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Chinese Journal of Polymer Science Vol. 26, No.

1, (2008), 31−37 Chinese Journal of


Polymer Science
©2008 World Scientific

EFFECTS OF NH4Cl ON THE INTERACTION BETWEEN POLY(ETHYLENE


OXIDE) AND IONIC SURFACTANTS IN AQUEOUS SOLUTIONS

Jing Li, Hua-zhen Li, Hai-yang Yang*, Ping-ping Zhu and Ping-sheng He
Department of Polymer Science & Engineering, University of Science & Technology of China, Hefei 230026, China

Abstract The interaction of poly(ethylene oxide) (PEO) with the ionic surfactants, sodium dodecylsulfate (SDS) and

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cetyltrimethylammonium chloride (CTAC) respectively in aqueous solutions containing a certain concentration of NH4Cl,
is studied by the viscosity measurement. It has been found that the ion-dipole interaction between PEO and ionic surfactants
is changed considerably by the organic salt. For anionic surfactant of SDS, the addition of NH4Cl into solution strengthens
the interaction between PEO and the headgroup of SDS. On the other hand, for cationic surfactant of CTAC, the interaction
between PEO and the headgroup of CTAC is screened significantly by NH4Cl dissolved in solution. These findings may
potentially be attributed to the negative property of the oxygen group of the PEO chain. In the presence of NH4Cl, the
cationic ions of the organic salt bind to the oxygen group of the PEO chain so that PEO can be referred to as a pseudo-
polyelectrolyte in solution.
Keywords: Viscosity; Ion-dipole interaction; Non-ionic polymer; Ionic surfactant; NH4Cl.

INTRODUCTION
Interactions between polymers and surfactants in aqueous solutions have attracted significant interests and have
been the subject of review papers because of their widespread applications and relatively complex behaviors[1−3].
With respect to ionic surfactants interacting with non-ionic polymers, the poly(ethylene glycol)/sodium dodecyl
sulfate/water (PEG or PEO/SDS/H2O) is one of the most extensively studied systems and has been investigated
by a great number of techniques, including isothermal titration calorimetry (ITC)[4−9], dynamic laser light
scattering (DLS)[4,5], NMR [6, 10−15], small-angle neutron scattering (SANS)[16], fluorescence spectroscopy[17−21],
viscosity[9, 16, 17, 22−24] and surface tension[11,19,20]. In contrast, little attention[25−27] has been devoted to studying the
interaction between PEO and cationic surfactants such as tetradecyltrimethylammonium chloride and bromide
(TTAC and TTAB), mainly due to the reason that PEO interacts strongly with anionic surfactants but weakly
with cationic surfactants. The most accepted model developed to coin the structure of the complex between PEO
and SDS was presented by Cabane[15]. It was suggested that the PEO chain is wrapped around the micelles with
a fraction of the ethylene oxide units directly adsorbed on the hydrocarbon/water interface, with the major part
of the polymer chain forming loops in the surrounding water. The driving force for the adsorption of ethylene
oxide units to the hydrocarbon/water interface is the hydrophobic interaction between the CH2 groups of ― ―
PEO and the hydrophobic interior of micelles. Due to the bulkiness of the headgroup of the cationic
― ―
surfactant[28], however, the hydrophobic interaction between the CH2 groups of PEO and the hydrophobic
interior of micelles is partly screened by the cationic headgroup. On such an occasion, the hydrophobic
interaction of PEO with the hydrophobic interior of micelles itself is not strong enough to encourage the
complex between PEO and micelles of cationic surfactants. This interprets why PEO interacts weakly with the
cationic surfactants. On the other hand, the ion-dipole interaction of PEO with the cationic surfactant headgroup,

*
Corresponding author: Hai-yang Yang ( 杨海洋
), E-mail: yhy@ustc.edu.cn
Received December 13, 2006; Revised March 29, 2007; Accepted May 10, 2007
32 J. Li et al.

