Salt acts as a plasticizer in polyelectrolyte complexes
(PECs),
which impacts the physical, thermal, and mechanical properties, thus
having implications in applications, such as drug delivery, energy
storage, and smart coatings. Added salt disrupts polycation–polyanion
intrinsic ion pairs, lowering a hydrated PEC’s glass transition
temperature (T
g). However, the relative
influence of counterion type on the PEC’s T
g is not well understood. Here, the effect of anion type
(NaCl, NaBr, NaNO3, and NaI) on the T
g of solid-like, hydrated PECs composed of poly(diallydimethylammonium)
(PDADMA)–poly(styrenesulfonate) (PSS) is investigated. With
increasing the chaotropic nature of the salt anion, the T
g decreases. The relative differences are attributed to
the doping level, the amount of bound water, the mobility of water
molecules within the PECs, and the strength of interactions between
the PEs. For all studied salt concentrations and salt types, the T
g followed the scaling of −1/T
g ≈ ln([IP]/[H2O]), in which
[IP]/[H2O] is the ratio of intrinsic pairs to water. The
scaling estimates that about 7 to 17% of the intrinsic ion pairs should
be weakened for the PEC to partake in a glass transition. Put together,
this study highlights that the T
g in PECs
is impacted by the salt anion, but the mechanism of the glass transition
remains unchanged.