Water Vapor Sorption and Diffusion in Secondary Dispersion Barrier Coatings: A Critical Comparison with Emulsion Polymers.

The conventional method for synthesizing waterborne polymer colloids is emulsion polymerization using surfactants. An emerging method is the use of secondary dispersions (SD) of polymers in water, which avoids the addition of any surfactant. Although there are numerous studies of the water barrier properties (sorption, diffusion, and permeability) of waterborne emulsion (Em) polymer coatings, the properties of SD coatings, in comparison, have not been thoroughly investigated. Here, dynamic water vapor sorption analysis is used to compare the equilibrium sorption isotherms of the two forms of styrene-acrylate copolymers (Em and SD) with the same monomer composition. From an analysis of the kinetics of vapor sorption, the diffusion coefficient of water in the polymer coatings is determined. The combined effects of particle boundaries and surfactant addition were investigated through a comparison of the properties of SD and Em coatings to those of (1) solvent-cast polymer coatings (of the same monomer composition), (2) Em polymers that underwent dialysis to partially remove the water-soluble species, and (3) SD polymers with added surfactants. The results reveal that both the particle boundaries and the surfactants increase vapor sorption. The diffusion coefficients of water are comparable in magnitude in all of the polymer systems but are inversely related to water activity because of molecular clustering. Compared to all of the other waterborne polymer systems, the SD barrier coatings show the lowest equilibrium vapor sorption and permeability coefficients at high relative humidities as well as the lowest water diffusion coefficient at low humidities. These barrier properties make SD coatings an attractive alternative to conventional emulsion polymer coatings.