is beneficial to the formation of the complex between PEO and cationic surfactant. It is already known that
―― ――
the O group of PEO is slightly negative[29, 30]. The ion-dipole interaction between the O group of PEO
and positively charged head of cationic surfactants is attractive. If the ionization of cationic surfactant in
――
solution is strong and therefore the sites for the ion-dipole interaction between the O group of PEO and
positively charged head of cationic surfactant is enough, the complex between PEO and the micelles of cationic
surfactants does exist as presented initially by Anthony et al.[26] and recently by Mya et al.[27]. In the presence of
――
organic salts, the cationic ions of organic salts bind to O group of PEO so that PEO becomes a puesdo-
polyelectrolyte in solution. On such an occasion, the various interactions, especially the ion-dipole interaction
between PEO and surfactants, is changed considerably by the organic salts. In particular, the ion-dipole
interaction of PEO with cationic surfactants such as cetyltrimethylammonium chloride (CTAC) will be screened
by the organic salts. On the contrary, the ion-dipole interaction of PEO with anionic surfactants such as SDS will
be strengthened by the organic salts. The viscosity measurements of PEO/SDS mixtures and PEO/CTAC
mixtures in aqueous solutions in the presence and absence of NH4Cl verify this presumption effectively.
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EXPERIMENTAL

Materials
Poly(ethylene oxide) (PEO) was a commercial product of Polyscience Inc. The weight-average molecular
weight was 9.0 × 105. Sodium dodecyl sulfate (SDS) with the purity above 99% was supplied by Xuzhou regent
Co. Cetyltrimetylammonium chloride (CTAC) with the purity above 98% was supplied by the Fine Chemistry
institute of Tianjin. Both SDS and CTAC are A.R. grade and used without further purification. NH4Cl was A.R.
grade and dried under vacuum before use. The deionized water was used for preparing solutions. Both solvent
and solution were filtered with 0.45 µm filters prior to use.
Viscosity Measurements
The viscosity measurements were carried out using an Ubbelohde viscometry that was placed in a
thermostatically controlled bath with a precision of 0.01°C. Measurements were initiated after approximately
10 min equilibrium time. The flow times were determined from an average of several readings (more than
5 readings). The relative viscosity of SDS and CTAC solutions, ηr, was calculated from ηr =t/t0 with t and t0 the
flow time of the solution and the solvent, respectively, neglecting the difference of the density between the
solution and the solvent as performed in our previous studies[31−36]. In particular, the PEO solution in the presence
or absence of NH4Cl was treated as the pseudo-solvent[35]. In other words, the flow time of PEO solution in the
presence or absence of NH4Cl is selected as t0 for determining the relative viscosity of either SDS or CTAC
solutions.
Surface Tension
Surface tension measurements were carried out by using JK99B a automatic interfacial tensionmeter, equipped
with a Pt-Au plate. The values of the critical micellar concentration (CMC) as well as the critical aggregation
concentration (CAC) were estimated by the intersections between the two linear portions of surface tension
versus lg[SDS] plots as presented by Zanette et al.[37].

RESULTS AND DISCUSSION


Figure 1 shows the relative viscosity ηr as a function of SDS for PEO with the concentration of 0.5 g/L in the
presence or absence of NH4Cl at 30°C. The PEO solution in the presence or absence of NH4Cl is treated as the
pseudo-solvent as presented in Experimental Section. The relative viscosity ηr determined according to this
method is renormalized as shown in Fig. 1. From Fig. 1 it can be seen that the two critical concentrations,
namely c1 and c2, exist in the absence of NH4Cl. The concentration c1, known as the critical aggregation
concentration (CAC), indicates SDS has bound to the PEO chain to form polymer-supported micelles along the
polymer chain. In our experiment c1 is 1.8 mmol/L, less than 2.2 mmol/L as presented by Jiang et al[22]. A
Effects of NH4Cl on the Interaction between Poly(ethylene oxide) and Ionic Surfactants in Aqueous Solutions 33

