Deposition behavior of polyaniline on carbon nanofibers by oxidative chemical vapor deposition

Oxidative chemical vapor deposition (oCVD) offers unique advantages as a liquid-free processing technique in synthesizing and integrating conducting polymers, including polyaniline (PANI), by enabling conformal coatings onto nanostructured substrates, like carbon nanofibers. With relatively thick nanofiber mats, the challenge is to ensure uniform coating thickness through the porous substrates. Here, the substrate temperature during oCVD is found to be a primary factor influencing PANI coating uniformity. Coating uniformity is enhanced by operating at a higher substrate temperature, where monomer adsorption is believed to be limiting relative to intrinsic reaction kinetics. Also, a higher substrate temperature leads to significantly less PANI oligomers and more PANI in the emeraldine oxidation state. A systematic study of oCVD kinetics with substrate temperature shows a reaction-limited regime at lower substrate temperatures with an activation energy of 12.0 kJ/mol, which is believed to be controlled by the self-catalyzed PANI polymerization reaction that transitions at higher substrate temperatures above 90 °C to an adsorption-limited regime as indicated by a negative activation energy of -18.8 kJ/mol. Overall, by operating within an adsorption-limited oCVD regime, more uniform oCVD PANI coatings on electrospun carbon nanofiber mats have been achieved.