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Moon, Josh
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article
Role of free volume in molecular mobility and performance of glassy polymers for corrosion protective coatings
Abstract
Glassy polymer coatings on metal substrates rely on their mechanical, physical, and transport properties for corrosion protection. These properties are known to be influenced by the free volume between the polymer chains that plays a critical role in coating performance.Free volume permits local segmental mobility that affects mechanical properties, such as yield and adhesion, and also permits the diffusion of small molecules (water, ions, oxygen) through the coating to the substrate.The fractional free volume is calculated from the specific volume and Bondi group contribution theory for the occupied volume.The free volume distribution (free volume element size and number) is measured by positron annihilation lifetime spectroscopy (PALS) using the ortho-positronium (oPs) probe. The oPs probe detects free volume elements that can be used to elucidate the barrier properties of glassy polymer coatings. The oPs probe is sensitive to phenomena that affect both the mechanical and barrier properties of coatings including physical aging, water sorption, and plasticization, making PALS a suitable allied testing method for corrosion protective coatings.