possible interpretation is that the molecular weight of PEO in our experiment is greater than reported. The
influence of polymer chain length upon the critical aggregation concentration has already been noted previously
by others[8, 20]. It is already known that the critical aggregation concentration can be determined by surface
tension measurements[37]. From Fig. 2 it can be seen that the critical aggregation concentration of SDS in PEO
solution is 1.8 mmol/L approximately, which is in good agreements with the results obtained by the viscosity
measurement. Obviously, the electric repulsion between polymer-supported micelles will produce the expansion
of PEO chains. As a result, the relative viscosity ηr increases with increasing concentration of SDS as the
concentration of SDS is higher than c1. The maximum of ηr at the critical concentration c2 indicates the saturation
of bound micelles to the polymer chain, and the subsequent decrease in the relative viscosity on the further
addition of SDS is due to the screening of charge interactions by excess counterions. If the concentration of PEO
is expressed as monomers and the parameter β is defined as [SDS]/[monomers], the value of β at c2 equals 1
approximately. The complex of poly(acrylic acid) (PAA) with cetyltrimethylammonium bromide (CTAB) has
been studied by Fundin et al[38]. Of peculiar interest is that the saturation of CTAB micelles bound to PAA chains
also occurs at β (= [CTAB]/[monomers]) equals 1 approximately, which is by coincidence consistent with our
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experimental result. In the presence of NH4Cl as indicated in Fig. 1, however, both c1 and c2 disappear on the
whole SDS concentration investigated. In particular, the relative viscosity ηr decreases with increasing
concentration of SDS and reaches the minimum at the critical concentration namely cM. The further addition of
SDS will increase the relative viscosity ηr as shown in Fig. 1. From Fig. 3 it can be seen that cM increases with
increasing NH4Cl whereas the relative viscosity at the critical concentration cM , namely [ηr]min, decreases with
increasing NH4Cl. Obviously, to gain a better understanding of the PEO/SDS mixtures in the presence of NH4Cl,
three critical questions have to be answered. The first one is why the relative viscosity ηr decreases with
increasing concentration of SDS and reaches the minimum at the critical concentration cM. The second one is
how to interpret the phenomenon that cM increases with increasing NH4Cl as indicated in Fig. 3. The last one is
why the critical concentration c2 corresponding to the saturation of bound micelles to the polymer chain
disappears in the presence of NH4Cl as shown in Fig. 1.

Fig. 1 The relative viscosity ηr as a function of SDS for Fig. 2 Surface tension plots of SDS in H2O, H2O +
PEO with the concentration of 0.5 g/L in the presence of PEO and H2O + NH4Cl at 30°C
NH4Cl with various levels of concentration at 30°C The CAC and CMC is determined by the interception
of the dashed lines.
34 J. Li et al.
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Fig. 3 The critical concentration namely cM and [ηr]min as a function of


