title: Stable Aqueous Dispersions of Hydrophobically Modified Titanium Dioxide Pigments through Polyanion Adsorption: Synthesis, Characterization, and Application in Coatings.
abstract: Polyanion dispersants stabilize aqueous dispersions of hydrophilic (native) inorganic oxide particles, including pigments currently used in paints, which are used at an annual scale of 3 million metric tons. While obtaining stable aqueous dispersions of hydrophobically modified particles has been desired for the promise of improved film performance and water barrier properties, it has until now required either prohibitively complex polyanions, which represent a departure from conventional dispersants, or multistep syntheses based on hybrid-material constructs. Here, we demonstrate the aqueous dispersion of alkylsilane-capped inorganic oxide pigments with conventional polycarboxylate dispersants, such as carboxymethylcellulose (CMC) and polyacrylate, as well as a commercial anionic copolymer. Contact-angle measurements demonstrate that the hydrophobically modified pigments retain significant hydrophobic character even after adsorbing polyanion dispersants. CMC adsorption isotherms demonstrate 92% greater polyanion loading on trimethylsilyl modified hydrophobic particles relative to native oxide at pH 8. However, consistent with prior literature, hydrophobically modified silica particles adsorb polyanions very weakly under these conditions. These data suggest that Lewis acidic heteroatoms such as Al(3+) sites on the pigment surface are necessary for polyanion adsorption. The adsorbed polyanions increase the dispersion stability and zeta potential of the particles. Based on particle sedimentation under centrifugal force, the hydrophobically modified pigments possess greater dispersion stability with polyanions than the corresponding native hydroxylated particles. The polyanions also assist in the aqueous wetting of the hydrophobic particles, facilitating the transition from a dry powder into an aqueous dispersion of primary particles using less agitation than the native hydroxylated pigment. The application of aqueous dispersions of hydrophobically modified oxide particles to waterborne coatings leads to films that display lower water uptake at high relative humidities and greater hydrophilic stain resistances. This improved film performance with hydrophobically modified pigments is the result of better association between latex polymer and pigment in the dry film.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley 201 Gilman Hall, Berkeley, California 94720-1462, United States.
authors.forename: Joseph
authors.initials: J
authors.lastname: Jankolovits
authors.affiliation: Energy Conversion Group, Lawrence Berkeley National Laboratory , MS 70-108B, 1 Cyclotron Rd., Berkeley, California 94720, United States.
authors.forename: Ahmet
authors.initials: A
authors.lastname: Kusoglu
authors.affiliation: Energy Conversion Group, Lawrence Berkeley National Laboratory , MS 70-108B, 1 Cyclotron Rd., Berkeley, California 94720, United States.
authors.forename: Adam Z
authors.initials: AZ
authors.lastname: Weber
authors.affiliation: The Dow Chemical Company, Collegeville, Pennsylvania 19426, United States.
authors.forename: Antony
authors.initials: A
authors.lastname: Van Dyk
authors.affiliation: The Dow Chemical Company, Collegeville, Pennsylvania 19426, United States.
authors.forename: James
authors.initials: J
authors.lastname: Bohling
authors.affiliation: The Dow Chemical Company, Midland, Michigan 48674, United States.
authors.forename: John A
authors.initials: JA
authors.lastname: Roper
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley 201 Gilman Hall, Berkeley, California 94720-1462, United States.
authors.forename: Clayton J
authors.initials: CJ
authors.lastname: Radke
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley 201 Gilman Hall, Berkeley, California 94720-1462, United States.
authors.forename: Alexander
authors.initials: A
authors.lastname: Katz