applied

sciences
Review
A Review of Degradation and Life Prediction of Polyethylene
Yang Wang 1 , Guowei Feng 1 , Nan Lin 2, *, Huiqing Lan 3 , Qiang Li 4 , Dichang Yao 5 and Jing Tang 6

1 School of Mechanical Engineering, Xinjiang University, Urumqi 830046, China

2 Pressure Pipe Department, China Special Equipment Inspection and Research Institute, Beijing 100013, China
3 Laboratory of Vehicle Advanced Manufacturing, Measuring and Control Technology (Ministry of Education),
Beijing 100044, China
4 Xinjiang Uygur Autonomous Region Inspection Institute of Special Equipment, Urumqi 830000, China
5 Xinjiang Agricultural Machinery Quality Supervision and Management Station, Urumqi 830054, China
6 International Cultural Exchange College, Xinjiang University, Urumqi 830046, China
* Correspondence: [email protected]

Abstract: After around 50 years of development, the key substance known as polyethylene has been
extremely influential in a variety of industries. This paper investigates how polyethylene materials have
been used in the domains of water, packaging, and medicine to advance contemporary society in order
to comprehend the physical and chemical alterations that polyethylene undergoes after being subjected
to long-term environmental variables (e.g., temperature, light, pressure, microbiological factors, etc.).
For the safe operation of polyethylene materials, it has always been of the utmost importance to evaluate
polyethylene’s service life effectively. This paper reviews some of the most common literature journals
on the influence of environmental factors on the degradation process of polyethylene materials and
describes methods for predicting the lifetime of degradable polyethylene materials using accelerated
aging tests. The Arrhenius equation, the Ozawa–Flynn–Wall (OFW) method, the Friedman method, the
Coats–Redfern method, the Kissinger method and Kissinger–Akahira–Sunose (KAS) method, Augis
and Bennett’s method, and Advanced Isoconversional methods are all discussed, as well as the future
development of polyethylene.

Keywords: polyethylene; degradation; kinetic models; thermal analysis; life prediction

Citation: Wang, Y.; Feng, G.; Lin, N.;

Lan, H.; Li, Q.; Yao, D.; Tang, J. A
Review of Degradation and Life 1. Introduction
Prediction of Polyethylene. Appl. Sci.
Polyethylene is one of the most significant and useful polymers that has been extensively
2023, 13, 3045. https://doi.org/
studied for use as a plastic material [1–8]. The benefits of using polyethylene as a commercial
10.3390/app13053045
plastic material include its excellent mechanical properties, good flexibility, good chemical
Academic Editor: Theodore resistance, lightweight properties, good thermal stability, and high-cost performance [9,10].
E. Matikas The piping sector has been impacted by the trend of replacing steel with plastic during the
Received: 15 February 2023
past few decades, resulting in the steady replacement of metal-based pipes with plastic pipes.
Revised: 23 February 2023
Polyethylene pipes are the most commonly utilized among them [11,12]. Consider the case
Accepted: 25 February 2023
of high-density polyethylene pipes. Its market worth was USD 15.975 billion in 2018, and
Published: 27 February 2023 9.283 million tons were consumed each year. The service life of polyethylene pipes will not
be less than 50 years, and it will continue to grow at a rate of at least 5% annually in the
upcoming years [13,14].
Polyethylene has numerous applications in a wide range of industries, including agri-
Copyright: © 2023 by the authors. culture [15], manufacturing [16,17], medicine [18–20], construction [21,22], packaging [23],
Licensee MDPI, Basel, Switzerland. energy [24], outdoor items [25], and others, due to its technical benefits and low cost when
This article is an open access article compared to other materials. In China alone, the use of agricultural films reached 2.6 million
distributed under the terms and tons in 2016, including 1.47 million tons of polyethylene films, covering 18.4 million hectares of
conditions of the Creative Commons land [26].
Attribution (CC BY) license (https://
Although polyethylene materials offer great resistance to microbial, peroxide, and
creativecommons.org/licenses/by/
degrading damage, they do have a tendency to alter their initial performance characteristics
4.0/).

Appl. Sci. 2023, 13, 3045. https://doi.org/10.3390/app13053045 https://www.mdpi.com/journal/applsci

Appl. Sci. 2023, 13, 3045 2 of 18

with time [27–30]. In general, three frequent and significant occurrences are bound to
happen when polyethylene is present in a gaseous or liquid environment for an extended
period of time. The first phenomenon demonstrates that the mobility of polyethylene
molecules is altered by the diffusion of gas or liquid molecules, just as it is by changes in
temperature, pressure, or time, which also have an impact on the material’s mechanical
properties. The second phenomenon relates to the fact that, due to the extremely adhesive
nature of the amorphous phase attached to the crystalline skeleton, the physical aging of
polyethylene materials is destined to occur over extended periods in glassy amorphous
polymers or semi-crystalline polymers [31,32]. The third phenomenon demonstrates that
polyethylene is subject to aging and degradation processes when exposed to chemically
active gases or liquids for extended periods. As a result, brittleness [33], fracture [34],
bending [35], and other phenomena may occur, which may shorten the service life of
polyethylene products.
In general, it’s critical to comprehend the mechanisms of degradation in addition to
the elements that influence how polyethylene materials deteriorate over time. Researchers
must investigate polyethylene’s deterioration behavior and offer theoretical backing to
enhance the material’s performance and service life. However, there has not been a study
conducted yet that completely explains the degradation mechanism of polyethylene.
The aging degradation process of polymeric materials is described in this work as being
influenced by several common external environmental conditions. First, it enumerates the
common ways that polyethylene degrades in the environment and describes the effects
that these different elements have on the process. Second, illustrations of the fundamental
hypotheses and technical approaches employed in the experimental research carried out
thus far are provided. Finally, some thoughts and views are shared along with predictions
about polyethylene’s future trends.

2. Aging Degradation of Polyethylene

2.1. The Process of Degradation
Catalytic peroxide decomposition, direct interactions of metal compounds with organic
substrates, oxidation, and energy transfer during photolysis are the primary mechanisms of the
chemical degradation of polymers [36]. While the chemical structure of a polymer frequently
does not change much, polymer degradation involves a reduction in the polymer’s molecular
weight [37]. A macromolecular complex called a polymer is made up of big molecules with
repeating structural elements. Polymers are typically combinations of substances with various
chain lengths or substances with various molecular weights. The properties of polymers are
strongly affected by their molecular weight, and this is also one of the processes through
which macromolecular substances are created [38].
The primary source of the polymer degradation process is the continuous interaction
between oxygen and the polymer’s macromolecules, as well as free radicals created as a
consequence of environmental factors such as temperature, humidity, light, mechanical stress,
and radiation [39]. In addition, it appears to suggest a decrease in molecular weight, potential
branching, and, in a few cases, the formation of cross-linked structures [40]. The unstable
oxidized substances formed by degradation gradually converge towards the formation of
stable macromolecules with oxidation groups and cause significant changes in the molecular
structure, such as molecular weight, polydispersity, branching, etc. While other polymers
often migrate in the direction of lower molecular weights, the development of cross-linked
structures as mentioned above occurs primarily in the degradation of polyethylene.
For polyethylene materials, aging is bound to occur with extended use. Both aging and
degradation can have a significant impact on the performance of polyethylene. Exposure
to numerous environmental variables, such as heat, UV radiation, ozone, chemical attack,
mechanical stress, and microbes, can cause polyethylene to degrade, eventually resulting
in embrittlement, cracking, discoloration, etc. [41,42]. Understanding the primary stages of
polyethylene breakdown is crucial for this reason.
Appl. Sci. 2023, 13, 3045 3 of 18

2.2. Types of Degradation

Premature failure of polyethylene materials is caused by irreversible chemical reactions or
physical alterations. Abiotic and biodegradation are the two categories into which polyethylene
degrades. Biodegradation is the term used to describe the degradation caused by the action
of microorganisms that alter and consume polyethylene and change its properties. Abiotic
degradation is defined as deterioration caused by external environmental variables, such as
temperature and UV irradiation. Even though each of these two degradation mechanisms can
be used to classify the deterioration of polyethylene, the two types work together in nature [43].

2.2.1. Biodegradation
The process of biodegradation happens when microbial populations, other decomposing
organisms, or abiotic forces work together to break down biodegradable materials into
minute parts [44]. Three primary processes make up the biodegradation of polyethylene:
(1) biodegradation, which occurs when microorganisms grow on the polyethylene’s surface or
within it, altering its mechanical, physical, and chemical qualities; (2) biodegradation, which is
the process of having microorganisms break down a polymer into oligomers and monomers;
(3) assimilation, which is the process by which microbes acquire the requisite carbon, energy,
and nutrients from the breakdown of polymers and transform the carbon in the material into
carbon dioxide, water, and biologically necessary chemicals [45]. The chemical composition,
molecular weight, and crystallinity of the polymer, as well as other physical, chemical, and
biological aspects, all affect how effectively a substance degrades [46].
Biological factors that may cause the biodegradation of polyethylene include bacteria,
fungi, and microorganisms. Over the past few decades, numerous bacterial strains have
been found to interact with polyethylene, and research studies have shown that there are
already several genera of bacteria and a small number of genera of fungus that are able
to degrade polyethylene. Some of the categories are shown in Table 1. In reality, enzymes
choose particular functional groups. Generally, shorter chains, more amorphous parts,
and less complicated structures in polymers make them more susceptible to microbial
biodegradation [47].

Table 1. Bacterial and fungal strains linked to polyethylene biodegradation [48].