NH4Cl concentrations for PEO/SDS mixtures in aqueous solution at 30°C

It is already known that the ether oxygen of PEO is slightly negative. In the presence of NH4Cl, a positive
charge of PEO chains arises from partial protonation of the ether oxygen of PEO as presented by Schwuger[29],
promoting the conformational change of PEO chains in solution. On the other hand, the addition of NH4Cl will
also promote micelle formation of SDS in solution. In particular, the interaction between PEO and SDS will be
changed by the addition of NH4Cl. It is therefore difficult to understand the viscosity behavior as shown in Fig. 1.
Figure 4 shows the relative viscosity ηr as a function of NH4Cl for PEO/SDS mixtures, PEO, SDS in aqueous
solutions at 30°C respectively. The relative viscosity in Fig. 4 is calculated from ηr = t/t0 with t0 the flow time of
the pure water. From the inset of Fig. 4 it can be seen that the relative viscosity ηr as a function of NH4Cl for
PEO or SDS in aqueous solutions keeps constant approximately in the whole concentration range of NH4Cl
investigated. On the other hand, the relative viscosity ηr of PEO/SDS mixtures in solution decreases
exponentially with NH4Cl as indicated by the dotted curve in Fig. 4. This suggests that the viscosity behavior as
shown in Fig. 1 is mainly dependent on the conformation of PEO/SDS mixtures which is greatly associated with
NH4Cl. It is therefore reasonable to postulate that the experimental result as shown in Fig. 1 indicates that the
size of PEO/SDS mixtures in the presence of NH4Cl should experience an initial decrease and a subsequent
increase with increasing SDS concentration. The effect of NH4Cl upon the ion-dipole interaction between PEO
and SDS should be responsible for the result. According to the model proposed by Cabane[15], a fraction of the
segments of the PEO chain binds to the hydrophobic interior of micelles whereas the major part of the PEO chain
forms loops in the surrounding water. The driving force for the PEO and SDS interaction is the hydrophobic
― ―
interaction between the CH2 groups of PEO and the hydrophobic interior of micelles. Potentially because of
――
the repulsive interaction between the O group of PEO and the negative charged head of SDS, the major part
of the PEO chain forms loops in the surrounding water. In the presence of NH4Cl, PEO chains become a pseudo-
――
polycation due to the binding of NH4+ with the O group of PEO. As a result, the electric interaction between
PEO chains and DS− ions increases significantly. Another possible interpretation is that NH4+ bridges O ――
group of PEO with DS− ions which increases the electric interaction between PEO chains and DS− ions. In a
word, the interaction between PEO chains and headgroup of SDS can be increased significantly in the presence
of NH4Cl as schematically illustrated in Fig. 5. On such an occasion, both the hydrophobic interaction and ion-
dipole interaction encourage the PEO chain to adsorb on SDS micelles so that the PEO chain no longer forms
loops but wrapped efficiently around the micelles of SDS. This suggests that the PEO chain wastes a lot of chain
length wraps around micelles so that the viscosity of polymer solution decreases considerably as shown in Fig. 1.
Considering that the critical concentration cM as shown in Fig. 1 is less than CMC of SDS in pure water as shown
in Fig. 2, it is therefore of interest to know whether the sphere micelles of SDS do exist or not as the
Effects of NH4Cl on the Interaction between Poly(ethylene oxide) and Ionic Surfactants in Aqueous Solutions 35

concentration of SDS is less than cM. From Fig. 2 it can be seen that CMC of SDS in the presence of NH4Cl is
less than 0.2 mmol/L, indicating our suggestion is reasonable. It should be noted that the screening of NH4Cl
upon the repulsive interaction between SDS micelles along the PEO chain can also result in the contraction of the
PEO chain in solution as presented by Chari et al[16]. However, the screening of NH4Cl can be effective only on
condition that the PEO chain has already expanded by the repulsive interaction between SDS micelles along the
PEO chain. From Fig. 1 it can be seen that the repulsive interaction between SDS micelles along the PEO chain
expands the PEO chain when the concentration of SDS is higher than c1. We therefore believe that ηr decreases at
the lower concentration of SDS (cSDS < cM) as shown in Fig. 1 is mainly due to efficient wrapping of the PEO
chain around micelles as indicated in Fig. 5. On the other hand, at the higher concentration of SDS (cSDS > cM),
the repulsion between the charge micelles along the PEO chain becomes dominant. This interprets why the
relative viscosity of SDS solution in the presence of NH4Cl increases gradually with increasing the concentration
of SDS. It is well known that the nonionic polymers interact strongly with anionic surfactants but weakly with
cationic surfactants. This is interpreted as due to the bulkiness of the cationic headgroup[28]. If no specific
――
interaction such as the electric interaction between the O group of PEO and the surfactants, the micelles
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cannot bind to PEO chains in solution. Considering that the degree of ionization of hexadecyltrimethylammonium
chloride (HTAC) is greater than that of hexadecyltrimethylammonium bromide (HTAB), the interaction between
PEO and the micelles of HTAC is stronger than that of HTAB. As a result, the micelles of HTAC can bind to
PEO chain as presented by Mya et al[25]. If the model schematically illustrated in Fig. 5 is correct, the addition of
――
NH4Cl into PEO/CTAC solution should screen the specific interaction between the O group of PEO and
CTA+. On such an occasion, the micelles of CTAC cannot bind to the PEO chain. From Fig. 6 it can be seen that
in the absence of NH4Cl, the micelles of CTAC can bind to the PEO chain, similar to the experimental results
presented by Mya et al.[25]. In the presence of NH4Cl, however, the relative viscosity of solution is almost
independent on the concentration of HTAC, indicating that in the presence of NH4Cl the micelles of CTAC
cannot bind to the PEO chain as expected. This suggests that our presumption is reasonable.

