Methanol degradation mechanisms and permeability phenomena in novolac epoxy and polyurethane coatings

On a global scale, methanol is one of the most important feedstocks and is used widely as solvent and co-solvent. However, due to the polar nature and associated ability to conduct current, the small molecule can take part in galvanic corrosion of metal storage tanks and degrade the barrier properties of protective coatings.

In the present work, we investigated the degradation of two novolac epoxy coatings and a polyurethane (PU) coating exposed to methanol with the aim of quantifying the various degradation paths. Absorption and desorption rates were measured and the thermomechanical properties followed by dynamic mechanical analysis.

For evaluation of the coating barrier properties (i.e., breakthrough time and steady state permeation rates of methanol), permeation cells were applied. During methanol absorption, simultaneous leaching of certain coating ingredients and bonding of methanol to the binder matrix via hydrogen bonds was evidenced.

In terms of classification, the bonding of methanol took place by two types of mechanisms. In Type I, the methanol molecule forms a single hydrogen bond to the coating network, thereby acting as a plasticizer, which decreases the coating storage modulus and glass transition temperature. For Type II bonding of methanol, on the other hand, two hydrogen bonds to the coating network form per molecule, resulting in so-called physical crosslinking.

The Type I mechanism boosted segmental mobility and contributed to the leaching of the plasticizer benzyl alcohol from the novolac epoxy coatings and residual solvents (i.e., naphtha and xylene) from the PU coating. Following the methanol desorption, and attributed to an increased effective crosslinking density from Type II bound methanol, the novolac epoxy and PU coatings exhibited significant increases in the glass transition temperatures.

In addition, for the three coatings, a gradual decline in the permeability rate of methanol was observed over time. These enhanced (and unexpected) barrier properties result from a combination of effects ascribed to Type II bound methanol and the leaching process.