polymers

Article
Degradation of Mechanical Properties of A-PET Films after
UV Aging
Marius Vasylius 1, *, Artūras Tadžijevas 1 , Deivydas Šapalas 1 , Valentinas Kartašovas 1, * , Jolanta Janutėnienė 2, *
and Pranas Mažeika 2

1 Marine Research Institute, Universiteto Av. 17, 92294 Klaipeda, Lithuania; [email protected] (A.T.);
[email protected] (D.Š.)
2 Department of Engineering, Klaipeda University, Bijūnu˛ st. 17, 91225 Klaipeda, Lithuania;
[email protected]
* Correspondence: [email protected] (M.V.); [email protected] (V.K.);
[email protected] (J.J.)

Abstract: In 2018, the European Commission adopted the European Strategy for Plastics in a Circular
Economy, which outlines key actions to reduce the negative impact of plastic pollution. The strategy
aims to expand plastic recycling capacity and increase the proportion of recycled materials in plastic
products and packaging. Using recycled plastic can save 50–60% energy compared to virgin plastic.
Recycled PET can be used in the production of A-PET films, which are predominantly used in thermo-
vacuum forming for food packaging. Storage conditions can influence the mechanical properties of
polymer materials. This work presents changes in the mechanical properties of A-PET films after
UV irradiation. An experimental investigation of the UV aging of A-PET films was conducted in
a UV aging chamber. The specimens were exposed to a UV radiation dose rate of 2.45 W/m2 for
1, 2, 4, 8, 16, 24, 32, and 40 h. UV measurements were also taken on a sunny day to compare the
acceleration of UV irradiation in the UV aging chamber. Mechanical tensile tests were performed
on two different three-layer A-PET films (100% virgin and 50% recycled). The tensile strength and
relative elongation of the A-PET films were determined, and the work required to break the film
was calculated. The total consumed work was divided into the work needed for elastic and plastic
Citation: Vasylius, M.; Tadžijevas, A.;
Šapalas, D.; Kartašovas, V.;
deformations. A study of the UV aging of A-PET films confirmed a significant effect on the films,
Janutėnienė, J.; Mažeika, P. including a loss of plasticity even after brief exposure to solar irradiance. The results of the puncture
Degradation of Mechanical impact test further confirmed the deterioration of the mechanical properties of A-PET material due to
Properties of A-PET Films after UV exposure to UV radiation, with a greater effect observed for the recycled material.
Aging. Polymers 2023, 15, 4166.
https://doi.org/10.3390/ Keywords: A-PET films; UV irradiation; tensile stress; degradation of properties; impact energy
polym15204166

Academic Editor: Cristian-Dragos

Varganici
1. Introduction
Received: 21 September 2023
The European Strategy for Plastics in a Circular Economy [1] notes that plastics and
Revised: 15 October 2023
plastic-containing products are designed for greater durability, reuse, and high-quality
Accepted: 18 October 2023
recycling. Polyethylene terephthalate (PET) is a widely used thermoplastic polymer that
Published: 20 October 2023
belongs to the polyester family of polymers. It is used to make water bottles, transparent
films, textile fibers (fabrics), and more. PET was first synthesized in the early 1940s, and its
popularity grew rapidly with the development of synthesis methods. Among other plastics,
Copyright: © 2023 by the authors. polyethylene terephthalate is notable for being durable and relatively strong, able to be
Licensee MDPI, Basel, Switzerland. made clear, colorless, or colored (high-density polyethylene is difficult to make completely
This article is an open access article transparent), almost impermeable to gas, inexpensive to produce, and fully recyclable
distributed under the terms and because its polymer chains do not break down during recycling.
conditions of the Creative Commons The application of PET in the bottle bottling industry started in the 1970s with the
Attribution (CC BY) license (https:// advancement of moldable resins. The PET material used to create the bottles is a semi-
creativecommons.org/licenses/by/
crystalline copolymer with a glass transition temperature of approximately 76 ◦ C and a
4.0/).

Polymers 2023, 15, 4166. https://doi.org/10.3390/polym15204166 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 4166 2 of 16

melting temperature of approximately 250 ◦ C. Its density ranges between 1.3 and 1.4 g/cm3 ,
and it has a minimum internal viscosity of 0.7 dL/g.
PET films are widely used as a thermoformable food packaging material. Therefore,
the prevalence of this substance is extremely wide. A change in its properties is a subject of
study for many researchers. Some of them study the degradability of this polymer using
microbiological methods to develop effective methods for the destruction of this substance,
in some cases for the primary decomposition of this substance with the additional use
of UV radiation; meanwhile, other scientists study the depreciation of the properties of
primary or recycled PET material, which defines the storage conditions and the possibilities
of high-quality use of the material [2–4]. These studies are particularly relevant for the
purpose of using all the collected recycled PET for further use. A comprehensive exam-
ination of the mechanical, thermal, rheological, morphological, and other properties of
composite materials made from recycled PET is presented in reference [5]. Amorphous
polyethylene terephthalate (A-PET) is a thermoplastic film produced through extrusion
from polyethylene terephthalate. A-PET is known for its excellent transparency, gloss,
mechanical properties, and thermoforming capabilities. It provides an effective barrier
against oxygen, nitrogen, and carbon dioxide, making it ideal for modified atmosphere
packaging (MAP). A-PET can be used in contact with food and is approved by various
food safety organizations in the European Union. Its antibacterial properties also make it a
common choice for pharmaceutical packaging. Products and packaging made from A-PET
can be recycled and reused to create the same films.
The degradation phenomena that occur during the life cycle and processing of PET
are discussed in reference [6]. The solar radiation that reaches the Earth’s surface has
wavelengths ranging from 295 nm to 2500 nm. It is classified into two categories: UV-B
(280–315 nm), with an energy of 426–380 kJ/mol; and UV-A (315–400 nm), with an energy of
389–300 kJ/mol. Fortunately, the most energetic part of UV-B from 280 to 295 nm is filtered
by the stratosphere and does not reach the Earth’s surface. UV-A is less harmful to organic
matter than UV-B. The visible spectrum consists of electromagnetic waves from 400 nm
to 760 nm and infrared radiation from 760 to 2500 nm [7]. The changes in the chemical
structure of the polymer were studied using Fourier transform infrared spectroscopy and
Raman spectroscopy in reference [8].
Many reactions can occur during exposure to sunlight, including chain decomposition
due to thermal degradation between the vinyl and carboxyl chain ends, photodegradation
of methylene groups leading to irreversible effects, degradation of polymer chains, and
changes in the clarity of PET (yellowing) due to substances used in the synthesis and
production process. Exposure to light and air causes PET photooxidation (photochemical
aging). It is known that PET absorbs UV waves with wavelengths ranging from 300 nm
to 330 nm. This leads to the degradation of a thin surface layer, which limits oxygen
diffusion and superficial light absorption [9]. In reference [10], the optical energy gap
of un-irradiated and irradiated PET samples at different wavelengths was determined
using UV–Visible spectra. The molecular bond structure was analyzed before and after
UV-irradiation. Thus, changes in the molecular weight distribution and morphology of
PET can result from temperature and photooxidation phenomena, affecting the mechanical
and thermal properties of the material.
The impact of various forms of radiation on the properties of PET is analyzed in
reference [11]. It has been found that the structure of PET can be altered through chain-
degradation reactions and the formation of new chemical bonds, leading to changes in its
properties. As a result, many researchers have focused on the effect of physical aging on the
mechanical properties of PET, using various methods to characterize both morphological
changes and physical properties [12]. In addition to equipment for measuring mechanical
properties (tensile strength, impact strength, and fatigue analysis), calorimetric analysis,
FT-IR (Fourier transform infrared) molecular spectrometry, X-rays, and nuclear magnetic
resonance (NMR) are also used.
Polymers 2023, 15, 4166 3 of 16