Fungiidae Fungal Species Bacteriaceae Bacterial Species

Simplicissimum Amyloliquefaciens
Penicillum Frequentans Bacillus Brevies
Pinophilum Cereus
Versicolor Streptomyces Badius
Aspergillus
Flavus Viridosporus
Phanerochaete Chrysosporium Rahnella Aquatilis
Verticillium Lecanii Rhodococcus Rhodochrous
Cladosporium Cladosporioides Brevibacillus Borstelensis

2.2.2. Non-Biodegradable
The abiotic degradation of polyethylene is influenced by environmental and molecular
factors. The breakdown of polyethylene is promoted and accelerated by environmental ele-
ments such as sunlight’s UV radiation, oxygen, heat, water, certain animals, and contaminants.
The combined action of these factors may have a synergistic effect on the degradation rate of
polyethylene [49]. Photoreactions and thermal oxidation reactions, which result in the creation
of new products during chain breakage, hydrogen atom detachment, or cage effects, are the
main environmental drivers of polymer degradation [50].
The interaction between oxygen and UV light causes polyethylene to begin to photode-
grade. While photodegradation is the process by which molecules produce free radicals,
photooxidation is the process by which polymers are destroyed by absorbing photons of visible,
 degradation rate
degradation rate ofof polyethylene
polyethylene [49]. [49]. Photoreactions
Photoreactions and and thermal
thermal oxidation
oxidation reactions,
reactions,
which result
which result in in the
the creation
creation of of new
new products
products during
during chain
chain breakage,
breakage, hydrogen
hydrogen atom atom de-de-
tachment, or
tachment, or cage
cage effects,
effects, are
are the
the main
main environmental
environmental drivers drivers of of polymer
polymer degradation
degradation [50]. [50].
The interaction
The interaction between
between oxygen
oxygen and and UVUV light
light causes
causes polyethylene
polyethylene to to begin
begin to to photo-
photo-
degrade. While
degrade. While photodegradation
photodegradation is is the
the process
process by by which
which molecules
molecules produce
produce free free radi-
radi-
Appl. Sci. 2023, 13, 3045 4 of 18
cals, photooxidation
cals, photooxidation is is the
the process
process by by which
which polymers
polymers are are destroyed
destroyed by by absorbing
absorbing pho- pho-
tons of
tons of visible,
visible, ultraviolet,
ultraviolet, or or infrared
infrared light
light in
in the
the presence
presence of of oxygen
oxygen [51].
[51]. Random
Random chain chain
breakage and
breakage and photooxidation
photooxidation are are the
the primary
primary outcomes
outcomes of of photodegradation,
photodegradation, and and these
these
ultraviolet,
processes in
processes orturn
in infrared
turn cause
causelight in the presence
secondary
secondary of oxygen
crystallization
crystallization [51].
and
and the
theRandom
creationchain
creation breakage
of several
of several and pho-
degradation
degradation
tooxidation
products, are the primary
products, including
including outcomes
carboxylic
carboxylic of photodegradation,
acids,
acids, ketones, and
ketones, and thesewhich
and aldehydes,
aldehydes, processes
which areincollectively
are turn cause
collectively
secondary
known as
known crystallization
as carbonyl
carbonyl compounds and the creation
compounds [52,53]. of
[52,53]. The several
The Norrish degradation
Norrish reaction products,
reaction can can result including
result inin the carboxylic
the synthesis
synthesis of
of
acids,
vinyl ketones,
vinyl groups
groups (suchand aldehydes,
(such as as unsaturatedwhich
unsaturated bonds are collectively
bonds and and conjugatedknown as
conjugated systems), carbonyl
systems), and compounds
and it it is
is crucial
crucial [52,53].
to re-
to re-
The
alizeNorrish
alize that reaction can result
that hydroperoxides
hydroperoxides are in the synthesis
are byproducts
byproducts of the
of theoffree
vinyl
free groups
radical
radical (such as process
formation
formation unsaturated [54].bonds
process [54]. In ad-
In ad-
and conjugated
dition to the systems),
breakdown and
of it is
hydrogen crucial to
peroxide,realize that
Norrish hydroperoxides
types
dition to the breakdown of hydrogen peroxide, Norrish types I and II processes involving I and II are
processesbyproducts
involving of
the free groups
ketone
ketone radical
groups formation
can also
can process
also start
start [54]. In additionof
the photooxidation
the photooxidation oftopolyethylene
the breakdown
polyethylene ofas
[55],
[55], hydrogen
as shown in
shown peroxide,
in Figures
Figures
Norrish types I and II processes involving ketone groups can also start the photooxidation
11 and
and 2.2. Chain
Chain breakage
breakage and and cross-linking
cross-linking are are the
the primary
primary and and secondary
secondary outcomes
outcomes of of
of polyethylene [55], as shown in Figures 1 and 2. Chain breakage and cross-linking are the
these three
these three starting
starting processes,
processes, respectively.
respectively.
primary and secondary outcomes of these three starting processes, respectively.

Figure1.
Figure
Figure 1.Polyethylene
1. Polyethylenebreakdown
Polyethylene breakdownproducts
breakdown productsare
products aredepicted
are depictedschematically
depicted schematically[56].
schematically [56].
[56].

Figure2.
Figure
Figure 2.Two
2. Twotypes
Two typesof
types ofNorrish
of Norrishreaction
Norrish reaction[57].
reaction [57].
[57].

Theprocess
The
The processby
process bywhich
by whichheat
which heatoror
heat orhigh
high
high temperatures
temperatures
temperatures are
areare applied
applied
applied atomaterial,
to to aa material,
material, product,
product,
product, or
component
or component
or component andandwhere
and thethe
where
where outcome
the outcome
outcome is is
ais loss
aa loss
lossofof
physical,
of physical,chemical,
physical, chemical,or
chemical, orelectrical
or electricalqualities
electrical qualities
qualities
is
is referred
is referred totoas
to as"thermal
as “thermal
"thermal degradation”
degradation"
degradation" [58].
[58]. [58].
Free Free
Free radical
radicalradical
chainschains
chains that are
that arethat are engaged
engaged
engaged in
in thermal
in thermal
thermal
and and photodegradation
and photodegradation
photodegradation have have fundamentally
have fundamentally
fundamentally identical identical
identical processes.processes.
processes. Typically,Typically,
Typically, degreethe
the degree
the to
to
degree
which the
which to which
the reaction the reaction
reaction with
with oxygenwith
oxygen takes oxygen
takes place takes
place has place has
has aa significant a significant
significant impact
impact on impact
on the on
the mechanism
mechanism the
mechanism
and rate
and rate of and rate of degradation.
of degradation.
degradation. molecularThe
The molecular
The molecular reactions
amplification
amplification amplification
reactions reactions
are mostly
are mostly are mostly
chain-breaking
chain-breaking
chain-breaking
reactions whenreactions
reactions when oxygen iswhen
oxygen is present
presentoxygen
[47]. is present [47].
[47]. Depending
Depending on the
on Depending
the physical and
physical on chemical
and the physical
chemical and
makeup
makeup
chemical makeup of the polymer, for which many thermal degradation mechanisms exist,
thermal degradation may cause molecular deterioration. The most frequent is the polymer’s
intermolecular links being broken or unchained, releasing oligomers and monomer units.
Some polymer backbone and side chain reactions will also contribute to the polymer’s final
decomposition [59].
One of the crucial components of abiotic degradation’s parameters is chemical degra-
dation. The characteristics of polyethylene macromolecules may change as a result of
reactions with atmospheric contaminants and some agrochemicals. Many materials must
come into contact with air when used in daily life, making reactions with oxygen in the air
simple. Free radicals are created when the covalent bonds in polyethylene react with the
oxygen molecules in the air. The covalent bonds of polyethylene are subject to oxidative
degradation, which is dependent on the chain structure of polyethylene and works in
conjunction with photodegradation to form free radicals. Peroxyl radicals from oxidative
Appl. Sci. 2023, 13, 3045 5 of 18

degradation can also act on polyethylene and cause cross-linking or chain breakage, just
like the byproducts of the Norrish reaction stated above. Another process that might lead to
the chemical breakdown of polymers is hydrolysis reaction [60–62]. It is significant to note
that because polyethylene molecules are entirely composed of alkyl groups and lack any
radical energy groups that could interact with water molecules, they cannot be hydrolyzed.
As the name suggests, catalytic degradation refers to the use of catalysts to break
down polyethylene. Typically, catalytic degradation is employed in scientific research or to
degrade polyethylene materials. The use of an appropriate catalyst and optimal processing
conditions might result in the development of the intended, more precise product, and, in
some situations, prevent the formation of inferior products, giving catalytic degradation
some advantages over the other degrading methods previously discussed [63]. The ability
to shorten experiment durations and lower reaction temperatures during studies is a more
significant benefit of catalytic degradation.
Polyethylene experiences mechanical degradation most frequently as a result of the
influence of various stresses on the material. These forces can occur for a variety of
reasons. For example, buried polyethylene pipes may experience operational issues during
installation, and wild animals may unintentionally harm them as a result of the pressure that
the soil and carried material exert on them [45]. This also applies to polyethylene products
used outside, such as mulch film and protective jackets used on some cables, which may
experience multiple mechanical degradations under unforeseen outdoor conditions [64–66].
In general, damage to polyethylene materials caused by macroscale factors, including soil
or water pressure, may not be immediately noticeable but may start to have an impact at the
microscopic molecule level. Even though mechanical causes are not the primary cause of
degradation, once a material has been mechanically traumatized, it may be more susceptible
to the effects of biodegradation [59]. Under field circumstances, mechanical forces and other
abiotic parameters (such as humidity, radiation, and contaminating substances) interact
with polyethylene material.

2.3. General Mechanism of Degradation

Various types of polymers have different degradation mechanisms. The deterioration of
polymeric materials may involve multiple degradation pathways at once [67]. Bond fractures
in the polymer’s backbone are the main method by which they degrade, and these breaks
can occur anywhere in the chain or at the ends of the chain due to random generation. A
frequently used mechanism in the breakdown of polymers is the chain-break decomposition
mechanism. A multi-step free radical chain reaction with the general properties of such
reaction mechanisms as initiation, proliferation, branching, and termination is involved in the
chain-breaking breakdown process [68].
Free radicals are produced in both induced reactions—when a chain break happens
at a random location in the main chain—and the terminal chain breaks reactions, where
such a tiny unit or group is broken at the end of the main chain [59]. The following is the
reaction sequence:
heat,light
R−H → R· + H · (1)
The proliferative process begins with a free radical reaction with oxygen molecules,
then produces a peroxide radical, a hydroperoxide group with hydrogen atoms, and finally,
a peroxide radical with oxygen molecules [69]. The resulting groups are extremely unstable
and readily decompose into renewable free radicals. The following is the reaction sequence:

R· + O2 → ROO· (2)

ROO· + RH → R· + ROOH (3)

ROOH → RO· + ·OH (4)
RO· + RH → R· + ROH (5)
Appl. Sci. 2023, 13, 3045 6 of 18

OH + RH → R· + H2 O (6)
Taking over a hydrogen atom or another atom on a carbon atom next to a radical from
another chain is known as a “termination reaction”. The following is the reaction sequence:

R· + R · → R − R (7)

2ROO· → ROOR + O2 (8)

R· + ROO· → ROOR (9)
R· + RO· → ROR (10)
HO· + ROO· → ROH + O2 (11)
Both biotic and abiotic circumstances, such as photooxygenation, can cause the afore-
mentioned degradation pathways to occur in polymeric materials. From a macro per-
spective, the biodegradation process can be broken down into three stages. In the first
stage, a particular enzyme secreted by microorganisms can lead to the depolymerization
of polyethylene molecular chains. In the second stage, the microorganisms absorb the
products of the first stage and transform them into the energy they need. In the third stage,
the microorganisms use these products to finish their own cellular metabolism and convert
them into other compounds [47].
In conclusion, the degradation of polymers under actual conditions is frequently a
combination of various degradation mechanisms because the mechanism of degradation of
polymers is quite complex and no one mechanism can fully describe the situation. For our
investigation into the service life of polyethylene materials, it is crucial to comprehend the
biotic and abiotic causes of degradation.

