Spontaneous Emergence of Nonlinear Light Waves and Self-Inscribed Waveguide Microstructure during the Cationic Polymerization of Epoxides

We report spontaneous pattern formation due to modulation instability (MI) of a broad, uniform, incandescent beam as it propagates through a fluid medium undergoing cationic ring-opening polymerization of epoxide moieties and show that the dynamics of the process can be controlled through polymerization kinetics. By strong contrast, MI in the half century-old field of nonlinear light propagation has until now been described predominantly in terms of optical parameters such as coherence, intensity and wavelength. The increase in refractive index (Δn) originating from the cross-linking polymerization of biscycloaliphatic epoxy monomers pushes the system into a nonlinear regime, where normally negligible spatial noise becomes greatly amplified. The perturbed optical field stabilizes by spontaneously dividing into thousands of self-trapped filaments of light. Because each filament inscribes a permanent microscopic channel along its propagation path, the initially isotropic fluid medium solidifies into a densely packed array of self-induced waveguides. These experiments demonstrated the strong correlation between the kinetics of cationic polymerization and dynamics of MI; the beam becomes unstable only within a narrow parameter range where a critical balance is struck between the photoresponse speed (determined by polymerization rate) and the magnitude of Δn (determined by extent of cross-linking). The former needs to be sufficiently fast to respond to noise while the latter must be large enough to generate high-refractive index seeds that trigger MI. Outside of this range, MI is entirely suppressed. This study reveals that nonlinear waveforms emerge in a familiar, widely employed epoxide photopolymer system, which for the first time highlights the possibility of tuning MI through the kinetics of a photochemical reaction.