1. Introduction
Plastic waste, or garbage generation and disposal, have grown to be an irksome global problem, especially in many industrialized nations. The waste generated was at 220 Mt per annum in 2020, with its end-of-life destination deemed to be mainly in the sediment, biota, and aquatic ecosystem, such as oceans and rivers, as macro, micro (<5 mm), and nanoplastics (<1.2 μm) [
1,
2]. Municipal solid waste (MSW) is the primary source of plastic garbage. Most plastic waste is either burned or dumped in landfills across the world [
3].
The destruction of waste by incineration is equally expensive and causes problems with high emissions and increasing environmental concerns, while the disposal of waste in landfills is still viewed as an unattractive and expensive operation [
3]. In addition, the direct burning of plastic waste produces harmful pollutants in addition to phosgene, dioxins, and carbon monoxide, all of which have been associated with human malignancies and endocrine disruption [
4]. However, it is conceivable to increase the value of this waste, while encouraging the circular economy by using procedures such as pyrolysis, solvent dissolution, gasification, and other valorization techniques [
5].
In the recycling industry, research is currently more heavily weighted toward tertiary recycling by utilizing cutting-edge technologies, such as pyrolysis, gasification, and catalytic cracking [
6]. Pyrolysis is the word used to describe the breakdown of organic polymers when they are exposed to high temperatures without oxygen. For low-volume products (gases, liquids, and char) that may be utilized as fuel, added to petroleum refinery feedstocks, or used as chemical feedstocks, pyrolysis offers certain benefits over other waste-disposal methods.
PET polymers are widely employed across a variety of industrial sectors and make up 40% of the worldwide plastic market, together with polyethylene [
7]. In addition, PET is the third-most popular polymer in Europe after PP and LDPE, and, by 2011, PET demand and consumption had reached 60 Mt globally, with annual growth rates of 4.5% [
8]. PET often degrades in MPs while in the environment, increasing environmental concerns. For example, they can be ingested by aquatic and terrestrial organisms, and can potentially accumulate in their tissues, leading to injury or death. MP can also act as vectors for toxic pollutants and pathogens, which can then be passed on to organisms that consume them [
3]. Additionally, microplastics can also be inhaled by humans, which can lead to respiratory problems and other health issues. Studies have also found microplastics in human organs, such as the liver and brain, which may cause endocrine disruption, genetic damage, and other malignancies [
3].
The pyrolysis and kinetic modelling of PET waste is now being explored in multiple studies [
9,
10,
11,
12]. Employing kinetic modelling is very important to better characterize the reaction process during the thermal cracking of plastic polymers, since the operating conditions can change both the product composition and the reaction route [
2]. Ganeshan et al. [
10] employed the Coats-Redfern technique to evaluate PET thermal degradation and reported activation energy (Ea) values in the range of 133–251 kJ/mol. They obtained a coefficient of determination (R
2 of 0.8) and concluded that the Coats-Redfern approach is not always appropriate for estimating kinetic parameters. Using the iso-conversional approach, Das and Tiwari [
12] examined the kinetic parameters for PET pyrolysis at high heating rates of 5, 10, 20, 40, and 50 °C/min. They provided Ea values between 196 and 217 kJ/mol. For the co-pyrolysis of PET with biomass seeds, Mishra et al. [
11] utilized the following models: the Coats-Redfern technique, the Kissinger-Akahira-Sunose (KAS) method, the Flynn-Wall and Ozawa (FWO) method, the Friedman method, and the Starink method. The PET pyrolysis KAS technique revealed that the average Ea was 230.7 kJ/mol. Under identical circumstances, the Ea averages for the FWO, Starink, and Friedman techniques were 230.5, 231.0 kJ/mol, and 225.6 kJ/mol, respectively.
There is a paucity of studies performed on the use of microplastics (MPs) made from polyethylene terephthalate (PET) as the material for thermal degradation. Cho [
13] used two analytical methods, TG-FTIR and TED-GC-MS, combined with thermogravimetric analysis, to evaluate the thermal-degradation process of individual and mixed samples of polypropylene (PP), polyethylene terephthalate (PET), and polyvinyl chloride (PVC). However, the kinetics and optimization of the degradation process was not studied. For proper kinetic evaluation of the degradation process, the International Confederation for Thermal Analysis and Calorimetry (ICTAC) recommended the use of thermal degradation data from multiple heating rates, as data measured at a single heating rate can give rise to striking examples of failure when estimating the thermal stability at ambient temperatures [
14,
15].
To optimize the rate of degradation of PET MPs at different heating rates, it is important to have a thorough understanding of the processes and kinetics involved [
14]. Thermogravimetric analysis (TGA) is a common technique used to study the thermal decomposition of solids, and has recently been used to study the pyrolysis of plastic waste as a way to convert it into valuable products or chemicals. In this particular study, the researchers looked at thermal degradation at different heating rates and found that the kinetic model they used could explain the data with a single set of parameters, regardless of the heating rate. Since it shows potent performance to represent linear and non-linear connection and, therefore, saves time, the majority of academics have recently been striving to construct an artificial neural network (ANN) model for the prediction of various data [
16,
17,
18]. As a result, ANN is utilized as a different strategy to assist in the prediction of TGA data [
18]. References to the use of artificial neural networks (ANN) for modelling the kinetics of various systems, such as fermentation and catalytic hydrogenation, oily sludge and high-density polyethylene can be found in the literature [
19]. Recent studies have also applied ANN in the study of polymer degradation [
6,
20]. In these studies, results showed good agreement between the ANN predicted and experimental data (R > 0.9999) from HDPE degradation. In terms of PET MPs, there is no prior study applying ANN for its degradation at different heating rates. This study fills this knowledge gap.
This investigation uses TGA to learn more about the kinetics of heat breakdown of PET MPs. One isoconversional approach and two non-isoconversional models have been used to determine the activation energy of the thermally degraded PET MPs as a function of conversion at three different heating rates. A very effective constructed ANN model based on multilayer perceptron has also made the first prediction of the pyrolytic behavior of PET MPs.