3. General Service Life of Polyethylene

Due to their strength, durability, and low cost when compared to other materials,
polyethylene-based products are frequently seen in daily life. This low cost significantly
lowers manufacturing costs and promotes the sustainable growth of the global economy.
Polyethylene materials are commonly used for the packaging of food products. The
materials used to create food packaging are produced in a way that does not detract from
the food’s flavor, appearance, or nutritional value. In order to ensure that the shelf life of
the packaging material is longer than the shelf life of the food itself, it is crucial to safeguard
the food’s quality. This is because the substances in the packaging material may spread
into the food and harm it.
High-density polyethylene, which is frequently used for cable sheathing and has an
initial design life of roughly 50 years, typically does not last as long as predicted outdoors
due to numerous uncontrollable circumstances. Due to prolonged exposure to UV light, the
cable sheath typically cracks after fewer than 10 years of operation in terms of ultraviolet
light alone [70].
Natural gas and drinking water are both transported via polyethylene pipes because
of their flexibility, light weight, ease of connecting between pipes, and comparatively low
installation costs [71]. The polyethylene material will deteriorate and age with continued
use, which will affect the pipe’s functionality. Premature pipe damage can result in major
safety issues, such as gas leaks, which can seriously endanger people’s lives and property.
Premature pipe damage also causes inconveniences in our daily lives. The DuPont Com-
pany has been employing polyethylene pipes to transmit natural gas on a massive scale
for about 57 years [72], but the lifespan of the pipeline cannot be ignored due to the rising
safety issues.
Notable medical uses for polyethylene include complete hip replacements. One of the
best therapies for advanced femoral head necrosis is total hip replacement, which typically
has a lifespan of at least ten years [20]. Traditional polyethylene has been replaced with highly
cross-linked polyethylene since it is extremely prone to wear and tear during use [73].
Appl. Sci. 2023, 13, 3045 7 of 18

Materials made of polyethylene are frequently employed in horticulture and agriculture.

Films are the primary form of application in agriculture [65], and they are typically used as mulch
to cover crops [74]. By more effectively blocking all types of weather that are not favorable for
crop growth, such as violent storms, polyethylene mulch can reduce the growth of weeds, retain
the moisture and nutrients needed by crops [66], and provide a desirable growing environment
for crops. In order to prevent soil contamination, polyethylene mulch is recycled after use and
normally lasts a few months to a year outdoors [75]. If polyethylene film breaks down while in
use, the ensuing degradation chemicals may be environmentally hazardous. They may also
seep into rivers and contaminate the water [76]. To prevent unwanted environmental pollution,
it is crucial to recycle polyethylene film within a set time range.
Polyethylene has many other applications that we will not discuss here, but in sum-
mary, it is critical to precisely estimate the material’s performance to precisely predict the
material’s life during its service life.

4. General Service Life of Polyethylene

Understanding the degradation process is crucial for polyethylene applications. To
gauge the degree of performance degradation of the product, or, in other words, to further
gauge the robustness of polyethylene products in long-term use situations, it is important
to first comprehend how long the process of degradation takes to become obvious [47]. As
a result, when carrying out pertinent experimental tests, the material’s aging must be sped
up [77]. Accelerated aging techniques are useful for estimating the remaining useful life
of polymeric materials like polyethylene, and they can be contrasted to choose the most
appropriate technique [78–83].
According to a widely used standard protocol for accelerated aging tests, polyethylene
materials are put through cyclic tests in one or more substances for a specified amount
of time or a specified number of cycles. To alter the effect of the same substance, the
content of the substance utilized as a variable in this test procedure should be significantly
different from the level of the substance itself during usage [84–86]. Depending on the
needs of the experiment, these studies are typically carried out in suitable climate chambers
where polyethylene samples may be exposed to high temperatures or humidity [87,88], UV
radiation [89,90], various acids, bases, salts, etc. [91]. The parameters, which are dependent
on the particular test conditions, must be decided upon as the initial stage in constructing
an accelerated aging technique [92]. The ability to manage whether environmental elements
are increasing or decreasing has a significant impact on the test’s dependability [93]. In a
perfect scenario, the environmental elements that the experiment simulates would be as
similar to those in the natural state as possible, and the experiment’s duration would be
kept to a minimum. The level of testing that is being conducted now, however, is still far
below what is optimal for experiments.

5. Prediction Techniques for Polyethylene Materials

5.1. Thermogravimetric Analysis for Kinetic Modeling
In recent decades, predicting the lifetime of polymeric materials such as polyethylene
has become a significant research issue [94–96]. The mass decomposition of materials that
are linearly dependent on time and temperature can be determined using thermogravimet-
ric analysis (TGA) [97], which is frequently used to research the mass decomposition and
kinetics of polyethylene materials. It is challenging to study each stage of the polyethylene
breakdown process separately using a straightforward kinetic model because of how com-
plex it is [98,99]. Approaches based on single-step approximations, either model-free or
model-fitting methods, are typically employed to explain polyethylene dynamics [100].
The degree of conversion that changes with time or temperature is referred to as
the reaction rate in thermogravimetric analysis research, and the conversion rate α is
determined using Equation (12) in terms of mass loss.

ωo − ωt ∆ω
α= = (12)
ωo − ω∞ ∆ωo
Appl. Sci. 2023, 13, 3045 8 of 18

where ωo , ωt , and ω∞ stand for the initial mass, the mass at temperature t, and the final
mass, which is the mass at which the mass loss is practically constant, respectively. The
product of two functions, one of which is dependent on temperature T and the other on
the rate of the reaction, is typically used to indicate the conversion rate of a kinetic process.
The general kinetic model of degradation is defined by Equation (13) [101]:

dα
= K ( T ) f (α) (13)
dt

where f (α) is the transformation function, and K(T) is the temperature-dependent function
given by the Arrhenius Equation (14) [102].
− Ea /RT
K ( T ) = Ae (14)

Thus, Equation (13) can be further written as:

 
dα Ea
= Aexp − f (α) (15)
dt RT

where A is the pre-exponential factor, Ea is the activation energy, and R is the gas constant.
The reaction model has various forms, some of which are shown in Table 2.

Table 2. Kinetic model and its conversion function [100].

Kinetic Model Symbol f(α)

n-order reactions
First order F1 1−α
Second order F2 (1 − α )2
nth order Fn (1 − α ) n
Diffusion
1-D diffusion D1 1/2α
2-D diffusion D2 [− ln(1h− α)]−1
2 1
i
3-D diffusion–Jander D3 3/2(1 − α) 3 1 − (1 − α) 3
1 −1
3-D diffusion–Ginstling–Brounshtein D4 3/2 [(1 − α)− 3 − 1]
Phase-boundary reactions
1
Contracting area R2 2(1 − α ) 2
2
Contracting volume R3 3(1 − α ) 3
Prout–Tompkins B1 α (1 − α )
expandedProut–Tompkins Bn (1 − α ) n α m
First order withautocatalysis C1 (1 − α)(1+KcatX )
nth order withautocatalysis Cn (1 − α)n(1+KcatX )
Nucleation and nuclei growth
1
Avrami–Erofeev A2 2(1 − α) [− ln(1 − α)] 2
2
Avrami–Erofeev A3 3(1 − α) [− ln(1 − α)] 3
n −1
Avrami–Erofeev An n(1 − α) [− ln(1 − α)] n

5.2. Arrhenius Equation

5.2.1. General Arrhenius Equation
Accelerated aging experiments offer a reliable foundation for estimating the life of
polyethylene materials. Temperature influences the time to failure or aging efficiency of
polyethylene materials, and both factors are important for more accurately estimating the
performance of polyethylene materials. The Arrhenius connection is the foundation of the
most significant method for polyethylene aging. Svante Arrhenius, a Swedish chemist,
Appl. Sci. 2023, 13, 3045 9 of 18

