At the same time, Tc and Xc in-
displayed in the literature that the gas in the high pressure device creased as migration time and nano-Ag content increased, which may
would dissolve in films under the increasing pressure, and it expanded be related to the migration of nano-Ag and the entry of isooctane into
rapidly in a short time of rapid pressure relief, which caused the for- the composite films [47].
mation of depressions [45,46]. Comprehensively, although the high By comparing the DSC curves of the same composite film during
pressure treatment played a positive role in the microstructure of the different migration time, it demonstrated that the films containing 1 wt
composite films, the long-term immersion of the food simulating liquid %, 10 wt% or 20 wt% nano-Ag showed exothermic peaks at 100–120 °C,
had a greater influence on the structures of the composite films. It can respectively. As migration time increased, the exothermic peaks gra-
be seen from Fig. 4 that the internal structures of the composite films dually moved toward the high temperature direction and the cold
treated by 200 Mpa has already appeared collapsed at the later stage of crystallization temperature increased from about 104.3 °C (sample: 1%,
migration, and they had not been applied to food packaging materials. 0 day) to 127 °C (sample: 20%, 49 days). Comparing the peaks of the
Therefore, we only studied the performances of the composite films films with different nano-Ag content, it demonstrated that the peak
treated by 400 Mpa in the following tests. shape of the exothermic peaks of the film with 1% nano-Ag were
sharper than the peak shape of the film with 10 wt% and 20 wt% nano-
Ag. The possible reason was that the crystallization reaction rate in-
3.3. Thermal performance
creased, which in turn shortened the crystallization reaction time
[48,49].
In order to show food preservation application, the packaging ma-
terials need to be thermally stable. DSC spectra have been carried out in

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Fig. 5. Microstructure changes of the composite during migration.

Fig. 6. DSC curves of the composite films (a) 1% nano-Ag, (b) 10% nano-Ag, and (c) 20% nano-Ag treated by 400 MPa for 20 min during migration.