The changes in the glass transition temperature (Tg) of PET during aging were ana-
lyzed in reference [13]. Over a period of 670 days, the glass transition temperature of aged
bottles in a dark room increased from 74 ◦ C to 78 ◦ C, and in a sunny outdoor location, it
increased from 74 ◦ C to 87 ◦ C. It was also observed that the endothermic glass transition
became sharper as PET aged. Indoor in the dark room, the melting temperature of aged
bottles decreased from 249.8 ◦ C to 243.1 ◦ C, and in a sunny outdoor location, it decreased
from 249.8 ◦ C to 245.6 ◦ C.
The physical aging of semi-crystalline PET was studied using differential scanning
calorimetry (DSC) at temperatures below the glass transition temperature (25 ◦ C and 45 ◦ C)
in reference [14]. The results showed that after 120 days at 25 ◦ C, the glass transition tem-
perature increased slightly from 73.26 ◦ C to 73.63 ◦ C, and at 45 ◦ C, it increased significantly
from 73.26 ◦ C to 86.33 ◦ C.
In reference [15], the anisotropy of the stress–optical properties of PET films under
uniaxial stress was investigated. In paper [16], the tensile properties of three-layer A-PET
films with different middle layer compositions were studied. It was found that increasing
the amount of recycled plastic from 20% to 100% reduced the tensile strength by 12–16%. In
reference [17], the plasticity and impact properties of thermoplastic materials were studied
through numerical analysis using the finite elements method, and a comparison was made
with experimental results.
The plasticity of materials can be determined through impact tests. The puncture im-
pact test of low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE)
was performed, and the force versus deformation was investigated in reference [18]. The
authors found that the average peak force values of LLDPE film were about 14% greater
than those of LDPE film.
In reference [19], three different types of recycled high-density polyethylene were ana-
lyzed and compounded with virgin medium density polyethylene (MDPE) in an extruder.
The impact resistance results showed that the 50/50 ratio produced results like those of
MDPE. In reference [20], six different methods for determining the ductile/brittle transition
temperature were analyzed, one of which was the Elastic energy ratio. In this method, the
peak load energy (Em ) is compared to elastic energy (Eel .).
In practice, recycled A-PET is used to produce food packaging films. From the pro-
duction of the film to its use for packaging, it must be stored under appropriate conditions.
Practical observations showed that the films can change their mechanical properties, be-
coming more brittle, making the molding process more challenging.
The objective of this study is to determine the mechanical properties of A-PET films
after aging in a UV aging chamber for various lengths of time, comparing virgin A-PET
and recycled R_A-PET materials.

2. Materials and Methods

Materials. Experimental tests of three-layer virgin and recycled A-PET films were
conducted. Two types of materials were tested: 100% virgin A-PET film (clear color) and
recycled R_A-PET in (black color), where the inner layer of the film consists of 50% recycled
and 50% virgin material, and the outer layer is made entirely of virgin A-PET. The thickness
of the R_A-PET (black) film is 0.5 mm, and the thickness of the virgin A-PET (clear) film is
0.35 mm.
Tensile test. Mechanical tensile testing of thin plastic films was performed in accor-
dance with the standard ASTM D882-2:2004 [21]. Specimens of 250 mm in length and
25 mm in width were cut from the A-PET roll. Both non-aged and UV-aged films were
tested using a Zwick/Roell Z020 universal testing machine (Figure 1a). Each test was
repeated three times, and the mean values of the results were calculated. The following
parameters were measured on the testing machine: tensile strength, relative elongation
at maximum force and film breakage, modulus of elasticity, and the work required to
break the film. From the measured total energy, the work consumed for elastic and plastic
deformation was determined.
 when the puncture probe hit the film specimen. The puncture impact test was performed
according to ISO 7765-2 standard [23]. Test specimens were cut into 80 × 80 mm size
squares. During the test, specimens were securely clamped with camping rings which
have an inside diameter of 40 mm. The test was performed with hemispherical, polished,
and hardened striker with a diameter of 20 mm. The main parameters of performed tests
Polymers 2023, 15, 4166 4 of 16
were as follows: drop weight, 9.421 kg; drop height, 987 mm; penetrator weight, 0.19 kg;
impact velocity, 4.4 m/s; potential energy, 96.51 J.

=
Figure
Figure 1. 1.Testing
Testingequipment.
equipment. (a)
(a)Universal
Universaltesting machine
testing machineZwick/Roell Z020:
Zwick/Roell 1—specimen-holding
Z020: 1—specimen-
clamps
holding “GRIPS”;
clamps 2—20 2—20
“GRIPS”; kN force
kN cell;
force3—machine controller;
cell; 3—machine 4—specimen.
controller; (b) UV-aging
4—specimen. chamber
(b) UV-aging
Atlas UVTest:
chamber 1—UV 1—UV
Atlas UVTest: sensors;sensors;
2—specimen holder; 3—specimen;
2—specimen 4—UV lamp.
holder; 3—specimen; 4—UV (c) lamp.
Drop-weight-test-
(c) Drop-
ing machine Zwick/Roell Amsler HIT200F: 1—variable weight carriage; 2—safety pins; 3—puncture
weight-testing machine Zwick/Roell Amsler HIT200F: 1—variable weight carriage; 2—safety pins;
probe; 4—pneumatic specimen holding grips.
3—puncture probe; 4—pneumatic specimen holding grips.