presented the Arrhenius equation (Equation (14)) in 1889. It is an empirical chemical kinetic
equation that describes the rate of reaction as a function of temperature [103]. The depen-
dence of the kinetics of some simple chemicals’ chemical reactions on the critical element of
temperature is extremely well described by the Arrhenius equation. The material produces
Appl. Sci. 2022, 12, x FOR PEER REVIEW 10 of 20
a very modest reaction rate at very low temperatures, according to the Arrhenius equation,
yet
Appl. Sci. 2022, 12, x FOR PEER REVIEW
the minimum value will not be zero. The following conditions must be met to
10 of 20
use the
Arrhenius equation: (1) There must be only one main chemical reaction that causes thermal
chemical reaction
deterioration should
within serve astemperature
a specific the test's starting
range,point
and[104–107]. (2) First-order
this significant chemical or other
reaction
fixed-order kinetics govern the process of degradation [105,108]. (3)
should serve as the test’s starting point [104–107]. (2) First-order or other fixed-order The degradation does
kinet-
chemical
not reaction
appreciably should
alter atofservezero.
time as the(4)
test's starting
There point no
has been [104–107].
phase (2) First-order
change or other
[106,107]. (5) The
ics govern the process degradation [105,108]. (3) The degradation
fixed-order kinetics govern the process of degradation [105,108]. (3) The degradation does
does not appreciably
experimental
alter study's(4)
at time zero. temperature range wasphase
somewhat constrained to(5)
prevent the accu-
not appreciably alter at There has (4)
time zero. been no
There has beenchange
no phase [106,107].
change [106,107].The (5)
experimental
The
racy
study’s of the test results
temperature from being impacted
range was somewhat by further
constrained degradation
to prevent mechanisms
the accuracy [109]. (6) test
of the
experimental study's temperature range was somewhat constrained to prevent the accu-
Throughout
results the test's deterioration range, the activation energy should remain constant
racy offrom being
the test resultsimpacted
from being byimpacted
further degradation mechanisms
by further degradation [109]. (6)
mechanisms Throughout
[109]. (6)
[110].
the The non-exponential
test’s deterioration
Throughout
form of Equation
range, therange,
the test's deterioration activation (16) can be used
energy energy
the activation
to
shouldshouldrepresent
remain the
constant
remain
Arrhenius
[110]. The
constant
equation,
[110]. Themaking
non-exponential it simpler
form
non-exponential to use
form of and
of Equation allowing
(16)
Equation can(16) for
be can
usedgraphical
be to tointerpretation
represent
used [111]: equation,
the Arrhenius
represent the Arrhenius
equation, making it simpler to use and allowing for graphical
making it simpler to use and allowing for graphical𝐸interpretation [111]: interpretation [111]:
𝑎
ln 𝐾(𝑇) = ln 𝐴 − (16)
𝐸𝑎𝑅𝑇Ea
ln
ln𝐾(𝑇)
K ( T )==lnln
𝐴− −
A 𝑅𝑇 (16) (16)
RT
However, it is not accurate enough to detect the aging process of the material with a
single experiment,
However,
However, it so
notitaccurate
it isisnot is necessary
accurate enough totolearn
enough more
detect about
the aging
to detect the the change
process
aging curve
of theofmaterial
of the material
process material
with a with
properties
single versus
experiment, time
so itunder
is several
necessary experimental
to learn more conditions,
about the as
changeshown
curve
a single experiment, so it is necessary to learn more about the change curve of materialin Figure
of 3,
materialand
properties
use it as a versus timefor
foundation under several
material experimental
life speculation. conditions, as shown in Figure 3, and
properties versus time under several experimental conditions, as shown in Figure 3, and
use it as a foundation for material life speculation.
use it as a foundation for material life speculation.

Figure
Figure 3.3.Variation
Figure3. Variation in
Variation in material
in material characteristics
materialcharacteristics asasaas
characteristics afunction
function
ofof temperature
temperature
a function of andand time
time
temperature and [112].
[112].
time [112].

By
By plotting
plotting the
Byplotting therelationship
the relationship
relationship between
between
between lnK(T)
lnK(T) and
and
lnK(T) 1/T
and1/T
in in
1/Tthethe equation's
inequation's
the linear
linear
equation’s relation-
relation-
linear relation-
ship,
ship, the
the least
least squares
squares method
method can
can be
be used
used totobest fit
best the
fit data.
the data.It is
It possible
is to
possible
ship, the least squares method can be used to best fit the data. It is possible to calculate calculate
to for for for
calculate
EEEa aand
a
andA
and AAthe
the slope
the slope and
slope andintercept
intercept
interceptof the
ofof
thefitted
fitted
the line
fitted asasshown
line
line shown
as in in
shown Figure
Figure4. 4. 4.
in Figure

Figure 4. Variation in material characteristics [112].

Figure 4.
Figure 4. Variation
Variation in
in material
materialcharacteristics
characteristics[112].
[112].
Appl. Sci. 2023, 13, 3045 10 of 18

5.2.2. The modified Arrhenius Equation

The Arrhenius equation has undergone several revisions, and the updated equation
now accounts for the impact of relative humidity on the rate of degradation (Equation (17))
[105,106,113–115]:
Ea
ln K ( T ) = ln A − + B(%RH ) (17)
RT
where lnK(T) is affected linearly by the humidity sensitivity component B at a constant
temperature. In the examined range, it is presumed that the relative humidity has an impact
only on the molecular mobility and not on the reaction route [106,114]. The frequency of
molecule collisions determines the degree and extent of a substance’s migration within a
material, which is known as molecular mobility [106]. Equation (18) can be used to get B
from the intercept of the line to B at constant temperature, where lna-Ea /RT is a constant
term. Equation (18) can also be used to calculate B from the slope of lnK(T) to %RH:

ln K ( T ) = intercept + B(%RH ) (18)

Numerous investigations have conclusively demonstrated that some degradation processes

can be adequately characterized by straightforward linear Arrhenius equations [116–119]. As
Arrhenius is dependable, time-efficient, and makes it simple to compute changes in aging
performance, it is the approach of choice for life prediction in the majority of studies. On the
basis of these examples, it can be demonstrated that the Arrhenius equation may be used to
forecast the life of polymeric materials other than polyethylene.

5.3. Equal Conversion Rate Method

One of the more trustworthy kinetic approaches for working with thermal analysis
data is the equal conversion rate method [120,121]. The main benefit of isoconversion
methods, which are based on the isoconversion principle, is that they do not necessitate the
assumption of any kind of reaction model f (α) in order to calculate the effective activation
energy Ea . Thermal analysis techniques can also be used to measure changes in the overall
reaction rate. Analyzing the change in Ea reveals the change in the response mechanism.
This method is known as Ea -dependence [122].
To create a more accurate activation energy Ea as a function of the degree of conversion
α, the equal conversion rate technique calls for trials at various temperatures. As a result
of the significant variation of Ea with α, which suggests that the process is kinetically
complex, the Ea -dependence was evaluated using the isotransformation rate method and
used as a foundation for kinetic analysis in order to comprehend the intricate nature of the
experiment’s process and produce accurate kinetic predictions [123].

5.3.1. Ozawa–Flynn–Wall (OFW) Method

Based on the mass loss and temperature data of the polyethylene material at various
heating rates, the Ozawa–Flynn–Wall (OFW) approach calculates the activation energy Ea
of the thermal degradation process [124]. The complexity of the decomposition mechanism
can be ascertained using this method, which does not necessitate prior knowledge of the
steps of the degradation mechanism used by the material. Instead, the activation energy
for various conversion rates can be assessed. The conversion rate α and the reaction model
g(α), which are integrated based on the Doyle approximation, are considered constants in
this method despite variations in the heating rate [125] as shown in Equation (19) [126,127]:

AEa Ea
ln β = ln − 5.331 − 1.052 (19)
Rg(α) RTp

where β is the heating rate, Ea is the activation energy, R is the gas constant, and Tp is the
peak temperature. The experimental thermal spectra captured at the heating rate can be
used to derive a linear regression of ln β = f (1/T ), and the slope of the straight line can be
used to calculate the activation energy Ea at a constant conversion rate α [126].
Appl. Sci. 2023, 13, 3045 11 of 18

The Ozawa–Flynn–Wall (OFW) method can be used in reaction systems where the
activation energy changes over time; however, it may not work when various reaction types
with various activation energies coexist. Additionally, competitive responses involving
a range of different products cannot be studied using the Ozawa–Flynn–Wall (OFW)
Method [128].

5.3.2. Friedman Method

The integral and differential approaches make up the equal conversion rate method [120,129].
In the differential approach, one of the simplest ways to determine the activation energy is by the
Friedman method [130] as shown in Equation (20):

dα Ea
ln = ln A + ln f (α) − (20)
dt RT

Equation (20) can be further expressed as follows when several runs with various
constant heating rates are taken into account and given values for [131]:

dα Ea
ln β = ln A + ln f (α) − (21)
dt RT

According to the experimental thermal spectrum captured at the heating rate, the
graph of ln( βdα /dt ) vs. 1/T should be a straight line for the conversion α = constant [100].
α is constant when ln A + ln f (α) is constant, despite the fact that the heating rate β is
varied [132]. By taking fixed readings of the conversion rate α, temperature T, and reaction
rate dα /dt , the activation energy Ea may be estimated from the slope denoted by ln(dα /dt )
for tests carried out at various heating rates [131].
The Friedman approach is more precise than the integral method while not using
mathematical approximations such as other integration methods. However, given the
potential variability of the reaction rate, the Friedman approach necessitates a high base of
thermal analysis equipment [120,133]. Any test, including dynamic and isothermal tests,
can be subjected to the Friedman model. Due to experimental flaws or the inherent uncer-
tainty of the differential approach, this method’s sensitivity to noise makes it potentially
less reliable for kinetic data acquired by thermogravimetric analysis (TGA) [131].

5.3.3. Coats–Redfern Method

The Coats–Redfern method is an integral approach based on an equation and con-
nected to the thermal deterioration mechanism (22) [134]:
   
g(α) AR Ea
ln 2
= ln − (22)
T βEa RT

where the finger front factor A can be calculated from the intercept of the straight
 line, the
activation energy Ea can be calculated from the slope of the line drawn between ln g(α)/T 2
and 1/T, and g(α) can vary depending on the model and mechanism of the reaction.

5.3.4. Kissinger Method and Kissinger–Akahira–Sunose (KAS) Method

The original Kissinger method was proposed in 1957, and Kissinger made the premise
that the experimental conditions barely affect the reaction rate and that it reaches a maximum
at a temperature Tp that corresponds to a specific conversion rate α. In this instance, only
non-isothermal conditions are suitable for determining the manifest activation energy Ea
of the crystallization process, which is proportional to the slope of the maximum value
corresponding to the crystal temperature. The heating rate β often affects the conversion rate
α. The Kissinger equation is shown in Equation (23) [135]:

β AR Ea
ln( 2
) = ln( )− (23)
Tp Ea RTp
Appl. Sci. 2023, 13, 3045 12 of 18

where Tp is the peak temperature, and the activation energy Ea can be obtained from the
slope of the line ln( β/Tp2 ) to 1/Tp .
According to the Kissinger–Akahira–Sunose (KAS) technique, the activation energy is
assumed to be constant for a specific conversion rate [136,137]. The method is based on
Equation (24) [138,139]:  
β AR Ea
ln( 2 ) = ln − (24)
Tp Ea f ( α ) RTp

where the ln( β/Tp2 ) versus 1/Tp curve is a straight line, and the slope and intercept can be
used to calculate the activation energy Ea and the value of pre-exponential factor A for a
given type.
The Kissinger–Akahira–Sunose (KAS) method corrects some biases in the Ozawa–Flynn–Wall
(OFW) method by using the Coats–Redfern approximation, and the Kissinger–Akahira–Sunose
(KAS) method provides a more accurate estimate of the activation energy [133,134].

