Mechanistic Atlas of Photocuring Pathways in Vat Photopolymerisation: From Optical Trigger to Network Formation and Structural Evolution
Segurola, Juan
2026-08-27 · Report · Version 0.2
Vat photopolymerisation combines photon absorption, reactive-species generation, bond-forming chemistry, network percolation, transport, process sequencing and post-cure evolution. These events are often compressed into labels such as radical, cationic, dual cure, volumetric, vitrimeric or recyclable even though they occupy different scientific levels. ER-83 established a six-axis taxonomy: trigger and activation event, active species, network-forming transformation, temporal or spatial control, structure-evolution overlay and qualification endpoint. ER-84 converts that taxonomy into a comparative mechanistic atlas. Ten source-controlled figures map conventional radical chain growth; thiol-ene, thiol-yne and mixed thiol-acrylate routes; cationic ring opening and vinyl-ether growth; radical-induced cationic initiation; photobase-mediated Michael and epoxide-opening reactions; the boundary with true anionic chain growth; reversible-deactivation radical reactivation; photochemical ROMP; radical ring-opening weak-link insertion; sequential dual cure; dual-wavelength hybrid cure; dual-colour chemical gating; gelation, vitrification, PIPS/PIMS, associative topology exchange and programmed cleavage. The figures do not reproduce the complete kinetic, formulation or patent analysis of the specialist reviews. They identify the productive transformation, the control layer, the material-state overlay and the minimum evidence needed to support each interpretation. Reactivatable RDRP is included after recovery of the exact ER-62 v1.1 manuscript and focused delta review. Long-wavelength and superlinear initiation remain context-only because the reviewed ER-77 v1.0 record identifies seven editorial P2 items and the exact corrected final manuscript is not available in the controlled working set [E10]. Latent platinum hydrosilylation, non-ROMP ruthenium catalysis, photochemical [2+2]/[4+4] network formation and photoinitiator-free charge-transfer-complex VPP remain excluded. ER-84 is therefore a visual mechanism and source gate rather than an exhaustive reaction-chemistry review.