Atomistic scale analysis of the carbonization process for C/H/O/N-based polymers with the ReaxFF reactive force field

TL;DR

This study uses atomistic simulations with an improved ReaxFF force field to analyze the chemical pathways during the initial carbonization of C/H/O/N polymers, revealing molecular mechanisms behind graphitic structure formation.

Contribution

Developed an enhanced ReaxFF force field based on DFT data for C/H/O/N polymers and applied it to simulate early-stage carbonization, elucidating molecular pathways of structure evolution.

Findings

Identified molecular pathways for gas species formation.

Revealed mechanisms for all-carbon ring development.

Provided insights into graphitic structure evolution.

Abstract

During the carbonization process of raw polymer precursors, graphitic structures can evolve. The presence of these graphitic structures affects mechanical properties of the carbonized carbon fibers. To gain a better understanding of the chemistry behind the evolution of these structures, we performed atomistic scale simulations using the ReaxFF reactive force field. Three different polymers were considered as a precursor: idealized ladder PAN (polyacrylonitrile), a proposed oxidized PAN and PBO (poly(p-phenylene-2,6-benzobisoxazole)). We determined the underlying molecular details of polymers conversion into a carbon fiber structure. Since these are C/H/O/N-based polymers, we first developed an improved force field for C/H/O/N chemistry based on the Density Functional Theory (DFT) data with a particular focus on N2 formation kinetics and its interactions with polymer-associated radicals formed during the carbonization process. Then, using this improved force field, we performed atomistic scale simulations of the initial stage of the carbonization process for the considered polymers. Based on our simulation data we determined the molecular pathways for the formation of low-molecular weight gas-species, all-carbon rings crucial for further graphitic structures evolution and possible alignment of the evolved all-carbon 6-membered rings clusters.