5.3.5. Augis and Bennett’s Method

The Kissinger method began by not specifying the number of reaction levels, thereby
determining the activation energy of the n-level reaction. Regardless of the fitted kinetic
model, the method allows for the determination of the reaction’s activation energy without
knowledge of the reaction mechanism [140]. Augis and Bennett proposed the following
equation as a complement to the Kissinger method, based on non-isothermal differential
thermal analysis (DTA) and differential scanning calorimetry (DSC):
 
β Ea
ln = ln A − (25)
Tp − T0 RTp

where β is the heating rate, Ea is the activation energy, R is the gas constant, Tp is the
temperature corresponding to the peak of the differential scanning calorimetry (DSC) or
differential thermal analysis (DTA) curve, and T0 is the starting temperature.
The accuracy of the DTA or DSC curve plotting and the heating rate β influence the
evaluation of Augis and Bennett’s method for the onset temperature T0 . Augis and Bennett
recommend using a single T0 value for all heating rates, i.e., one that is lower than the
lowest starting temperature corresponding to the lowest heating rate [141].

5.3.6. Advanced Isoconversional Methods

The differential method has the advantage of not requiring approximations and can be
applied to isothermal, non-isothermal, or more complex temperature tests of any type. The
main disadvantage of the differential method is the possibility of experimental result value
instability [142]. To address some of the shortcomings of the commonly used integration
method, some researchers pioneered the advanced equal conversion method [120,143,144].
The Vyazovkin method, which is one of the more sophisticated isotransformation techniques,
is represented by Equations (26) and (27):
n n
J [ Eα , T (tα )]
Φ( Eα ) = ∑ ∑ J Eα , Ti (tα ) (26)
i =1 j 6 = i j

Ztα
− Eα
J [ Eα , T (tα )] = exp [ ] (27)
RT (t)
tα −∆α

where Ea is the effective activation energy and the value of Ea is the value that minimizes
the function Φ( Eα ). This nonlinear kinetic approach (NLN) deals with a set of n experi-
ments performed at different temperatures Ti (t), which can be numerically integrated over
time using the trapezoidal method. Exact interpolation using the Lagrangian algorithm
determines the time tα,i and temperature Tα,i associated with the selected value of α for
each ith temperature program [145].
Appl. Sci. 2023, 13, 3045 13 of 18

6. Conclusions
In modern society, polyethylene materials are utilized in a variety of applications, but
as their use increases, their initial performance qualities tend to change. Temperature, light,
pressure, chemical attack, mechanical stress, microorganisms, and other factors can all
affect the degradation of polyethylene materials. This influence is frequently synergistic,
making polyethylene degradation extremely complex. Many researchers have developed
various kinetic methods for predicting the lifetime of polyethylene materials, and this paper
describes the most common and widely used kinetic methods.
The isoconversion method derives from the Ozawa–Flynn–Wall (OFW) method and
the Friedman method, both of which do not require a mathematical model and instead
use several curves at different heating rates to calculate the kinetic parameters at the same
conversion rate and obtain the activation energy. The multi-curve method is another name
for the equal conversion rate method. With the introduction of the Kissinger–Akahira–
Sunose (KAS) method, the accuracy of the equal conversion rate method has improved.
Kissinger and OFW are model-free analyses, which means that the activation energy is
calculated without taking into account the kinetic model of the reaction process. Friedman’s
method has the advantage of not being limited to linear changes in heating rate and
exhibiting simplicity, adequacy, and accuracy. The advanced isotransformation rate method
is now widely acknowledged as one of the most precise methods for estimating activation
energies from TGA experiments.
Due to the numerous applications of polyethylene materials in people’s lives, the
extensive use of polyethylene materials can lead to environmental pollution. Extending
the service life of polyethylene can promote the development of the 5Rs [146] for reducing
environmental pollution, therefore, the life prediction of polyethylene and other polymeric
materials is critical.

Author Contributions: Conceptualization, Y.W.; Writing—original draft, G.F.; Funding acquisition,

Y.W.; Investigation, Y.W. and D.Y.; Resources, Y.W. and N.L.; Supervision, Y.W. and H.L.; Validation,
Q.L.; Writing—review and editing, J.T. and G.F. All authors have read and agreed to the published
version of the manuscript.
Funding: This work was supported by the Natural Science Foundation of Xinjiang Uygur Au-
tonomous Region (no. 2022D01C389), the Xinjiang University Doctoral Start-up Foundation (no.
620321029), and the Science and Technology Planning Project of State Administration for Market
Regulation (no. 2022MK201).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data are not publicly available.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Dehbi, A.; Mourad, A.-H.I.; Bouaza, A. Ageing effect on the properties of tri-layer polyethylene film used as greenhouse roof.
Procedia Eng. 2011, 10, 466–471. [CrossRef]
2. Fouad, H.; Mourad, A.-H.; Barton, D. Effect of pre-heat treatment on the static and dynamic thermo-mechanical properties of
ultra-high molecular weight polyethylene. Polym. Test. 2005, 24, 549–556. [CrossRef]
3. Mohamed, F.H.; Mourad, A.-H.I.; Barton, D.C. UV irradiation and aging effects on nanoscale mechanical properties of ultra high
molecular weight polyethylene for biomedical implants. Plast. Rubber Compos. 2008, 37, 346–352. [CrossRef]
4. Tiffour, I.; Dehbi, A.; Mourad, A.-H.I.; Belfedal, A. Synthesis and characterization of a new organic semiconductor material. Mater.
Chem. Phys. 2016, 178, 49–56. [CrossRef]
5. Mourad, A.-H.I.; Elsayed, H.F.; Barton, D.C.; Kenawy, M.; Abdel-Latif, L.A. Ultra high molecular weight polyethylene deformation
and fracture behaviour as a function of high strain rate and triaxial state of stress. Int. J. Fract. 2003, 120, 501–515. [CrossRef]
6. Mourad, A.-H.I.; Mozumder, M.S.; Mairpady, A.; Pervez, H.; Kannuri, U.M. Optimization of injection molding parameters for
HDPE/TiO2 nanocomposites fabrication with multiple performance characteristics using the Taguchi method and grey relational
analysis. Materials 2016, 9, 710. [CrossRef]
Appl. Sci. 2023, 13, 3045 14 of 18

7. Paxton, N.C.; Allenby, M.C.; Lewis, P.M.; Woodruff, M.A. Biomedical applications of polyethylene. Eur. Polym. J. 2019, 118,
412–428. [CrossRef]
8. Mozumder, M.S.; Mourad, A.-H.I.; Mairpady, A.; Pervez, H.; Haque, E. Effect of TiO2 nanofiller concentration on the mechanical,
thermal and biological properties of HDPE/TiO2 nanocomposites. J. Mater. Eng. Perform. 2018, 27, 2166–2181. [CrossRef]
9. Weon, J.-I. Effects of thermal ageing on mechanical and thermal behaviors of linear low densit y polyethylene pipe. Polym. Degrad.
Stab. 2010, 95, 14–20. [CrossRef]
10. Holder, S.L.; Hedenqvist, M.S.; Nilsson, F. Understanding and modelling the diffusion process of low molecular weight substances
in polyethylene pipes. Water Res. 2019, 157, 301–309. [CrossRef]
11. Zanasi, T.; Fabbri, E.; Pilati, F. Qualification of pipe-grade HDPEs: Part I, development of a suitable accelerated ageing method.
Polym. Test. 2009, 28, 96–102. [CrossRef]
12. Contino, M.; Andena, L.; Rink, M.; Marra, G.; Resta, S. Time-temperature equivalence in environmental stress cracking of
high-density polyethylene. Eng. Fract. Mech. 2018, 203, 32–43. [CrossRef]
13. Gong, Y.; Wang, S.-H.; Zhang, Z.-Y.; Yang, X.-L.; Yang, Z.-G.; Yang, H.-G. Degradation of sunlight exposure on the high-density
polyethylene (HDPE) pipes for transportation of natural gases. Polym. Degrad. Stab. 2021, 194, 109752. [CrossRef]
14. Frank, A.; Pinter, G. Evaluation of the applicability of the cracked round bar test as standardized PE-pipe ranking tool. Polym.
Test. 2014, 33, 161–171. [CrossRef]
15. Yeh, C.-L.; Nikolić, M.A.; Gomes, B.; Gauthier, E.; Laycock, B.; Halley, P.; Bottle, S.E.; Colwell, J.M. The effect of common
agrichemicals on the environmental stability of polyethylene films. Polym. Degrad. Stab. 2015, 120, 53–60. [CrossRef]
16. Setnickova, K.; Petrychkovych, R.; Reznickova, J.; Uchytil, P. A novel simple and efficient procedure for the pervaporation
transport study of binary mixtures through polymeric membranes: Tested systems propanol isomers—Water–polyethylene
membrane. J. Taiwan Inst. Chem. Eng. 2016, 58, 49–56. [CrossRef]
17. Kircheva, N.; Outin, J.; Perrier, G.; Ramousse, J.; Merlin, G.; Lyautey, E. Bio-electrochemical characterization of air-cathode micro-
bial fuel cells with microporous polyethylene/silica membrane as separator. Bioelectrochemistry 2015, 106, 115–124. [CrossRef]
18. Kindsfater, K.A.; Pomeroy, D.; Clark, C.; Gruen, T.A.; Murphy, J.; Himden, S. In vivo performance of moderately crosslinked,
thermally treated polyethylene in a prospective randomized controlled primary total knee arthroplasty trial. J. Arthroplast. 2015,
30, 1333–1338. [CrossRef]
19. So, K.; Goto, K.; Kuroda, Y.; Matsuda, S. Minimum 10-year wear analysis of highly cross-linked polyethylene in cementless total
hip arthroplasty. J. Arthroplast. 2015, 30, 2224–2226. [CrossRef]
20. Min, B.-W.; Cho, C.-H.; Son, E.-S.; Lee, K.-J.; Lee, S.-W.; Song, K.-S. Highly cross-linked polyethylene in total hip arthroplasty in
patients younger than 50 years with osteonecrosis of the femoral head: A minimum of 10 years of follow-up. J. Arthroplast. 2020,
35, 805–810. [CrossRef]
21. Azeko, S.T.; Mustapha, K.; Annan, E.; Odusanya, O.S.; Soboyejo, W.O. Recycling of polyethylene into strong and tough earth-based
composite building materials. J. Mater. Civ. Eng. 2016, 28, 04015104. [CrossRef]
22. Azeko, S.T.; Arthur, E.K.; Danyuo, Y.; Babagana, M. Mechanical and physical properties of laterite bricks reinforced with
reproce-ssed polyethylene waste for building applications. J. Mater. Civ. Eng. 2018, 30, 04018039. [CrossRef]
23. Tajeddin, B.; Arabkhedri, M. Polymers and food packaging. In Polymer Science and Innovative Applications; Elsevier: Amsterdam,
The Netherlands, 2020; pp. 525–543. [CrossRef]
24. Kahlen, S.; Jerabek, M.; Wallner, G.; Lang, R. Characterization of physical and chemical aging of polymeric solar materials by
mechanical testing. Polym. Test. 2010, 29, 72–81. [CrossRef]
25. Pleşa, I.; Noţingher, P.V.; Stancu, C.; Wiesbrock, F.; Schlögl, S. Polyethylene nanocomposites for power cable insulations. Polymers
2018, 11, 24. [CrossRef] [PubMed]
26. Wang, T.; Ma, Y.; Ji, R. Aging processes of polyethylene mulch films and preparation of microplastics with environmental
characteristics. Bull. Environ. Contam. Toxicol. 2021, 107, 736–740. [CrossRef] [PubMed]
27. Leja, K.; Lewandowicz, G. Polymer biodegradation and biodegradable polymers—A review. Pol. J. Environ. Stud. 2010, 19,
255–266.
28. Kasirajan, S.; Ngouajio, M. Polyethylene and biodegradable mulches for agricultural applications: A review. Agron. Sustain. Dev.
2012, 32, 501–529. [CrossRef]
29. Vázquez-Morillas, A.; Beltrán-Villavicencio, M.; Alvarez-Zeferino, J.C.; Osada-Velázquez, M.H.; Moreno, A.; Martínez, L.; Yáñez,
J.M. Biodegradation and ecotoxicity of polyethylene films containing pro-oxidant additive. J. Polym. Environ. 2016, 24, 221–229.
[CrossRef]
30. Ammala, A.; Bateman, S.; Dean, K.; Petinakis, E.; Sangwan, P.; Wong, S.; Yuan, Q.; Yu, L.; Patrick, C.; Leong, K. An overview of
degradable and biodegradable polyolefins. Prog. Polym. Sci. 2011, 36, 1015–1049. [CrossRef]
31. Struik, L.C.E. The mechanical and physical ageing of semicrystalline polymers: 1. Polymer 1987, 28, 1521–1533. [CrossRef]
32. Castagnet, S.; Thilly, L. High-pressure dependence of structural evolution in polyamide 11 during annealing. J. Polym. Sci. Part B
Polym. Phys. 2009, 47, 2015–2025. [CrossRef]
33. Gill, T.; Knapp, R.; Bradley, S.; Bradley, W. Long term durability of crosslinked polyethylene tubing used in chlorinated hot water
systems. Plast. Rubber Compos. 1999, 28, 309–313. [CrossRef]
34. Chandran, K.R. Mechanical fatigue of polymers: A new approach to characterize the SN behavior on the basis of macroscopic
crack growth mechanism. Polymer 2016, 91, 222–238. [CrossRef]
Appl. Sci. 2023, 13, 3045 15 of 18

