4 research outputs found
Doping and Diffusion in an Extruded Saloplastic Polyelectrolyte Complex
Doping constants and diffusion coefficients
for an extruded, stoichiometric,
dense polyelectrolyte complex, PEC, were determined for a Hofmeister
series of anions. These thermodynamic and kinetic parameters describe
the extent and speed to which a complex of poly(styrenesulfonate)
and poly(diallyldimethylammonium) may be doped. Both parameters followed
a Hofmeister ordering and covered a wide range of response. Differences
between doping and undoping kinetics were observed, with the latter
adhering well to classical diffusion from the cylindrical geometry
employed. Tracer diffusion of radiolabeled Na<sup>+</sup>, compared
with coupled diffusion of NaCl, revealed slightly faster diffusion
of Na<sup>+</sup> compared to Cl<sup>–</sup> ions within the
PEC
Asymmetric Growth in Polyelectrolyte Multilayers
Radioactive
counterions were used to track the ratio of positive
to negative polymer repeat units within a polyelectrolyte multilayer
made from poly(diallyldimethylammonium chloride), PDADMAC, and poly(styrene
sulfonate), PSS. For this widely employed pair of “linearly”
assembled polyelectrolytes it was found that the accepted model of
charge overcompensation for each layer is incorrect. In fact, overcompensation
at the surface occurs only on the addition of the polycation, whereas
PSS merely compensates the PDADMAC. After the assembly of about a
dozen layers, excess positive sites begin to accrue in the multilayer.
Treating the surface as a reaction–diffusion region for pairing
of polymer charges, a model profile was constructed. It is shown that
different reaction–diffusion ranges of positive and negative
polyelectrolyte charge lead to a blanket of glassy, stoichiometric
complex growing on top of a layer of rubbery, PDADMAC-rich complex.
Though overcompensation and growth was highly asymmetric with respect
to the layer number, entirely conventional “linear”
assembly of the multilayer was observed. The impact of asymmetric
growth on various properties of multilayers is discussed
Roughness and Salt Annealing in a Polyelectrolyte Multilayer
The surface roughness
of polyelectrolyte multilayers made from poly(diallyldimethylammonium
chloride),
PDADMAC, and poly(styrene sulfonate), PSS, was measured as a function
of film deposition conditions. For dry multilayers, the significant
roughness which builds up for thicker films is much more apparent
for multilayers terminated with PSS. Corresponding roughness for PDADMA-capped
multilayers may be seen by imaging in situ under electrolyte. Roughness
may be substantially reduced, but not eliminated, by annealing in
salt. Annealing does not lead to loss of polyelectrolyte from the
film, even under conditions where the salt concentration is high enough
to place the film properties beyond the glass transition. Roughness
does not correlate with the molecular weight of the polyelectrolyte
and is thus not caused by solution or film polymer chain conformations.
The wavelength of the roughness features is approximately proportional
to film thickness, which supports a mechanism whereby roughness is
generated by anisotropic swelling due to water and polyelectrolyte
addition in a manner similar to water uptake in hydrogels. Roughness
is preserved by the glassy PSS layer and probably incorporated within
the film as it grows
Thermal Transformations in Extruded Saloplastic Polyelectrolyte Complexes
Extruded, salt-plasticized complexes of hydrated poly(styrenesulfonate),
PSS, and poly(diallyldimethylammonium), PDADMA, were analyzed by differential
scanning calorimetry and dynamic mechanical thermal analysis. Whereas
the enthalpic signatures were weak, the latter technique revealed
a strong transition in modulus, identified as a glass transition.
The temperature of this transition, <i>T</i><sub>g</sub>, varied with deformation rate as expected from time/temperature
superposition. <i>T</i><sub>g</sub> also decreased with
increasing salt doping, which breaks ion pairing in the complexes,
confirming the plasticizing effect of doping. Time, temperature, and
salt concentration data were superposed to demonstrate the trends/equivalence
of these three variables, and an empirical equation was used to connect
them. Measurement time regimes were discussed with reference to the
average lifetime of an ion pair