Associations in mixtures of hydrophobically modified polymer and surfactant in dilute and semidilute aqueous solutions. A rheology and PFG NMR self-diffusion investigation
S. Nilsson et al., Associations in mixtures of hydrophobically modified polymer and surfactant in dilute and semidilute aqueous solutions. A rheology and PFG NMR self-diffusion investigation, MACROMOLEC, 33(26), 2000, pp. 9641-9649
Viscosity (dilute regime) and surfactant and polymer NMR self-diffusion (di
lute and semidilute regime) measurements were carried out on aqueous soluti
ons of ethyl(hydroxyethyl)cellulose (EHEC) and of a hydrophobically modifie
d analogue, with (HM4-EHEC) and without (HM0-EHEC) a spacer, in the presenc
e of various amounts of sodium dodecyl sulfate (SDS). Strong polymer-surfac
tant interactions were revealed. From the binding isotherm the critical agg
regation concentration (cac approximate to 3 mm) was obtained for the EHEC/
SDS system. By comparing the results from the binding isotherms with those
from the rheological measurements, molecular interactions could be correlat
ed to macroscopic properties. The polymer self-diffusion results suggest th
at the spin-echo attenuation can be described by a log-normal distribution
(distribution of self-diffusion coefficients), giving a median polymer self
-diffusion coefficient D-ME There is no difference in the trend of D-ME bet
ween EHEC and the hydrophobically modified analogues at various SDS concent
rations. The NMR signal decays of highly viscous samples of the modified an
alogues are initially described by a distribution mode followed by a single
exponential (slow component). The effect of hydrophobic modification is se
en in the existence of a slowly diffusing component (D-net approximate to 1
0(-14) m(2) s(-1)) (not observed for the unmodified analogue) that is relat
ed to a strong and long-lived network, at least of the order of the NMR tim
e scale (ca. 0.5 s).