35. Rueda, F.; Torres, J.; Machado, M.; Frontini, P.; Otegui, J. External pressure induced buckling collapse of high density polyethylene
(HDPE) liners: FEM modeling and predictions. Thin-Walled Struct. 2015, 96, 56–63. [CrossRef]
36. Gorghiu, L.; Jipa, S.; Zaharescu, T.; Setnescu, R.; Mihalcea, I. The effect of metals on thermal degradation of polyethylenes. Polym.
Degrad. Stab. 2004, 84, 7–11. [CrossRef]
37. Desai, V.; Shenoy, M.; Gogate, P. Ultrasonic degradation of low-density polyethylene. Chem. Eng. Process. Process Intensif. 2008, 47,
1451–1455. [CrossRef]
38. Mierzwa-Hersztek, M.; Gondek, K.; Kopeć, M. Degradation of polyethylene and biocomponent-derived polymer materials: An
overview. J. Polym. Environ. 2019, 27, 600–611. [CrossRef]
39. La Mantia, F.P.; Morreale, M.; Botta, L.; Mistretta, M.C.; Ceraulo, M.; Scaffaro, R. Degradation of polymer blends: A brief review.
Polym. Degrad. Stab. 2017, 145, 79–92. [CrossRef]
40. Rolón-Garrido, V.H.; Kruse, M.; Wagner, M.H. Size exclusion chromatography of photo-oxidated LDPE by triple detection and its
relation to rheological behavior. Polym. Degrad. Stab. 2015, 111, 46–54. [CrossRef]
41. Osawa, Z.; Kurisu, N.; Nagashima, K.; Nakano, K. The effect of transition metal stearates on the photodegradation of polyethylene.
J. Appl. Polym. Sci. 1979, 23, 3583–3590. [CrossRef]
42. Gugumus, F. Effect of temperature on the lifetime of stabilized and unstabilized PP films. Polym. Degrad. Stab. 1999, 63, 41–52.
[CrossRef]
43. Hakkarainen, M.; Albertsson, A.-C. Environmental degradation of polyethylene. Long Term Prop. Polyolefins 2004, 177–200.
[CrossRef]
44. Saiz-Jimenez, C. Biodeterioration vs biodegradation: The role of microorganisms in the removal of pollutants deposited on
historic buidlings. Int. Biodeterior. Biodegrad. 1997, 40, 225–232. [CrossRef]
45. Lucas, N.; Bienaime, C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.-E. Polymer biodegradation: Mechanisms and
estimation techniques–A review. Chemosphere 2008, 73, 429–442. [CrossRef]
46. Wilkes, R.; Aristilde, L. Degradation and metabolism of synthetic plastics and associated products by Pseudomonas sp.:
Capabilities and challenges. J. Appl. Microbiolo-Gy 2017, 123, 582–593. [CrossRef]
47. Emadian, S.M.; Onay, T.T.; Demirel, B. Biodegradation of bioplastics in natural environments. Waste Manag. 2017, 59, 526–536.
[CrossRef]
48. Restrepo-Flórez, J.-M.; Bassi, A.; Thompson, M.R. Microbial degradation and deterioration of polyethylene–A review. Int.
Biodeterior. Biodegrad. 2014, 88, 83–90. [CrossRef]
49. Rizzarelli, P.; Rapisarda, M.; Ascione, L.; Degli Innocenti, F.; La Mantia, F.P. Influence of photo-oxidation on the performance and
soil degradation of oxo-and biodegradable polymer-based items for agricultural applications. Polym. Degrad. Stab. 2021, 188,
109578. [CrossRef]
50. Gardette, M.; Perthue, A.; Gardette, J.; Janecska, T.; Földes, E.; Pukánszky, B.; Therias, S. Photo-and thermal-oxidation of
polyethylene: Comparison of mechanisms and influence of unsaturation content. Polym. Degrad. Stab. 2013, 98, 2383–2390.
[CrossRef]
51. Anju, S.; Prajitha, N.; Sukanya, V.; Mohanan, P. Complicity of degradable polymers in health-care applications. Mater. Today Chem.
2020, 16, 100236. [CrossRef]
52. Carrasco, F.; Pagès, P.; Pascual, S.; Colom, X. Artificial aging of high-density polyethylene by ultraviolet irradiation. Eur. Polym. J.
2001, 37, 1457–1464. [CrossRef]
53. Pages, P.; Carrasco, F.; Surina, J.; Colom, X. FTIR and DSC study of HDPE structural changes and mechanical properties variation
when exposed to weathering aging during Canadian winter. J. Appl. Polym. Sci. 1996, 60, 153–159. [CrossRef]
54. François-Heude, A.; Richaud, E.; Desnoux, E.; Colin, X. A general kinetic model for the photothermal oxidation of polypropylene.
J. Photochem. Photobiol. A Chem. 2015, 296, 48–65. [CrossRef]
55. Hsu, Y.-C.; Weir, M.P.; Truss, R.W.; Garvey, C.J.; Nicholson, T.M.; Halley, P.J. A fundamental study on photo-oxidative degradation
of linear low density polyethylene films at embrittlement. Polymer 2012, 53, 2385–2393. [CrossRef]
56. Wiles, D.M.; Scott, G. Polyolefins with controlled environmental degradability. Polym. Degrad. Stab. 2006, 91, 1581–1592.
[CrossRef]
57. Feldman, D. Polymer weathering: Photo-oxidation. J. Polym. Environ. 2002, 10, 163–173. [CrossRef]
58. Carpenter, K.; Janssens, M. Using heat release rate to assess combustibility of building products in the cone calorimeter. Fire
Technol. 2005, 41, 79–92. [CrossRef]
59. Briassoulis, D. The effects of tensile stress and the agrochemical Vapam on the ageing of low density polyethylene (LDPE)
agricultural films. Part I. Mechanical behaviour. Polym. Degrad. Stab. 2005, 88, 489–503. [CrossRef]
60. Müller, R.-J.; Witt, U.; Rantze, E.; Deckwer, W.-D. Architecture of biodegradable copolyesters containing aromatic constituents.
Polym. Degrad. Stab. 1998, 59, 203–208. [CrossRef]
61. Tsuji, H.; Ikada, Y. Properties and morphology of poly (L-lactide) 4. Effects of structural parameters on long-term hydrolysis of
poly (L-lactide) in phosphate-buffered solution. Polym. Degrad. Stab. 2000, 67, 179–189. [CrossRef]
62. He, Y.; Qian, Z.; Zhang, H.; Liu, X. Alkaline degradation behavior of polyesteramide fibers: Surface erosion. Colloid Polym. Sci.
2004, 282, 972–978. [CrossRef]
63. Krushelnitzky, R.; Brachman, R. Antioxidant depletion in high-density polyethylene pipes exposed to synthetic leachate and air.
Geosynth. Int. 2011, 18, 63–73. [CrossRef]
Appl. Sci. 2023, 13, 3045 16 of 18