TheInplastic
accordance with thewere
film specimens recommendations
aged in an AtlasofUVthetest
ASTM D882-2
UV aging standard
chamber [21],1b)
(Figure and
based on
following the relative
ASTM elongation[22].
G154 procedures of the filmUVA-351
A 40W measured during the
fluorescent preliminary
lamp was used,break
whichtest
simulates the UV energy in sunlight passing through a window glass. Both types of and
(up to 20%), the crosshead speed of the testing machine was set to 12.5 mm/min, filmsthe
distance between the grippers was 125 mm. The test was stopped when
were aged in the chamber for 1, 2, 4, 8, 16, 24, 32, and 40 h. The UV irradiance dose the tensile load
2
rate received by the films from the fluorescent lamps was 2.45 W/m . The machine has
24 specimen holders, with a total area of 6848 cm2 . The distance between machine UV
lamps and specimens is 52 mm. The machine is also capable to perform condensation
weathering tests.
The dose rate is the amount of UV energy falling on an object per unit area. The
temperature in the UV aging chamber was maintained at 60 ◦ C. The total UV doses
received by the different films are shown in Table 1.

Table 1. Accelerated UV aging hours and total UV irradiance.

Accelerated UV Accelerated UV Natural Solar UV

Film Type Aging, Irradiance, Aging,
Hours Wh/m2 Hours
1 1 2.45 4.3
2 2 4.9 8.6
3 4 9.8 17.2
4 8 19.6 34.4
5 16 39.2 68.8
6 24 58.8 103.2
7 32 78.4 137.5
8 40 98 171.9

Puncture impact test. The puncture impact testing of A-PET films was performed
using a drop weight testing machine (Figure 1c), measuring the force dependency over time
when the puncture probe hit the film specimen. The puncture impact test was performed
according to ISO 7765-2 standard [23]. Test specimens were cut into 80 × 80 mm size
squares. During the test, specimens were securely clamped with camping rings which have
an inside diameter of 40 mm. The test was performed with hemispherical, polished, and
hardened striker with a diameter of 20 mm. The main parameters of performed tests were
as follows: drop weight, 9.421 kg; drop height, 987 mm; penetrator weight, 0.19 kg; impact
velocity, 4.4 m/s; potential energy, 96.51 J.
R PEER REVIEW 5 of 16
Polymers 2023, 15, 4166 5 of 16

decreased by more than In accordance

80%. The with the recommendations
ambient conditions of the ASTM
during theD882-2
tests standard
were as[21], and
follows:
based on the relative elongation of the film measured during the preliminary break test
21.1 °C ambient temperature;
(up to 20%), the43% relative
crosshead speedhumidity.
of the testing machine was set to 12.5 mm/min, and the
UV irradiation. The between
distance amounttheofgrippers
UV energy
was 125 in
mm. sunlight under
The test was real-world
stopped conditions
when the tensile load
decreased
was estimated and compared. by more than 80%. The ambient conditions during the
UV measurements were taken on June 17 2020 on a sunny tests were as follows:
21.1 ◦ C ambient temperature; 43% relative humidity.
day with no clouds. The measurements
UV irradiation. were
The amount taken
of UV energyfrom 10:30under
in sunlight to 17:00 in three
real-world direc-
conditions
tions— southeast, was
south, and and
estimated southwest—with the instrument
compared. UV measurements tilted
were taken 45°17towards
on June 2020 on a the
sunnysky
day with no clouds. The measurements were
from the horizon. The geographical coordinates of the UV measurementtaken from 10:30 to 17:00 in three directions—
location were
southeast, south, and southwest—with the instrument tilted 45◦ towards the sky from the
55.7274° latitude and 21.1260°
horizon. longitude.coordinates
The geographical The UV doseof the rate was measured
UV measurement location using
were a55.7274
UV test
◦
calibration radiometer UVA
latitude at 351 longitude.
and 21.1260 ◦ nm, andThe a one-day
UV dose rategraph is shown
was measured using ina Figure 2.
UV test calibration
radiometer UVA at 351 nm, and a one-day graph is shown in Figure 2.

Figure 2. Results of UV dose

Figure rate measurements.
2. Results of UV dose rate measurements.

3. Results and Discussion

3. Results and Discussion
As shown in Figure 2, the results of the UV dose rate measurements indicate that
the maximum amount of UV energy from sunlight in the normal direction occurs for 2 h
As shown in Figure 2, the results of the UV dose rate measurements indicate that the
per day.
maximum amount of UV Theenergy
maximum from sunlight
measured UV in
dosetherate
normal direction
was 2.91–2.93 occurs
W/m 2 . Thefor 2h
total perUV
daily day.
2 2
The maximum measured
irradiance UVfrom
received dose rate was
sunlight was12.572.91–2.93
Wh/m W/m 2 . The total
in the southeast, 13.27daily
Wh/mUV irra-
in the
south, and 13.68 Wh/m2 in the southwest. The one-hour average was 0.52 2Wh/m2 in the
diance received from sunlight was 12.57 Wh/m in the southeast, 13.27 Wh/m in the south,
2
southeast, 0.55 Wh/m2 in the south, and 0.57 W/m2 in the southwest. The recalculated
and 13.68 Wh/m inUV
2 the southwest.
irradiance The one-hour
is presented average
in Table 1, allowing was
us to see 0.52 Wh/m
the amount
2 in the southeast,
of UV the film would
0.55 Wh/m2 in the have
south, and if0.57
received W/m
it had in the southwest.
been2 naturally The recalculated UV irradiance
exposed to sunlight.
is presented in Table 1,A-PET specimen strips were inserted into the grippers of the testing machine using
allowing us to see the amount of UV the film would have received
rubber gaskets to prevent significant deformation of the specimen strips and slippage of
if it had been naturally exposed
the specimens to sunlight.
within the gripper. The fixed specimens in the grippers of the Zwick/Roell
A-PET specimen
Z020 strips were inserted
testing machine are showninto the 3.grippers of the testing machine using
in Figure
rubber gaskets to prevent significant deformation of the specimen strips and slippage of
the specimens within the gripper. The fixed specimens in the grippers of the Zwick/Roell
Z020 testing machine are shown in Figure 3.
 0.55 Wh/m2 in the south, and 0.57 W/m2 in the southwest. The recalculated UV irradiance
is presented in Table 1, allowing us to see the amount of UV the film would have received
if it had been naturally exposed to sunlight.
A-PET specimen strips were inserted into the grippers of the testing machine using
rubber gaskets to prevent significant deformation of the specimen strips and slippage of
Polymers 2023, 15, 4166 6 of 16
the specimens within the gripper. The fixed specimens in the grippers of the Zwick/Roell
Z020 testing machine are shown in Figure 3.