Fig. 4 The relative viscosity ηr as a function of NH4Cl for PEO/SDS mixtures,


PEO, SDS in aqueous solutions at 30°C

If the model as indicated by Fig. 5 is correct, then, the electric interaction between the PEO chain and SDS
micelles should increase considerably in the presence of NH4Cl. On such an occasion, the PEO chain wastes a
lot of chain length wrapping around micelles of SDS micelles. This explains why the relative viscosity ηr
decreases with increasing concentration of SDS and reaches the minimum at the critical concentration cM as
shown in Fig. 1. In particular, in the presence of NH4+ with the higher concentration, the interaction between the
PEO chain and micelles of SDS becomes stronger and the conformation of PEO/SDS mixtures becomes much
36 J. Li et al.

compact. As a result, the relative viscosity ηr at the critical concentration cM decreases accordingly as shown in
Figs. 1 and 3. On the other hand, if the interaction between PEO chains and micelles of SDS becomes stronger in
the presence of NH4+ with the higher concentration, the diffusing and adsorption of the free micelles in solution
on to the PEO chains becomes more difficult. In other words, only at the higher concentration of SDS, the free
micelles in solution can bind to PEO chains and swell the PEO chain efficiently. This explains the phenomenon
why cM increases with increasing NH4Cl as indicated in Fig. 3. Considering that it is difficult for the free micelles
to diffuse and adsorb on to the PEO chain in the presence of NH4+, the critical concentration c2 corresponding to
the saturation of bound micelles to polymer chains should increase to the higher concentration of SDS. This
explains why c2 in the presence of NH4Cl disappears in the whole concentration range of SDS investigated as
shown in Fig. 1.
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Fig. 5 Scheme of the conformation of PEO/SDS mixtures in aqueous NH4Cl solutions


The grey curve line indicates the PEO chain whereas the blue sphere indicates micelles of SDS.

Fig. 6 The relative viscosity ηr as a function of CTAC for PEO in


aqueous solutions in the presence and absence of NH4Cl at 30°C

CONCLUSIONS
The interaction between PEO and ionic surfactants in aqueous solutions is changed considerably in the presence
――
of NH4Cl. The experimental result indicates that the ion-dipole interaction between the O group of PEO
and negative charged head of SDS is strengthened by adding NH4Cl into the solution. On such an occasion, the
PEO chain no longer forms loops but wraps efficiently around the micelles of SDS so that the relative viscosity
of polymer solution decreases considerably at the lower concentration of SDS. The excessive adsorption of
micelles on the PEO chain, however, expands the polymer chain. The relative viscosity of polymer solutions
therefore increases significantly at the higher concentrations of SDS. In contrast, the ion-dipole interaction
Effects of NH4Cl on the Interaction between Poly(ethylene oxide) and Ionic Surfactants in Aqueous Solutions 37

between the ――
O group of PEO and positive charged head of HTAC is screened completely by adding NH4Cl
into solution. As a result, the relative viscosity of the polymer solution is almost independent on the concentration
of HTAC in the presence of NH4Cl.

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