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Table 1 Table 3
Thermal Characteristics of different nano-Ag content of composite films treated Water vapor permeability of different nano-Ag content of composite films
by 400 Mpa for 20 min during migration. treated by 400 Mpa for 20 min during migration.
samples (wt%) migration time (d) Tg (°C) Tc (°C) Tm (°C) Xc nano-Ag (wt%) migration time (d) WVP × 10−2 (g mm/m2·h·KPa)
(%)
1 0 3.27 ± 0.12b
1 0 51.3 104.3 166.5 2.12 1 14 11.97 ± 0.18d
1 14 55.6 108.2 166.3 4.96 1 28 15.12 ± 0.16g
1 28 56.5 114.5 165.5 6.16 1 49 18.73 ± 0.03j
1 49 57.6 115.6 165.0 6.32 10 0 2.37 ± 0.10a
10 0 51.3 110.2 167.0 2.22 10 14 11.05 ± 0.17c
10 14 55.5 120.2 166.8 5.40 10 28 14.36 ± 0.21f
10 28 55.9 121.7 166.6 7.74 10 49 18.06 ± 0.05i
10 49 56.7 125.3 165.8 8.39 20 0 2.28 ± 0.215a
20 0 51.2 111.8 166.9 5.03 20 14 10.88 ± 0.21c
20 14 53.2 123.9 166.6 5.58 20 28 13.25 ± 0.11e
20 28 55.8 124.4 165.9 8.97 20 49 17.31 ± 0.03h
20 49 56.6 127.0 165.3 9.16
a–j values followed by different superscripts in the same column represent
significant difference (p < 0.05), where a is the highest value.
3.4. Mechanical property
nano-Ag. After the PLA-based films were immersed in the food simu-
Films used for food preservation need to withstand external stresses lating liquid, a large number of channels were formed inside, which
and maintain their integrity, so excellent mechanical properties are made the internal structures loose, so that the water vapor easily en-
critical [50]. Table 2 listed the TS, EM and ε of the composite films to tered between the inside of the composite films and the external en-
characterize the mechanical properties. It can be seen from Table 2 that vironment. In the same migration time, the WVP of the composite films
there was no significant difference in TS. The EM of the composite films decreased as the nanoparticle content increased. The reason for this
reduced as the nano-Ag content and migration time increased, and the ε phenomenon was that after the addition of nano- Ag to PLA, the in-
decreased as the migration time increased. The EM of the composite teraction between molecular chains in the composite materials was
film containing 1% nano-Ag decreased from 1751.54 Mpa (0 days) to enhanced, and the internal inter-molecular distance and free volume
1118.56 Mpa (49 days). At 14 days, the EM (1344.63 Mpa) of the were reduced [51]. The films formed more tightly tortuous system
composite film containing 20% nano-Ag was lower than the EM network structures, which led to increase in the path of water vapor
(610.78 Mpa) of the composite film containing 1% nano-Ag. The ε of diffusion, and decrease in the effective diffusion coefficient and solu-
the 10% nano-Ag composite film decreased from 10.25% (0 days) to bility coefficient [52].
7.02% (49 days). This was because that the nanoparticles constantly
moved out as the immersion time increased. From a microscopic point
of view, the migration of nanoparticles would change the inter- 4. Conclusion
molecular bonding strength and crystal structure of the composite
films, and stable structures between the molecules of the composite film In this study, nano-Ag was embedded into PLA by melt blending to
were destroyed [50]. form PLA/nano-Ag composite materials, then the films were treated by
100, 200, 300, 400 Mpa for 10, 20, 30 min respectively, and were
soaked in isooctane food simulant for 49 days. The dissolved amount of
3.5. Water vapor transmission rate nano-Ag and various properties of composite films during the migration
process were tested and compared. It was found by AAS test that under
The barrier properties of the composite films were characterized by the storage conditions of 40 °C, the migration of nano-Ag in all these
Water vapor permeability (WVP). Table 3 listed the WVP of different composite films into the oily food simulated liquid increased with the
composite films treated at 400 Mpa for 20 min during soaking. It can be increase of initial nano-Ag content, pressure, and treatment time.
seen from Table 3 that the WVP of the composite films of the same During the 49-day migration storage period, the most influential factor
nanoparticle content increased as the migration time increased, and this for the dissolution of nanoparticles was migration time, and the mi-
tendency was more pronounced in the composite films having a higher gration amount and migration rate of nano-Ag increased with the mi-
gration time. SEM morphology revealed that in the long-term soaking
Table 2 environment of food simulating liquid, as the initial nano-Ag content
Mechanical properties of different nano-Ag content of composite films treated and migration time of the composite films increased, a large number of
by 400 Mpa for 20 min during migration.
clusters, micropores and longitudinal folds appeared on the cross sec-
nano-Ag migration TS (Mpa) EM (Mpa) ε (%) tions, and the films became more and more rough. For the influence of
(wt%) time (d) the microstructure of the composite films, high pressure treatment was
1 0 34.12 ± 1.82abc 1751.54 ± 95.55c 14.62 ± 2.87d
a secondary positive factor, and migration time was the dominant ne-
1 14 32.36 ± 2.40abc 1344.63 ± 42.72c 4.40 ± 0.00a gative factor. DSC curves and mechanical performance analysis in-
1 28 35.94 ± 0.69bc 1693.77 ± 62.93ab 4.40 ± 0.00a dicated separately that the increase of migration time and addition of
1 49 27.48 ± 0.25ab 1118.56 ± 43.85ab 7.04 ± 1.67abc nano-Ag could raise the crystallization temperature of the composite
10 0 34.58 ± 2.58bc 1872.68 ± 121.58c 10.25 ± 1.21c
films, and reduce the modulus of elasticity. Barrier performance ana-
10 14 34.34 ± 1.42abc 1498.13 ± 131.85c 4.40 ± 0.00a
10 28 38.18 ± 0.76c 1444.31 ± 100.91ab 4.40 ± 0.00a lysis illustrated that WVP increased with the migration time and de-
10 49 36.32 ± 0.72bc 830.86 ± 79.13ab 7.02 ± 0.80abc creased with the increase of initial nano-Ag content. By comprehensive
20 0 30.74 ± 1.86abc 1641.04 ± 74.16ab 9.12 ± 2.32bc analysis, we could find that the high pressure treatment and the addi-
20 14 29.47 ± 1.08abc 610.78 ± 110.41ab 4.46 ± 0.44ab tion of nano-Ag had improved the performances of the composite films.
20 28 34.93 ± 7.06bc 1413.78 ± 139.97ab 4.40 ± 0.00a
20 49 24.89 ± 4.26a 775.57 ± 131.13a 5.05 ± 0.00ab
When the PLA/nano-Ag composite films are used for oily food packa-
ging for a long time, its performances will be destroyed, so the pre-
a–c values followed by different superscripts in the same column represent servation time should not exceed 35 days. This discovery is critical to
significant difference (p < 0.05), where a is the highest value. the development of safe food packaging materials with excellent

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C. Fan, et al. Polymer Testing 76 (2019) 73–81

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