Equilibrium-gated pattern formation: How molecular dissociation thermodynamics drive emergent behavior in dissipative...

Area of Science:

• Materials Science
• Chemical Engineering
• Polymer Chemistry

Background:

• Biological systems exhibit emergent patterns via dissipative processes balancing reaction and transport.
• Synthetic fabrication typically lacks self-organizing capabilities, relying on multistep, user-controlled methods.

Purpose of the Study:

• To identify and investigate chemical systems that integrate reaction and transport phenomena for self-organization.
• To develop synthetic methods inspired by nature for creating functional materials.

Main Methods:

• Utilized frontal ring-opening metathesis polymerization (FROMP) with discrete molecular initiators for controlled polymerization.
• Employed an integrated computational and experimental framework to study pattern formation dynamics.
• Investigated the influence of near-equilibrium inhibition and far-from-equilibrium kinetics on material properties.

Main Results:

• Discovered that equilibrium-gated pattern formation drives pattern formation in frontally polymerized materials.
• Demonstrated that initiator chemistry tuning allows for programmable macroscale properties.
• Identified a broader compositional window, away from the quenching regime, where emergent behavior reliably manifests in FROMP systems.

Conclusions:

• Emergent behavior in FROMP is not limited to a narrow compositional space but occurs in an inhibition-dominated regime.
• This expanded design space enhances operational flexibility and self-organization capabilities of reactive systems.
• Provides a roadmap for designing bioinspired materials with self-organizing properties for synthetic manufacturing.