Figure 3.
Figure 3. Tensile
Tensile tests
tests of
of non-aged
non-aged virgin
virgin A-PET
A-PET and
and recycled
recycled R_A-PET
R_A-PET specimens:
specimens: (a)
(a) non-aged
non-aged
Polymers 2023, 15, x FOR PEER REVIEW
virgin A-PET specimen before test; (b) non-aged virgin A-PET specimen after test; (c) recycled6 R_A-
of 16
virgin A-PET specimen before test; (b) non-aged virgin A-PET specimen after test; (c) recycled
PET specimen
R_A-PET before
specimen test; (d)
before test;recycled R_A-PET
(d) recycled specimen
R_A-PET afterafter
specimen test. test.

The
The specimen
specimenin
inthe
thegrippers
grippersduring
duringthe
thepuncture
punctureimpact
impacttest
testisisshown
shownin
inFigure
Figure4.4.

Figure4.4. Puncture
Figure Puncture impact
impact test
test of
of A-PET
A-PET film:
film: (a)
(a) before
before test;
test; (b)
(b) after
after test
test (side
(side view);
view); (c)
(c) after
after test
test
(topview).
(top view).

The A-PET
The A-PET film
film specimens
specimens after
after the
the tensile
tensile and
and puncture
puncture impact
impact tests
tests are
are shown
shown in
in
Figure 5.
Figure 5. As
As the
the data
data indicate,
indicate, the
the specimens
specimens made
made fromfrom virgin
virgin material
material (clear
(clear film)
film) began
began
tobreak
to breakbrittlely
brittlelyafter
afterbeing
beingexposed
exposedto toUV
UVradiation
radiationforfor44h,
h,while
whilethe
thespecimens
specimenscomposed
composed
of recycled
of recycled material
material (black film) exhibited
exhibited brittle
brittle fracture
fractureeven
evenafter
afterjust
just11hhofofUV
UVaging.
aging.
The curves of tensile stresses and strain obtained during the tests are shown in
Figures 6 and 7. From these curves, we can see that even with the slight aging of the
A-PET films in the UV aging machine, the material loses its plasticity. The R_A-PET mate-
rial loses its plasticity faster than virgin material. As we can see in Figure 7, when exposed
to UV, polymer bonds decompose faster and lose the important plasticity property of
the film.
The dependencies of tensile strength and strain at maximum force on UV irradiance
are shown in Figures 8 and 9, respectively. These dependencies show that the tensile
strength of R_A-PET films is 20% higher than that of virgin films. After more than 8 h of UV
exposure (or 19.6 Wh/m2 ), the tensile strength does not change; it remains almost the same;
i.e., the R_A-PET films are about 59.2 MPa and the virgin A-PET films are about 49.4 Mpa.
The relative elongation (strain) of maximum tensile strength films also has a limiting UV
aging time. Figure 9 shows that after UV aging for 1–4 h (up to 9.8 Wh/m2 ), the relative
elongation of films increases, but when they are UV-aged for more time, their relative
elongation begins to decrease, the material becomes harder, and its plasticity decreases. In
graphs, error bars indicate the standard deviation of the measurements and show how the
set of experimental results tend to be close to the mean.
 Figure 4. Puncture impact test of A-PET film: (a) before test; (b) after test (side view); (c) after test
(top view).

The A-PET film specimens after the tensile and puncture impact tests are shown in
Polymers 2023, 15, 4166
Figure 5. As the data indicate, the specimens made from virgin material (clear film) began 7 of 16
to break brittlely after being exposed to UV radiation for 4 h, while the specimens composed
of recycled material (black film) exhibited brittle fracture even after just 1 h of UV aging.

Polymers 2023, 15, x FOR PEER REVIEW 7 of 16

The curves of tensile stresses and strain obtained during the tests are shown in Fig-
ures 6 and 7. From these curves, we can see that even with the slight aging of the A-PET
films in the UV aging machine, the material loses its plasticity. The R_A-PET material loses
itsFigure
plasticity faster
5. View
View of than virgin material. Asfilm
we specimens:
can see in Figure 7,tensile
whentest;
exposed topuncture
UV,
Figure 5. of virgin
virgin and
andrecycled
recycledA-PET
A-PET film (a)(a)
specimens: after
after (b) after
tensile test; (b) after puncture
polymer bonds
impact test. decompose faster and lose the important plasticity property of the film.
impact test.

Figure6.6.
Figure Tensile
Tensile stress
stress andand strain
strain curves
curves of virgin
of virgin A-PETA-PET
films films aged
aged at at different
different durations.
durations.
Polymers 2023, 15, 4166 8 of 16
Figure 6. Tensile stress and strain curves of virgin A-PET films aged at different durations.

Polymers
Polymers2023,
2023,15,
15,xxFOR
FORPEER
PEERREVIEW
REVIEW 88 of
of 16
16

In
Ingraphs,
graphs,error
errorbars
barsindicate
indicatethe
thestandard
standarddeviation
deviationof
ofthe
themeasurements
measurementsand
andshow
showhow
how
the
theset
7. of
set
Figure
Figure ofexperimental
7. experimental
Tensile
Tensile stress
stress results
results
andand tend
tend
strain
strain to be
curves
curves of ofclose
toR_A-PET
be closeto
tothe
R_A-PET the
films mean.
mean.
films
aged ataged at different
different durations.
durations.