64. Briassoulis, D. Mechanical design requirements for low tunnel biodegradable and conventional films. Biosyst. Eng. 2004, 87,
209–223. [CrossRef]
65. Briassoulis, D. Mechanical behaviour of biodegradable agricultural films under real field conditions. Polym. Degrad. Stab. 2006,
91, 1256–1272. [CrossRef]
66. Briassoulis, D. Analysis of the mechanical and degradation performances of optimised agricultural biodegradable films. Polym.
Degrad. Stab. 2007, 92, 1115–1132. [CrossRef]
67. Król-Morkisz, K.; Pielichowska, K. Thermal decomposition of polymer nanocomposites with functionalized nanoparticles. In
Polymer Composites with Functionalized Nanoparticles; Elsevier: Amsterdam, The Netherlands, 2019; pp. 405–435. [CrossRef]
68. Beyler, C.L.; Hirschler, M.M. Thermal decomposition of polymers. SFPE Handb. Fire Prot. Eng. 2002, 2, 111–131.
69. Plota, A.; Masek, A. Lifetime prediction methods for degradable polymeric materials—A short review. Materials 2020, 13, 4507.
[CrossRef] [PubMed]
70. Hu, W.; Liu, W.; Ren, X. The study on aging behaviors and critical stress of cross-linked high-density polyethylene during stress
and photo-oxidative aging. J. Polym. Res. 2019, 26, 114. [CrossRef]
71. Bachir-Bey, T.; Belhaneche-Bensemra, N. Investigation of Polyethylene Pipeline Behavior after 30 Years of Use in Gas Distribution
Network. J. Mater. Eng. Perform. 2020, 29, 6652–6660. [CrossRef]
72. Brown, N. Intrinsic lifetime of polyethylene pipelines. Polym. Eng. Sci. 2007, 47, 477–480. [CrossRef]
73. Dowd, J.E.; Sychterz, C.J.; Young, A.M.; Engh, C.A. Characterization of long-term femoral-head-penetration rates: Association
with and prediction of osteolysis. JBJS 2000, 82, 1102. [CrossRef] [PubMed]
74. Lan, T.; Wang, T.; Cao, F.; Yu, C.; Chu, Q.; Wang, F. A comparative study on the adsorption behavior of pesticides by pristine and
aged microplastics from agricultural polyethylene soil films. Ecotoxicol. Environ. Saf. 2021, 209, 111781. [CrossRef] [PubMed]
75. Hou, L.; Xi, J.; Liu, J.; Wang, P.; Xu, T.; Liu, T.; Qu, W.; Lin, Y.B. Biodegradability of polyethylene mulching film by two
Pseudomonas bacteria and their potential degradation mechanism. Chemosphere 2022, 286, 131758. [CrossRef] [PubMed]
76. Derraik, J.G.B. The pollution of the marine environment by plastic debris: A review. Mar. Pollut. Bull. 2002, 44, 842–852. [CrossRef]
[PubMed]
77. Arhant, M.; Le Gall, M.; Le Gac, P.-Y. Fracture test to accelerate the prediction of polymer embrittlement during aging–Case of
PET hydrolysis. Polym. Degrad. Stab. 2022, 196, 109848. [CrossRef]
78. Goliszek, M.; Podkościelna, B.; Sevastyanova, O.; Fila, K.; Chabros, A.; Paczkowski,
˛ P. Investigation of accelerated aging of
lignin-containing polymer materials. Int. J. Biol. Macromol. 2019, 123, 910–922. [CrossRef] [PubMed]
79. Hukins, D.; Mahomed, A.; Kukureka, S. Accelerated aging for testing polymeric biomaterials and medical devices. Med. Eng.
Phys. 2008, 30, 1270–1274. [CrossRef]
80. Schoenbeck, M.A. Durability of chlorosulfonated polyethylene geomembrane seams after accelerated aging tests. Geotext.
Geomembr. 1990, 9, 337–341. [CrossRef]
81. Huang, J.S.; Lu, R.G.; Shi, Y.X.; Zhao, Y.F.; Fang, X.H.; Liu, G.; Li, Z.J. Changes on structural and electrical properties of
retired cross-linked polyethylene (XLPE) cable insulation under electro-thermal aging test. In IOP Conference Series: Earth and
Environmental Science; IOP Publishing: Bristol, UK, 2019; Volume 354. [CrossRef]
82. Sebaa, M.; Servens, C.; Pouyet, J. Natural and artificial weathering of low-density polyethylene (LDPE): Calorimetric analysis.
J. Appl. Polym. Sci. 1993, 47, 1897–1903. [CrossRef]
83. Baukh, V.; Huinink, H.P.; Adan, O.C.; van der Ven, L.G. Natural versus accelerated weathering: Understanding water kinetics in
bilayer coatings. Prog. Org. Coat. 2013, 76, 1197–1202. [CrossRef]
84. Philip, M.; Al-Azzawi, F. Effects of natural and artificial weathering on the physical properties of recycled poly (ethylene
terephthalate). J. Polym. Environ. 2018, 26, 3139–3148. [CrossRef]
85. Therias, S.; Rapp, G.; Masson, C.; Gardette, J.-L. Limits of UV-light acceleration on the photooxidation of low-density polyethylene.
Polym. Degrad. Stab. 2021, 183, 109443. [CrossRef]
86. Geng, P.; Song, J.; Tian, M.; Lei, Z.; Du, Y. Influence of thermal aging on AC leakage current in XLPE insulation. Aip Adv. 2018, 8,
025115. [CrossRef]
87. Li, H.; Li, J.; Ma, Y.; Yan, Q.; Ouyang, B. The role of thermo-oxidative aging at different temperatures on the crystal structure of
crosslinked polyethylene. J. Mater. Sci. Mater. Electron. 2018, 29, 3696–3703. [CrossRef]
88. Hedir, A.; Moudoud, M.; Lamrous, O.; Rondot, S.; Jbara, O.; Dony, P. Ultraviolet radiation aging impact on physicochemical
properties of crosslinked polyethylene cable insulation. J. Appl. Polym. Sci. 2020, 137, 48575. [CrossRef]
89. Doğan, M. Ultraviolet light accelerates the degradation of polyethylene plastics. Microsc. Res. Tech. 2021, 84, 2774–2783. [CrossRef]
90. Bredács, M.; Frank, A.; Bastero, A.; Stolarz, A.; Pinter, G. Accelerated aging of polyethylene pipe grades in aqueous chlorine
dioxide at constant concentration. Polym. Degrad. Stab. 2018, 157, 80–89. [CrossRef]
91. Bolland, J.L. Kinetics of olefin oxidation. Q. Rev. Chem. Soc. 1949, 3, 1–21. [CrossRef]
92. Gandhi, K.; Hein, C.L.; van Heerbeek, R.; Pickett, J.E. Acceleration parameters for polycarbonate under blue LED photo-thermal
aging conditions. Polym. Degrad. Stab. 2019, 164, 69–74. [CrossRef]
93. Nichols, M.; Boisseau, J.; Pattison, L.; Campbell, D.; Quill, J.; Zhang, J.; Smith, N.; Henderson, K.; Seebergh, J.; Berry, D.; et al. An
improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings. J. Coat. Technol. Res. 2013, 10,
153–173. [CrossRef]
Appl. Sci. 2023, 13, 3045 17 of 18

