PtBS-PSSNa

Salt effects in polyelectrolyte block copolymer micelles are particularly pronounced because the polyelectrolyte chains are closely assembled in the micellar shell [217]. The situation is quite reminiscent of tethered polymer brushes, to which polyelectrolyte block copolymer micelles have been compared, as summarized in the review of Forster [15]. The analogy to polyelectrolyte brushes was investigated by Guenoun in the study of the behavior of a free-standing film drawn from a PtBS-PSSNa-solution [218] and by Hari-haran et al., who studied the absorbed layer thickness of PtBS-PSSNa block copolymers onto latex particles [219,220]. When the salt concentration exceeded a certain limit, a weak decrease in the layer thickness with increasing salt concentration was observed. Similar results have been obtained by Tauer et al. on electrosterically stabilized latex particles [221]. 

Systematic studies on micellar size and structure have been published for poly(styrene-h-acrylic acid) (PS-PAAc) [7, 8], poly(styrene-fr-sodium acrylate) (PS-PAAcNa) [9], or quaternized poly(styrene-h-4-vinyl-pyridine) (PS-P4VPMeI) [10, 11]. It was concluded that the polyelectrolyte chains in the micellar corona are almost fully stretched [8]. The effect of salt concentration was investigated by Guenoun et al. on poly(f-butylstyrene-fr-sodium styrene sulfonate) (PtBS-PSSNa) who observed a weak decrease of micellar size and aggregation number when the salt concentration was increased beyond 0.01 mol/1 [12]. Using small-angle neutron scattering (SANS), the authors could provide additional support for the rod-like conformation of the polyelectrolyte chains in the micellar corona [13]. 

It was already noted in previous studies, that added salt affects the micellar structure only above a certain value of the salt concentration cs. In studies of PtBS-PSSNa block copolymers a dependence of the brush dimension on the added salt concentration appeared above cs=0.01 mol/1. The thickness of a free-standing black films drawn from a diblock polyelectrolyte solution exhibited a steady drop above ionic strengths of 0.2 mol/1 [39]. 

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