The dependencies of tensile strength and strain at maximum force on UV irradiance

are shown in Figures 8 and 9, respectively. These dependencies show that the tensile
strength of R_A-PET films is 20% higher than that of virgin films. After more than 8 h of
UV exposure (or 19.6 Wh/m2), the tensile strength does not change; it remains almost the
same; i.e., the R_A-PET films are about 59.2 MPa and the virgin A-PET films are about 49.4
Mpa. The relative elongation (strain) of maximum tensile strength films also has a limiting
UV aging time. Figure 9 shows that after UV aging for 1–4 h (up to 9.8 Wh/m2), the relative
elongation of films increases, but when they are UV-aged for more time, their relative
elongation begins to decrease, the material becomes harder, and its plasticity decreases.

Figure
Figure8.8.
Figure 8.Dependence
Dependence
Dependenceof tensile
ofof
tensilestrength
strength
tensile and UV
andand
strength irradiance.
UVUVirradiance.
irradiance.

Figure
Figure9.9.
Figure 9.Dependence
Dependence
Dependenceof relative
ofof
relativeelongation
elongation
relative at
atmaximum
elongation maximum force and
andUV
forceforce
at maximum UVirradiance.
andirradiance.
UV irradiance.

The
Thebreaking
breakingpoint
pointofofthe
thespecimens
specimensalsoalsoclearly
clearlydemonstrates
demonstratesthe theimpact
impactofofUV
UVag-
ag-
ing
ing on
onA-PET
A-PET material.
material. The
The tensile
tensile stress
stress of
of the
the breaking
breaking point
point of
of the
the recycled
recycled materials
materials
increased
increasedfrom
from15.5
15.5 Mpa
Mpa toto an
an average
averagevalue
value of
of 54.43
54.43Mpa
Mpa after
after just
just11 hh of
of UV
UVexposure
exposure
(4.9
(4.9Wh/m
Wh/m22))and
andremained
remainedsimilar
similareven
evenafter
afterprolonged
prolongedaging
aging(Figure
(Figure10).
10).
 Polymers 2023, 15, x FOR PEER REVIEW 9 of 16
Polymers 2023, 15, 4166 9 of 16

The breaking point of the specimens also clearly demonstrates the impact of UV
aging on A-PET material. The tensile stress of the breaking point of the recycled materials
Polymers 2023, 15, x FOR PEER REVIEW
increased from 15.5 Mpa to an average value of 54.43 Mpa after just 1 h of 9UV of 16
exposure
2
(4.9 Wh/m ) and remained similar even after prolonged aging (Figure 10).

Figure 10. Dependence of tensile stresses at break and UV irradiance.

The values of the relative elongation at the breaking force show a strong influence of
UV on the plastic properties (this dependence is shown in Figure 11). We observed a
strong decrease of the R_A-PET (black) films’ relative elongation from 16,84% to an aver-
age value of 5.61% after 1 h of UV exposure (2.45 Wh/m2), and one from 20.64% to an
Figure
Figure10.
average 10.Dependence
value of 5.19%
Dependence offor
tensile stresses
A-PET
of tensile at break
(clear)
stresses film and
afterUV
at break 2 hirradiance.
and of UV
UV exposure (4 Wh/m2).
irradiance.
The values of the relative elongation at the breaking force demonstrate the significant
impact Theofvalues
The onofthe
values
UV theplastic
of relative
the elongation
relative asatshown
elongation
properties, theatbreaking
the force
breaking
in Figure 11. show
Thereashow
force isstrong influence
a strong
a sharp of
influence
decrease of
UV
inUV on
theon the plastic
the plastic
relative properties
properties
elongation (this dependence
(this dependence
of the R_A-PET is shown
is shown in
(black) films—that in Figure
Figure
is, from 11). We
11). We
16.84% observed
averageaa strong
observed
to an
strong
of 5.61%decrease
decrease after
of the ofR_A-PET
just 1the R_A-PET
h of UV(black) (black)
exposure films’
(2.45
films’ relative
Wh/m
relative elongation
2). Similarly,
elongation from
the
from 16,84%
relative
16,84% totoananaverage
elongationaver-
of value
age
the value
of A-PET of 5.61%
(clear)1 film
5.61% after after 1 h
h of decreases of
UV exposure UV exposure
from(2.45
20.64% (2.452 Wh/m
to an average
Wh/m
2), and one from 20.64% to an
), and oneof 5.19%
from after
20.64% 2 h to
of UV expo- value
an average
average
sure value2).of 5.19% for A-PET (clear) film after 2 h of UV exposure (42 Wh/m2).
(4 Wh/m
of 5.19% for A-PET (clear) film after 2 h of UV exposure (4 Wh/m ).
The values of the relative elongation at the breaking force demonstrate the significant
impact of UV on the plastic properties, as shown in Figure 11. There is a sharp decrease
in the relative elongation of the R_A-PET (black) films—that is, from 16.84% to an average
of 5.61% after just 1 h of UV exposure (2.45 Wh/m2). Similarly, the relative elongation of
the A-PET (clear) film decreases from 20.64% to an average of 5.19% after 2 h of UV expo-
sure (4 Wh/m2).

Figure
Figure11.11.
Dependence of relative
Dependence elongation
of relative at break
elongation and UV
at break irradiance.
and UV irradiance.

The
Theeffect
valuesof UV aging
of the on plastics
relative is clearly
elongation demonstrated
at the by the
breaking force dependencethe
demonstrate of the
significant
work required to break the film, as shown in Figure 12. In this graph, we can see that even
impact of UV on the plastic properties, as shown in Figure 11. There is a sharp decrease in
the relative elongation of the R_A-PET (black) films—that is, from 16.84% to an average of
5.61% after just 1 h of UV exposure (2.45 Wh/m2 ). Similarly, the relative elongation of the
Figure 11. Dependence of relative elongation at break and UV irradiance.
A-PET (clear) film decreases from 20.64% to an average of 5.19% after 2 h of UV exposure
(4 Wh/m 2 ).
The effect of UV aging on plastics is clearly demonstrated by the dependence of the
work required to break the film, as shown in Figure 12. In this graph, we can see that even
Polymers 2023, 15, 4166 10 of 16

Polymers 2023, 15, x FOR PEER REVIEW 10 of 16

Polymers 2023, 15, x FOR PEER REVIEW 10 of 16
The effect of UV aging on plastics is clearly demonstrated by the dependence of the
work required to break the film, as shown in Figure 12. In this graph, we can see that even
after
afterexposing
exposing thethe
film to UV
film for 1for
to UV h (2.45 Wh/mWh/m
1 h (2.45 2 ), the
2), the work required to break the
work required to film de-
break
after exposing the film to UV for 1 h (2.45 Wh/m2), the work required to break the film de-the film
creases by
decreases about 2.26
by about times for recycled material and about 2.77 times for virgin material.
creases by about 2.262.26
timestimes for recycled
for recycled material
material and2.77
and about about 2.77
times fortimes
virginfor virgin material.
material.

