We describe experiments pertaining to the formation of surface-anchored poly(acrylic acid) (PAA) brushes with a gradual variation of the PAA grafting densities on flat surfaces and provide detailed analysis of their properties. The PAA brush gradients are generated by first covering the substrate with a molecular gradient of the polymerization initiator, followed by the “grafting from” polymerization of tert-butyl acrylate (tBA) from these substrate-bound initiator centers, and finally converting the PtBA into PAA. We use spectroscopic ellipsometry to measure the wet thickness of the grafted PAA chains in aqueous solutions at three different pH values (4, 5.8, and 10) and a series of ionic strengths (IS). Our measurements reveal that at low grafting densities, σ, the wet thickness of the PAA brush (H) remains relatively constant, the polymers are in the mushroom regime. Beyond a certain value of σ, the macromolecules enter the brush regime, where H increases with increasing σ. For a given σ, H exhibits a nonmonotonic behavior as a function of the IS. At large IS, the H is small because the charges along PAA are completely screened by the excess of the external salt. As IS decreases, the PAA enters the so-called salt brush (SB) regime, where H increases. At a certain value of IS, H reaches a maximum and then decreases again. The latter is a typical brush behavior in so-called osmotic brush (OB) regime. We provide detailed discussion of the behavior of the grafted PAA chains in the SB and OB regimes.

We show that assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates can be generated by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from the substrate-bound initiator centers (“grafting from”). We apply this technique to prepare grafting density gradients of poly(acrylamide) (PAAm) on flat silica substrates. We demonstrate that using the grafting density gradient geometry, the mushroom-to-brush transition can be accessed on a single sample. This transition is detected by monitoring the dependence of the thickness of the grafted PAAm in a good solvent using variable angle spectroscopic ellipsometry. Wettability experiments performed on the gradient PAAm substrate provide complementary information about the nature of the mushroom-to-brush transition.

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