A thermo-chemo-mechanical model for material extrusion of frontally polymerizing thermoset polymers

Kumar, Aditya; Zakoworotny, Michael; Bonner, Francisco Javier Balta; Aw, Jia En; Sottos, Nancy R.; Tawfick, Sameh H.; Geubelle, Philippe H.

doi:10.1016/j.addma.2024.103972

Cited by 1 publication

(1 citation statement)

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“…While informative, − the existing computational FROMP models are phenomenological in their description of FP-kinetics, with cure kinetics parameters { A , E a , g (α)} extracted from thermal analysis by differential scanning calorimetry (DSC) performed at different heating rates (cf. Figure (a)). ,, Compounding to this, the standard DSC heating rates vary between 2 and 20 °C/min, making the interface between experiments and computational models costly (∼5 h/resin formulation), while significantly under representing the localized FROMP rapid heating rates.…”

Section: Introductionmentioning

confidence: 99%

A Mechanism-Based Reaction–Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis

Bistri,

Arretche,

Lessard

et al. 2024

J. Am. Chem. Soc.

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Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction−diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations. In this work, we formulate a chemically meaningful model grounded in the established mechanism of ring-opening metathesis polymerization (ROMP). Our study aims to validate the hypothesis that the ROMP mechanism, applicable to monomer-initiator solutions below 100 °C, remains valid under the nonideal conditions encountered in FROMP, including ambient to >200 °C temperatures, sharp temperature gradients, and neat monomer environments. Through extensive simulations, we demonstrate that our mechanism-based model accurately predicts the FROMP behavior across various resin compositions, including polymerization front velocities and thermal characteristics (e.g., T max ). Additionally, we introduce a semi-inverse workflow that predicts FROMP behavior from a single experimental data point. Notably, the physiochemical parameters utilized in our model can be obtained through DFT calculations and minimal experiments, highlighting the model's potential for rapid screening of new FROMP chemistries in pursuit of thermoset polymers with superior thermo-chemo-mechanical properties.

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