Figure 12.
12.Dependence
Dependenceof UV irradiation on the
ontotal workwork
required to break
to the filmthe
(tensile test).
Figure
Figure 12. Dependence ofof
UV UV irradiation
irradiation on the the
totaltotal required
work required to break break
the film film (tensile
(tensile test). test).

By
Bydividing
dividing thethe
workworkrequired
requiredto break the specimens
to break of filmofinto
filmelastic and plastic
By dividing the work required to break the the specimens
specimens of film into into elastic
elastic and plastic
and plastic
zones,
zones, wewecan
can analyze
analyze thethe
details more
details closely.
more As we
closely. Ascan
we see
caninsee
Figure
in 13, even
Figure 13,after aging
even after aging
zones, we can analyze the details more closely. As we can see in Figure 13, even after aging
the
thefilms,
films, a alittle
littlemore
more workwork is required
is to perform
required to performelastic deformations,
elastic deformations, as the film
as thehasfilm has
the films, a little more work is required to perform elastic deformations, as the film has
hardened
hardened after
afterreceiving
receiving UVUV radiation.
radiation.After 4 h (19.6
After Wh/m 2), these2 ), values are almost
hardened after receiving UV radiation. After 4 h 4(19.6
h (19.6
Wh/m Wh/m
2), these these
valuesvalues are almost
are almost
unchanged,
unchanged, with thethework required to perform elastic deformations for thefor virgin film
unchanged, with the work required to perform elastic deformations for the virgin film film
with work required to perform elastic deformations the virgin
being
being about
about1.381.38J, and that for for
recycled material beingbeing
2.43 J. However, the work therequired
being about 1.38 J,J,and
and that
that recycled
for recycled material
material being 2.43 J.2.43 J. However,
However, the work work required
required
to perform plastic deformations decreases significantly, as we can see in Figure 14. The
to perform
performplastic
plasticdeformations
deformations decreases
decreases significantly, as weascan
significantly, wesee caninseeFigure 14. The14. The
in Figure
values of plastic deformations for unaged recycled film decrease from 4.42 J to 0.33 J and
values of
values ofplastic
plasticdeformations
deformations forfor
unaged
unaged recycled film film
recycled decrease from 4.42
decrease fromJ to 0.33
4.42 J and
J to 0.33 J and
remain similar for aged film. The virgin film decreases from 3.29 J to 0.23 J, a drop of 13.4
remain similar
remain similarforfor aged
agedfilm. The The
film. virginvirgin
film decreases from 3.29
film decreases J to 3.29
from 0.23 J,J atodrop
0.23ofJ,13.4
a drop of
times for recycled films and 14.3 times for virgin films.
timestimes
13.4 for recycled films and
for recycled films 14.3
andtimes
14.3for virgin
times forfilms.
virgin films.

Figure 13.
13.Dependence
Dependenceof UV irradiation on elastic region energy (tensile test). test).
Figure
Figure 13. Dependence ofof
UV UV irradiation
irradiation on elastic
on elastic region
region energy
energy (tensile
(tensile test).
Polymers 2023, 15, x FOR PEER REVIEW 11 of 16
Polymers 2023,
Polymers 2023,15,
15,4166
x FOR PEER REVIEW 11
11 of 16
of 16

Figure 14. Dependence of UV irradiation on plastic region energy (tensile test).

Figure 14. Dependence
Figure 14. Dependence of
of UV
UV irradiation
irradiation on
on plastic
plastic region
region energy
energy (tensile
(tensiletest).
test).

Puncture
Puncture impact
impacttests
testswere
wereperformed
performed to determine the the
nature of fracture during im-
Puncture impact tests were performed totodetermine
determine nature
the nature of fracture
of fracture during
during im-
pact, which
impact, can
which be
can either
be ductile
either or
ductile orbrittle. The
brittle. The Zwick/Roell
Zwick/Roell drop
drop weight
weight tester
testerrecorded
recorded
pact, which can be either ductile or brittle. The Zwick/Roell drop weight tester recorded
the
theforce during the short impact process, as shown in Figure 15. The force–time graphs
the force
force during
during thethe short
short impact
impact process,
process, as as shown
shown in in Figure
Figure 15.
15. The
The force–time
force–time graphs
graphs
reveal
revealthe first part of the impact, i.e., when the puncture probe hits the specimen. The
reveal the first part of the impact, i.e., when the puncture probe hits thespecimen.
the first part of the impact, i.e., when the puncture probe hits the specimen. TheThe
magnitudes
magnitudes of force and deflection were calculated to determine the energy required to
magnitudes of of force
force and
and deflection
deflection were
were calculated
calculated to to determine
determine the
the energy
energy required
required to
to
penetrate
penetrateA-PET
A-PETfilm filmspecimens.
specimens.
penetrate A-PET film specimens.

Figure 15. Force versus time diagram (100% virgin material, not UV-aged).
Figure 15. Force versus time diagram (100% virgin material, not UV-aged).
Figure 15. Force versus time diagram (100% virgin material, not UV-aged).
The force and deflection dependence curves of 100% virgin A-PET are presented in
The16
Figures force
andand deflection
17. The dependence
force and deflection curves of 100%
dependence virgin
curves A-PET are(50%
of R_A-PET presented
recycled in+
The force and deflection dependence curves of 100% virgin A-PET are presented in
Figures 16 and
50% virgin) 17. at
films The force and
different deflection
accelerated UV dependence
aging timescurves of R_A-PET
are presented (50% 18.
in Figure recycled
These
Figures 16 and 17. The force and deflection dependence curves of R_A-PET (50% recycled
+graphs
50% virgin) films atthat
demonstrate different
when accelerated
the films are UV aging times
exposed to UVare presented
aging, in Figureforce
the maximum 18.
+ 50% virgin) films at different accelerated UV aging times are presented in Figure 18.
These graphs
required demonstrate
to penetrate that whenofthe
the specimens films
virgin are exposed
A-PET to UV aging,
films decreases by 15%the maximum
and R_A-PET
These graphs demonstrate that when the films are exposed to UV aging, the maximum
force required
by 25%. This to penetrate
indicates the specimens
a significant of virginofA-PET
degradation filmsstrength
the film’s decreases by UV
after 15%aging.
and
force required to penetrate the specimens of virgin A-PET films decreases by 15% and
R_A-PET by 25%. of
The degradation This
theindicates a significant
film’s plasticity is alsodegradation
evident, as ofthethe film’s strength
deflection afteratUV
of the film the
R_A-PET by 25%. This indicates a significant degradation of the film’s strength after UV
maximum
aging. force decreases
The degradation to 25%
of the of plasticity
film’s virgin A-PET films
is also and even
evident, to 60%
as the of R_A-PET
deflection of the films.
film
aging. The degradation of the film’s plasticity is also evident, as the deflection of the film
at the maximum force decreases to 25% of virgin A-PET films and even to 60% of R_A-
at the maximum force decreases to 25% of virgin A-PET films and even to 60% of R_A-
PET films.
PET films.
 Polymers 2023, 15, x FOR PEER REVIEW 12 of 16
Polymers 2023, 15, x FOR PEER REVIEW 12 of 16
Polymers 2023, 15, x FOR PEER REVIEW 12 of 16
Polymers 2023, 15, 4166 12 of 16

