The conventional method to synthesize 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 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 after dialysis to remove partially the water-soluble species, and (3) SD polymers with added surfactants. The results reveal that particle boundaries Materials and Interfaces (2015) 7, pp 12147-12157 2 and surfactants both 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 coefficient at high relative humidities and also the lowest water diffusion coefficient at low humidities. These barrier properties make SD coatings an attractive alternative to conventional emulsion polymer coatings. Published in ACS Applied

The loss of optical transparency when polymer films are immersed in water, which is called “water whitening,” severely limits their use as clear barrier coatings. It is found that this problem is particularly acute in films deposited from polymers synthesized via emulsion polymerization using surfactants. Water whitening is less severe in secondary dispersion (SD) polymers, which are made by dispersing solution polymers in water without the use of surfactants. NMR relaxometry in combination with optical transmission analysis and electron microscopy reveal that some of the water sorbed in emulsion polymer films is contained within nanosized “pockets” or bubbles that scatter light. In contrast, the water in SD polymer films is mainly confined at particle interfaces, where it scatters light less strongly and its molecular mobility is reduced. The addition of surfactant to a SD creates a periodic structure that displays a stop band in the optical transmission. The total amount of sorbed water is not a good indicator of polymers prone to water whitening. Instead, the particular locations of the water within the film must be considered. Both the amount of water and the size of the local water regions (as are probed by NMR relaxometry) are found to determine water whitening. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1658–1674

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