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Thermal oxidation characteristics of polystyrene with different particle sizes based on the traditional kinetic approaches and distributed activation energy model

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Abstract

Ultrafine materials with unique characteristics have a broad range of utilization. The motivation of this paper was to investigate the size effect on the thermo-oxidative degradation behaviors and chemical kinetics of polystyrene (PS) solid particles. In this study, microscopic PS particles with four different-diameter distributions, containing 5, 10, 15, and 50 μm, were picked as tested samples. Then, the thermogravimetry analysis test of PS samples was conducted under an air atmosphere with three different heating rates. Activation energies were calculated and validated by multiple traditional kinetic approaches, and a linear relationship between activation energy and the reciprocal of the particle diameter has been concluded. A distributed activation energy model (DAEM) with two pseudo-components was developed and employed to decouple the polyurethane pyrolysis in the air atmosphere. A set of nth-order reactions is hypothesized to occur with a constant pre-exponential factor and having a continuous activation energy distribution pattern conforming to the Gaussian density function in each kinetic process. A multi-parameter optimization program was developed to calculate ten DAEM parameters based on the experimental data from three different heating rates by avoiding the ill condition resulting from the kinetic compensation effect. Moreover, the numerical relationship between activation energies and particle diameter has been analyzed. The results of this study are instructive for the determination method of kinetic triplets, the modification of reaction models, and especially the construction of waste polymer kinetics and combustion models.

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Acknowledgements

The authors would like to thank the National Natural Science Foundation of China (NSFC, Grants 52306145, 52176114), Natural Science Foundation of Jiangsu Province (BK20230929), China Postdoctoral Science Foundation (2023M731693), and the Jiangsu Funding Program for Excellent Postdoctoral Talent.

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Authors and Affiliations

  1. School of Mechanical Engineering, Nanjing University of Science and Technology, Nanjing, China

    Mi Li, Zhong-Xuan Han & Lin Jiang

  2. School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, China

    Dan Zhang

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  1. Mi Li
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  2. Dan Zhang
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Correspondence to Lin Jiang.

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Li, M., Zhang, D., Han, ZX. et al. Thermal oxidation characteristics of polystyrene with different particle sizes based on the traditional kinetic approaches and distributed activation energy model. J Therm Anal Calorim 149, 993–1001 (2024). https://doi.org/10.1007/s10973-023-12755-4

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  • DOI: https://doi.org/10.1007/s10973-023-12755-4

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