Figure 16. Force and total energy versus deflection plots (specimen is 100% virgin film not UV-aged).
Figure 16. Force and total energy versus deflection plots (specimen is 100% virgin film not UV-aged).
Figure16.
Figure Forceand
16.Force andtotal
totalenergy
energyversus
versusdeflection
deflectionplots
plots(specimen
(specimenisis100%
100%virgin
virginfilm
filmnot
notUV-aged).
UV-aged).

Figure 17. Force versus deflection plots after UV aging of 100% virgin A-PET films.
Figure 17. Force versus deflection plots after UV aging of 100% virgin A-PET films.
Figure 17. Force versus deflection plots after UV aging of 100% virgin A-PET films.

Figure
Figure 18. Force versus
18. Force versus deflection
deflection plots
plots after
after UV
UV aging
aging of
of R_A-PET
R_A-PET films.
films.
Figure 18. Force versus deflection plots after UV aging of R_A-PET films.
FigureThe
18. Force versus
moment deflection
of the initial plots
crackafter UV agingcan
appearance of R_A-PET films.in tests of unaged A-PET
be observed
The moment of the initial crack appearance can be observed in tests of unaged A-PET
films,The
where
momentthe force
of thesuddenly decreases
initial crack appearanceslightly
can when
be thethe crack
observed opens.
in tests However,
of unaged this
A-PET
films,
Thewhere
momentthe force
of thesuddenly
initial decreases
crack slightlycan
appearance when
be crack in
observed opens.
tests However,
of unaged this
A-PETmo-
moment
films, could
whereonly only
the force be clearly
suddenly identified
decreases in unaged
slightly films.
when With
the even even
crackaopens. a little UV
However, aging, the
thisfilms
mo-
mentwhere
films, could the be clearly
force identified
suddenly in unaged
decreases slightly films.
when With
the crack little UV
opens. aging, this
However, the mo-
films become
ment could onlymorebe brittle,
clearly and the testing
identified machine
in unaged is no
films. longer
With evenable to capture
a little UV aging,the the
moment
films
ment
of thecould only
initial be clearly
crack opening. identified in unaged
Thus, only the graphsfilms.ofWith even a little
maximum forceUV andaging, theversus
energy films
 ance reaches 98 Wh/m2 (or after 40 h of accelerated UV aging).

become more brittle, and the testing machine is no longer able to capture the moment of the
initial crack opening. Thus, only the graphs of maximum force and energy versus UV irradi-
ance, presented in Figures 19–21, will be considered in the further analysis of the test results.
Polymers 2023, 15, 4166 Puncture resistance is a measure of the maximum force or energy required to 13 of 16
pene-
trate an A-PET film. Almost twice as much force is needed to penetrate R_A-PET films
compared to 100% virgin films (about 1150 N and 630 N for unaged films, respectively).
In
UVFigure 19, wepresented
irradiance, can see maximum
in Figures force
19–21,decreases by about 15–25%
will be considered when analysis
in the further the UV irradi-
of the
ance reaches 98 Wh/m (or after 40 h of accelerated UV aging).
test results. 2

Figure 19. Dependence of maximum force on UV irradiance.

The dependencies of the energy at the maximum force and the total energy required to
penetrate the specimens on UV irradiation were also obtained, and they are presented in
Figures 20 and 21. After the films receive 20 Wh/m2 of UV irradiation (or 8 h of accelerated
UV aging), the total energy required to penetrate the R_A-PET films decreases by 60%, and
that of the virgin films by 50%. After longer UV irradiation, the energy required to penetrate
the specimens decreases a little more (by about 5%) and remains similar. The total energy of
both film types aged with 98 Wh/m2 UV irradiation was almost equal (3.8 J and 3.0 J), alt-
Figure
hough 19.
theDependence
energies of of
themaximum force
new films differed
on UVby almost twice the amount (13.1 J and 6.6 J).
irradiance.

The dependencies of the energy at the maximum force and the total energy required to
penetrate the specimens on UV irradiation were also obtained, and they are presented in
Figures 20 and 21. After the films receive 20 Wh/m2 of UV irradiation (or 8 h of accelerated
UV aging), the total energy required to penetrate the R_A-PET films decreases by 60%, and
that of the virgin films by 50%. After longer UV irradiation, the energy required to penetrate
the specimens decreases a little more (by about 5%) and remains similar. The total energy of
both film types aged with 98 Wh/m2 UV irradiation was almost equal (3.8 J and 3.0 J), alt-
hough the energies of the new films differed by almost twice the amount (13.1 J and 6.6 J).

Figure 20.
20.Dependence
Dependenceofof
UV irradiation
UV on on
irradiation energy at maximum
energy forceforce
at maximum consumed to break
consumed A-PETA-PET
to break films.
films.

