Spectroscopic probing of ultraviolet-induced degradation in elastomeric polyurea

Aromatic polyurea has garnered assiduous research due to its excellent impact, shock, abrasion, moisture, and chemical resistance properties. Polyurea can be used in protective coating and impact mitigation applications but is inevitably exposed to harsh deployment conditions such as extended ultraviolet (UV) radiation. Fourier Transform Infrared (FTIR) spectroscopy, Terahertz-time domain spectroscopy (THz-TDS), and Excitation-Emission Matrix spectroscopy (EEMS) deciphered the effects of UV radiation on radiated polyurea samples under ambient and nitrogen-rich conditions. Samples were radiated continuously for up to 15 weeks in increments of 3 weeks. Comprehensive FTIR analyses revealed a monotonic increase in disordered hydrogen bonding as a function of exposure duration in an ambient environment. Otherwise, marginal changes were observed in UV-radiated samples under nitrogen. The hydrogen bond length exhibited significant variations in the former compared to their nitrogen atmosphere counterparts. The results infer the nitrogen shielding effect, protecting polyurea from the photodegradation and photo-oxidation observed in samples radiated under the ambient atmosphere. THz-TDS spectra affirmed the FTIR results by probing changes in the complex refractive index. Terahertz spectral peaks associated with torsional vibrations of intermolecular hydrogen bonds in polyurea were notably correlated with increased exposure duration in the ambient atmosphere. Changes in the complex index as a function of exposure duration under nitrogen are minimal. The excitation-emission spectra of polyurea samples reveal a strong fluorescent behavior in 9-week and 12-week ambient-exposed polyurea due to cluster-triggered emission mechanisms. The results synthesized based on three different spectroscopy techniques paint a holistic portrait of the adverse effects of extended ultraviolet radiation of macromolecules deployed in harsh environmental conditions.