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doi:10.1006/jcis.2001.8066
I. INTRODUCTION
0021-9797/02 $35.00
C 2002 Elsevier Science (USA)
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POLYMER/SURFACTANT INTERACTION
FIG. 2.
region (shown by the lower dotted line in Fig. 2). This behavior
was reported (10) for PNIPAM microgel/SDS systems: apparently the reactivity of the polymer toward SDS is retained in
bulk phase, leading to a clearly defined T1 transition, but not
at the air/water interface because of the limited surface activity
of the microgel particles. This behavior contrasts with a conventional response of molecular PNIPAM shown, for example, by
the work of Jean et al. (11) in which interaction of this highly
surface-active polymer and SDS was clearly evident from the
surface behavior.
In closing this section, it is noted that the feebly surface-active
polymer PAAM has been found to display virtually no reactivity
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E. D. GODDARD
toward SDS, just the opposite of hydrophobically modified polymers which are markedly surface active (8).
2. Other Surface Analyses, Films, Foams
In a series of papers, Thomas, Penfold, and co-workers
(1214), using specular neutron reflection techniques on PEO/
SDS and PVP/SDS systems, demonstrated in general terms that
below T1 , mixed surface films of polymer and surfactant are
present, but above T1 the polymer is displaced. Increases in surfactant concentration in the surface occur beyond T1 and can
occur to some extent beyond T2 : the actual concentration of
polymer affects the particular behavior observed. In the case of
PEO/SDS the presence of polymer tends to depress somewhat
the surface concentration of SDS: with PVP/SDS up to T1 there
is an increase and beyond it a slight decrease. A discordant note
remains on comparing these results with the radiotracer work of
Chari and Hossein in which a 30% reduction in surface concentration of SDS was observed in the presence of PVP (15), but,
in general terms, the above trends are in accord with neutron reflectance data on PNIPAM/SDS systems, although differences
in degree result from the much higher surface activity of this
polymer versus PVP or PEO (11).
The case of adsorption in a mixed surfactant uncharged polymer system has been analyzed thermodynamically by de Gennes
(16). If the polymer adsorbs one can expect a change in adsorption of the surfactant and of its foaming and thin-film properties,
including drainage rate, when the layers of polymer overlap and
the surface viscosity changes (increases). The result would be
more stable films and foams (see Fig. 4). Testing to date of these
concepts has been limited. In film drainage studies on a series
of polymer/surfactant systems Cohen-Addad and diMeglio (17)
found rather small effects of the polymer even in the case of
the strongly interacting PEO/SDS system. It should be noted,
however, that the concentration of SDS was well above the cmc.
On the other hand, in very recent work, involving foam and
single-film studies by Folmer and Kronberg (4) on the PVP/SDS
system, definite improvements in stability were found up to a
surfactant concentration approximating T21 ; beyond this, progressive removal of polymer from the interface rendered any
improvement negligible (or even negative). More work in this
important area can be expected (18).
B. Charged Polymer/Oppositely Charged Surfactant
1. Surface Tension
It was shown, evidently for the first time, by the author and
co-workers in 19751976 (1921) and reported at the 1977
Mittal symposium, that the surface tension behavior of the title
systems can be quite different from those involving uncharged
polymers (see Fig. 3). As observed in bulk phase, interaction
at the surfaceevident from pronounced lowering of surface
tensioncan be detected at very low concentrations of surfactant (104 M or less) in the cationic cellulosic Polymer
JR/SDS system. Even in the precipitation zone, when most of the
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POLYMER/SURFACTANT INTERACTION
d = RT d ln[SDS].
The net aggregate area/molecule (1/ ) of the surfactant ion
computed from the above equation, for all molecular weights of
2 /mol, to be almost the same as
polylysine, turned out, at 43 A
that of SDS in simple aqueous solution, possibly reflecting the
flexibility and high charge density of this polymer. It should be
noted that the assumptions made in deriving the above equation
are that the surface excess values of all the simple ions present
(Na+ , Br ) approximate zero and that variations in the actual
concentration of the polyion present are, for practical purposes,
without effect.
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E. D. GODDARD
POLYMER/SURFACTANT INTERACTION
233
FIG. 8. Drainage films (pictorial) for SDS (1%) observed after 5 s (a)
and after 30 s (b) and for SDS (0.01%)/Polymer JR 400 (0.01%) after 30 s
(c). Reproduced, with permission, from Regismond et al. (39).
FIG. 10. Polycation adsorption on a negatively charged solid. Top (a): with
a cationic surfactant (depressed flotation); bottom (c): with an anionic surfactant (elevated flotation). Reproduced, with permission, from Somasundaran
et al. (49).
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E. D. GODDARD
TABLE 1
Experimental Techniques (Solid/Liquid)
Adsorption analysis (43)
Atomic force microscopy (44)
Calorimetry (45)
Ellipsometry (46)
Electron spin resonance (47)
Fluorescence (48)
Flotation/wetting (42, 49)
Infrared (50)
Microscopy (51)
Neutron reflection (52)
FIG. 11. Adsorption of LiDS and PVP on alumina from PVPLiDS mixed
solution. Reproduced, with permission, from Otsuka and Esumi (47).
POLYMER/SURFACTANT INTERACTION
IV. CONCLUSIONS
235
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