Puncture resistance is a measure of the maximum force or energy required to penetrate

an A-PET film. Almost twice as much force is needed to penetrate R_A-PET films compared
to 100% virgin films (about 1150 N and 630 N for unaged films, respectively). In Figure 19,
we can see maximum force decreases by about 15–25% when the UV irradiance reaches
98 Wh/m2 (or after 40 h of accelerated UV aging).
The dependencies of the energy at the maximum force and the total energy required
to penetrate
Figure the specimens
20. Dependence on UV irradiation
of UV irradiation on energy were also obtained,
at maximum and they
force consumed are presented
to break in
A-PET films.
Figures 20 and 21. After the films receive 20 Wh/m2 of UV irradiation (or 8 h of accelerated
UV aging), the total energy required to penetrate the R_A-PET films decreases by 60%,
and that of the virgin films by 50%. After longer UV irradiation, the energy required to
penetrate the specimens decreases a little more (by about 5%) and remains similar. The total
energy of both film types aged with 98 Wh/m2 UV irradiation was almost equal (3.8 J and
Polymers 2023, 15, 4166 14 of 16

3.0 J), although the energies of the new films differed by almost twice the amount (13.1 J
and 6.6 J).
This experimental research clearly shows that the film rapidly and significantly loses
its plasticity when it is even slightly exposed to UV light. As a result, the use of film in
thermal molding can become challenging. Products such as various packaging materials
Polymers 2023, 15, x FOR PEER REVIEW 14 of or
16
other products may crack or tear during the manufacturing process, due to the loss of the
film’s plasticity after exposure to UV light.

Figure 21. Dependence

Figure 21. Dependence of
of UV
UV irradiation
irradiation on
on the
the total
total energy
energy consumed
consumed to
to break
break A-PET
A-PET films.
films.
4. Conclusions
This experimental research clearly shows that the film rapidly and significantly loses
Two types of A-PET films were analyzed: A-PET (pure virgin material) and R_A-PET
its plasticity when it is even slightly exposed to UV light. As a result, the use of film in
(50% recycled and 50% virgin material). The films were aged in a UV chamber for 1 to
thermal molding can become challenging. Products such as various packaging materials
40 h; in other words, up to 98 Wh/m2 dose, with 2.45 W/m2 irradiation intensity. The
or other products may crack or tear during the manufacturing process, due to the loss of
results confirmed the significant impact of UV on the mechanical properties of the films,
the film’s plasticity after exposure to UV light.
particularly in the case of the R_A-PET material. The degradation of the properties was
best demonstrated by the calculated work required for elastic and plastic deformations. It
4. Conclusions
was found that exposing the A-PET film to UV light for just 1–2 h (up to 5 Wh/m2 under
Two types
2.45 W/m of A-PET
2 irradiation films were
intensity) analyzed:
caused A-PETloss
a significant (pure of virgin material)
its plasticity and R_A-PET
properties. Thus,
(50% recycled and 50% virgin material). The films were aged in a
films used in the thermoforming of packaging should be protected from direct sunlight. UV chamber for 1 to 40
h; in According
other words, upanalysis
to an to 98 Wh/m 2 dose, with 2.45 W/m2 irradiation intensity. The results
of chemical transformations in the PET under UV irradiation,
confirmed
there themain
are few significant
causesimpact
of theof UV on in
changes thethemechanical
mechanical properties
properties.of the
Thefilms,
mainparticu-
cause
larly intothe
seems be case of the R_A-PET
a crystalline material. The
amount increment in adegradation
PET. Authors of who
the properties
have analyzed was best
this
demonstrated
process in depthbyusing
the calculated work required
three different methods—DSC for elastic and plasticFTIR-ATM
thermogram, deformations. It was
spectrum,
found
and that exposing
density the A-PET
changes—have film to UV light
demonstrated for just
that there 1–2 h (up
is direct to 5 Wh/m
relationship 2 under 2.45
between crys-
W/m 2 irradiation intensity) caused a significant loss of its plasticity properties. Thus, films
talline amount and UV irradiation dose [13]. Moreover, this explains a plasticity decrement
used in UV
during the irradiation
thermoforming and aoftensile
packaging should
strength be protected
increment. Anotherfromresearcher
direct sunlight.
group states
that aAccording
decrementtoofan analysis ofproperties
mechanical chemical transformations
in PET can be induced in the PET under UV
via carboxyl irradia-
formation
tion, there
under are few main
UV irradiation causes of thethat
in environments changes in the
partially have mechanical
oxygen [24]. properties. The main
causePuncture
seems toimpact
be a crystalline
test resultsamount
showedincrement in a PET.PET
that the examined Authors
films who have analyzed
are extremely sensi-
this to
tive process in depth using
photodegradation three
under UV different methods—DSC
exposure. By contrast, virginthermogram,
PET is bitFTIR-ATM spec-
less sensitive; it
shows
trum, and50%density
of the fracture energy decrement
changes—have demonstrated afterthat
the there
first 8ish direct
of artificial UV exposure
relationship between in
acrystalline
UV agingamount
chamber, and 2 semi recycled PET film, marked
and UVitsirradiation
approximately 20 Wh/m
dose [13]. Moreover, this explains a plasticity dec-
R_A-PET,
rement duringshows UVhigher sensitivity
irradiation and a to UV irradiation
tensile (after theAnother
strength increment. same exposure,
researcher fracture
group
energy decreased
states that by 60%).
a decrement of mechanical properties in PET can be induced via carboxyl for-
mationA-PET
underfilms
UV used in the in
irradiation thermoforming
environmentsof packages
that partiallymust havebe protected
oxygen [24].from direct
sunlight
Puncture impact test results showed that the examined PET films are increases
when they are stored. Since the glass transition temperature extremelyafter sen-
sitive to photodegradation under UV exposure. By contrast, virgin PET is bit less sensitive;
it shows 50% of the fracture energy decrement after the first 8 h of artificial UV exposure
in a UV aging chamber, and its approximately 20 Wh/m2 semi recycled PET film, marked
R_A-PET, shows higher sensitivity to UV irradiation (after the same exposure, fracture
Polymers 2023, 15, 4166 15 of 16

UV aging [13,14], the technological process of thermoforming food packages and bottles
changes, and low-quality packages are obtained.
Since recycled PET is also used in personal protection products (e.g., face shields,
glasses, etc.), long-term use of these products outdoors in the sun (i.e., under UV exposure)
makes them not only less transparent but also more fragile, so they may break after
mechanical impact and injure the face.

Author Contributions: Methodology, data curation, project management, A.T.; methodology, experi-
mental investigation, validation, writing, M.V.; resources, experimental investigation, D.Š.; method-
ology, validation, writing, V.K.; data analysis, validation, review and editing, J.J.; resources, ex-
perimental investigation, P.M. All authors have read and agreed to the published version of the
manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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