94. Celina, M.; Gillen, K.; Assink, R. Accelerated aging and lifetime prediction: Review of non-Arrhenius behaviour due to two
competing processes. Polym. Degrad. Stab. 2005, 90, 395–404. [CrossRef]
95. Celina, M.; Gillen, K.; Assink, R. Lifetime predictions for semi-crystalline cable insulation materials: I. Mechanical properties and
oxygen consumption measurements on EPR materials. Polym. Degrad. Stab. 2006, 91, 2146–2156. [CrossRef]
96. Lainé, E.; Bouvy, C.; Grandidier, J.-C.; Vaes, G. Methodology of Accelerated Characterization for long-term creep prediction of
polymer structures to ensure their service life. Polym. Test. 2019, 79, 106050. [CrossRef]
97. Kple, M.; Girods, P.; Fagla, B.; Anjorin, M.; Ziegler-Devin, I.; Rogaume, Y. Kinetic study of low density polyethylene using
thermogravimetric analysis, Part 2: Isothermal study. Waste Biomass Valorization 2017, 8, 707–719. [CrossRef]
98. Chrissafis, K.; Efthimiadis, K.G.; Polychroniadis, E.K.; Chadjivasiliou, S.C. Crystallization Kinetics of Amorphous Fe78-xMoxSi9B13;
Aristotle University of Thessaloniki: Thessaloniki, Greece, 2003; No. IKEEART-2010-364. [CrossRef]
99. Chrissafis, K.; Kyratsi, T.; Paraskevopoulos, K.M.; Kanatzidis, M.G. Crystal/glass phase change in KSb5S8 studied through
thermal analysis techniques. Chem. Mater. 2004, 16, 1932–1937. [CrossRef]
100. Chrissafis, K. Kinetics of thermal degradation of polymers. J. Therm. Anal. Calorim. 2009, 95, 273–283. [CrossRef]
101. Vyazovkin, S. Computational aspects of kinetic analysis.: Part C. The ICTAC Kinetics Project—The light at the end of the tunnel?
Thermochim. Acta 2000, 355, 155–163. [CrossRef]
102. Budrugeac, P. Theory and practice in the thermoanalytical kinetics of complex processes: Application for the isothermal and
non-isothermal thermal degradation of HDPE. Thermochim. Acta 2010, 500, 30–37. [CrossRef]
103. Arrhenius, S. Über die Reaktionsgeschwindigkeit bei der Inversion von Rohrzucker durch Säuren. Z. Für Phys. Chem. 1889, 4,
226–248. [CrossRef]
104. Baird, J.A.; Taylor, L.S. Evaluation of amorphous solid dispersion properties using thermal analysis techniques. Adv. Drug Deliv.
Rev. 2012, 64, 396–421. [CrossRef]
105. Gil-Alegre, M.; Bernabeu, J.; Camacho, M.; Torres-Suarez, A. Statistical evaluation for stability studies under stress storage
conditions. Il Farm. 2011, 56, 877–883. [CrossRef]
106. Waterman, K.C.; Adami, R.C. Accelerated aging: Prediction of chemical stability of pharmaceuticals. Int. J. Pharm. 2005, 293,
101–125. [CrossRef]
107. Waterman, K.C. Understanding and predicting pharmaceutical product shelf-life. In Handbook of Stability Testing in Pharmaceutical
Development; Springer: New York, NY, USA, 2009; pp. 115–135. [CrossRef]
108. Peleg, M.; Normand, M.D.; Corradini, M.G. The Arrhenius equation revisited. Crit. Rev. Food Sci. Nutr. 2012, 52, 830–851.
[CrossRef]
109. Oliva, A.; Fariña, J.; Llabrés, M. An improved methodology for data analysis in accelerated stability studies of peptide drugs:
Practical considerations. Talanta 2012, 94, 158–166. [CrossRef] [PubMed]
110. Budrugeac, P. On the evaluation of the thermal lifetime of polymeric materials which exhibit a complex mechanism of thermal
degradation consisting of two successive reactions. Polym. Degrad. Stab. 2000, 67, 271–278. [CrossRef]
111. Tsuji, T.; Mochizuki, K.; Okada, K.; Hayashi, Y.; Obata, Y.; Takayama, K.; Onuki, Y. Time–temperature superposition principle for
the kinetic analysis of destabilization of pharmaceutical emulsions. Int. J. Pharm. 2019, 563, 406–412. [CrossRef] [PubMed]
112. Le Huy, M.; Evrard, G. Methodologies for lifetime predictions of rubber using Arrhenius and WLF models. Die Angew. Makromol.
Chem. 1998, 261, 135–142. [CrossRef]
113. Waterman, K.C.; Carella, A.J.; Gumkowski, M.J.; Lukulay, P.; Macdonald, B.C.; Roy, M.C.; Shamblin, S.L. Improved protocol and
data analysis for accelerated shelf-life estimation of solid dosage forms. Pharm. Res. 2007, 24, 780–790. [CrossRef]
114. Waterman, K.C. The application of the accelerated stability assessment program (ASAP) to quality by design (QbD) for drug
product stability. AAPS PharmSciTech 2011, 12, 932–937. [CrossRef]
115. Li, N.; Taylor, L.S.; Mauer, L.J. Degradation kinetics of catechins in green tea powder: Effects of temperature and relative humidity.
J. Agric. Food Chem. 2011, 59, 6082–6090. [CrossRef]
116. Wang, Y.; Lan, H.-Q.; Meng, T.; Chen, S.; Zuo, J.-D.; Lin, N. A Lifetime Prediction Method of Pressured Gas Polyethylene Pipes by
Thermal-Oxidative Aging Test and Tensile Test. J. Press. Vessel Technol. 2018, 140, 011404. [CrossRef]
117. Wise, J.; Gillen, K.; Clough, R. An ultrasensitive technique for testing the Arrhenius extrapolation assumption for thermally aged
elastomers. Polym. Degrad. Stab. 1995, 49, 403–418. [CrossRef]
118. Madej-Kiełbik, L.; Kośla, K.; Zielińska, D.; Chmal-Fudali, E.; Maciejewska, M. Effect of accelerated ageing on the mechanical and
structural properties of the material system used in protectors. Polymers 2019, 11, 1263. [CrossRef] [PubMed]
119. Koga, Y.; Arao, Y.; Kubouchi, M. Application of small punch test to lifetime prediction of plasticized polyvinyl chloride wire.
Polym. Degrad. Stab. 2020, 171, 109013. [CrossRef]
120. Vyazovkin, S.; Burnham, A.K.; Criado, J.M.; Pérez-Maqueda, L.A.; Popescu, C.; Sbirrazzuoli, N. ICTAC Kinetics Committee
recommendations for performing kinetic computations on thermal analysis data. Thermochim. Acta 2011, 520, 1–19. [CrossRef]
121. Vyazovkin, S.; Burnham, A.K.; Favergeon, L.; Koga, N.; Moukhina, E.; Pérez-Maqueda, L.A.; Sbirrazzuoli, N. ICTAC Kinetics
Committee recommendations for analysis of multi-step kinetics. Thermochim. Acta 2020, 689, 178597. [CrossRef]
122. Sbirrazzuoli, N. Determination of pre-exponential factor and reaction mechanism in a model-free way. Thermochim. Acta 2020,
691, 178707. [CrossRef]
123. Sbirrazzuoli, N. Advanced isoconversional kinetic analysis for the elucidation of complex reaction mechanisms: A new method
for the identification of rate-limiting steps. Molecules 2019, 24, 1683. [CrossRef]
Appl. Sci. 2023, 13, 3045 18 of 18

124. Dowdy, D.R. Meaningful activation energies for complex systems II: Evaluation of the Friedman method when applied to multiple
reactions, and comparison with the Ozawa-Flynn-Wall method. J. Therm. Anal. Calorim. 1987, 32, 1177–1187. [CrossRef]
125. Doyle, C.D. Kinetic analysis of thermogravimetric data. J. Appl. Polym. Sci. 1961, 5, 285–292. [CrossRef]
126. Singh, S.; Patil, T.; Tekade, S.P.; Gawande, M.B.; Sawarkar, A.N. Studies on individual pyrolysis and co-pyrolysis of corn cob and
polyethylene: Thermal degradation behavior, possible synergism, kinetics, and thermodynamic analysis. Sci. Total Environ. 2021,
783, 147004. [CrossRef] [PubMed]
127. Kropidłowska, A.; Rotaru, A.; Strankowski, M.; Becker, B.; Segal, E. Heteroleptic cadmium (II) complex, potential precursor for
semiconducting CDS layers: Thermal stability and non-isothermal decomposition kinetics. J. Therm. Anal. Calorim. 2008, 91,
903–909. [CrossRef]
128. Venkatesh, M.; Ravi, P.; Tewari, S.P. Isoconversional kinetic analysis of decomposition of nitroimidazoles: Friedman method vs
Flynn–Wall–Ozawa method. J. Phys. Chem. A 2013, 117, 10162–10169. [CrossRef] [PubMed]
129. Sbirrazzuoli, N.; Vincent, L.; Mija, A.; Guigo, N. Integral, differential and advanced isoconversional methods: Complex
mechanisms and isothermal predicted conversion–time curves. Chemom. Intell. Lab. Syst. 2009, 96, 219–226. [CrossRef]
130. Friedman, H.L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic
plastic. J. Polym. Sci. Part C Polym. Symposia. 1964, 6, 183–195. [CrossRef]
131. Huidobro, J.A.; Iglesias, I.; Alfonso, B.F.; Espina, A.; Trobajo, C.; Garcia, J.R. Reducing the effects of noise in the calculation of
activation energy by the Friedman method. Chemom. Intell. Lab. Syst. 2016, 151, 146–152. [CrossRef]
132. Zubair, M.; Shehzad, F.; Al-Harthi, M.A. Impact of modified graphene and microwave irradiation on thermal stability and
degradation mechanism of poly (styrene-co-methyl meth acrylate). Thermochim. Acta 2016, 633, 48–55. [CrossRef]
133. Starink, M.J. The determination of activation energy from linear heating rate experiments: A comparison of the accuracy of
isoconversion methods. Thermochim. Acta 2003, 404, 163–176. [CrossRef]
134. Coats, A.W.; Redfern, J.P. Kinetic parameters from thermogravimetric data. Nature 1964, 201, 68–69. [CrossRef]
135. Kissinger, H.E. Reaction kinetics in differential thermal analysis. Anal. Chem. 1957, 29, 1702–1706. [CrossRef]
136. Du, J.; Gao, L.; Yang, Y.; Chen, G.; Guo, S.; Omran, M.; Chen, J.; Ruan, R. Study on thermochemical characteristics properties and
pyrolysis kinetics of the mixtures of waste corn stalk and pyrolusite. Bioresour. Technol. 2021, 324, 124660. [CrossRef]
137. Singh, R.K.; Patil, T.; Sawarkar, A.N. Pyrolysis of garlic husk biomass: Physico-chemical characterization, thermodynamic and
kinetic analyses. Bioresour. Technol. Rep. 2020, 12, 100558. [CrossRef]
138. Ivanovski, M.; Petrovic, A.; Ban, I.; Goricanec, D.; Urbancl, D. Determination of the Kinetics and Thermodynamic Parameters of
Lignocellulosic Biomass Subjected to the Torrefaction Process. Materials 2021, 14, 7877. [CrossRef] [PubMed]
139. Mohomane, S.M.; Motaung, T.E.; Revaprasadu, N. Thermal degradation kinetics of sugarcane bagasse and soft wood cellulose.
Materials 2017, 10, 1246. [CrossRef] [PubMed]
140. Criado, J.; Ortega, A. Non-isothermal transformation kinetics: Remarks on the Kissinger method. J. Non-Cryst. Solids 1986, 87,
302–311. [CrossRef]
141. Augis, J.A.; Bennett, J.E. Calculation of the Avrami parameters for heterogeneous solid state reactions using a modification of the
Kissinger method. J. Therm. Anal. 1978, 13, 283–292. [CrossRef]
142. Sbirrazzuoli, N. Is the Friedman method applicable to transformations with temperature dependent reaction heat? Macromol.
Chem. Phys. 2007, 208, 1592–1597. [CrossRef]
143. Vyazovkin, S.; Sbirrazzuoli, N. Isoconversional kinetic analysis of thermally stimulated processes in polymers. Macromol. Rapid
Commun. 2006, 27, 1515–1532. [CrossRef]
144. Vyazovkin, S. Some basics en route to isoconversional methodology. In Isoconversional Kinetics of Thermally Stimulated Processes;
Springer: Cham, Switzerland, 2015; pp. 1–25. [CrossRef]
145. Sbirrazzuoli, N. Interpretation and physical meaning of kinetic parameters obtained from isoconversional kinetic analysis of
polymers. Polymers 2020, 12, 1280. [CrossRef]
146. Tony, M.A. Valorization of undervalued aluminum-based waterworks sludge waste for the science of “The 5 Rs’ criteria”. Appl.
Water Sci. 2022, 12, 20. [CrossRef]

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