ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. 2008; 3: 579585

Published online in Wiley InterScience
(www.interscience.wiley.com) DOI:10.1002/apj.212

Research Article

Interaction between aqueous solutions of polymer

and surfactant and its effect on physicochemical properties
Mohammad Yunus Khan, Abhijit Samanta, Keka Ojha and Ajay Mandal*
Department of Petroleum Engineering, Indian School of Mines University, Dhanbad, India

Received 19 June 2008; Revised 30 July 2008; Accepted 18 August 2008

ABSTRACT: Interaction between water-soluble polymers and anionic surfactants has been studied by surface tension
and conductivity measurements. Sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) were
used as surfactant while polyacrylamide (PAA), commercial grade partially hydrolyzed polyacrylamide (PHPA), and
xanthan gum were used as water-soluble polymers for the present study. The behavior of surfactantpolymer interaction
was found to be dependent on both surfactant and polymer concentrations. After the critical aggregation concentration
(CAC), interaction between the water-soluble polymer and surfactants was started and above the polymer saturation
point (PSP) polymer was saturated by surfactant with no further change of surface tension and conductivity of the
solution. It has also been found that alkali (NaOH) and salts (Na2 CO3 , NaCl) have significant influence on the
polymersurfactant interaction. 2008 Curtin University of Technology and John Wiley & Sons, Ltd.
KEYWORDS: polymer; surfactant; surface tension; conductivity; aggregation; saturation

INTRODUCTION
Interaction between the polymer and surfactant has been
extensively studied for its widespread applications in
industries. In fact, they play an outstanding role in
pharmaceuticals, cosmetics, detergents, pesticides, and
enhanced oil recovery. Specific interests on the polymer and ionic surfactant systems are because of its
characteristic physicochemical properties at different
possible combinations. The basic principles of the polymersurfactant interactions are discussed by Kwak,[1]
Goddard and Ananthapadmanabhan[2] , and others.[3 5]
Still there are a lot of controversies and uncertainties on
the behavior of surfactantpolymer systems because of
their complex behavior in aqueous solution.
The interaction between surfactant and polymer
depends on the molecular structure of the two components and the net charges either on the molecule of
one of the components or both of them.[6 8] Brackman and Engberts[9] discussed the effect of functional
group and the chain length of the surfactant on polymersurfactant interaction. The anionic surfactants are
found to have stronger interaction with nonionic polymer compared with other type of polymers.[10] The
characteristic behavior of polymer with surfactant is
similar to surfactant micellization in solution and occurs
*Correspondence to: Ajay Mandal, Department of Petroleum
Engineering, Indian School of Mines University, Dhanbad-826
004, India. E-mail: ajay mandal@yahoo.com
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

above a critical aggregation concentration (CAC) which

is lower than the corresponding critical micellization
concentration (CMC).[11] It is well known that the
hydrophobic character of both the polymer and surfactant is responsible for the interaction. The nature of
these interactions has been investigated and reported
by Brackman and Engberts,[12] Shirahama et al .,[13]
and Hou et al .[14] . Jean et al .[15] reported that surfactants at high concentration can displace polymer
from the air/water interface depending on the system.
Avranas and Iliou[3] have done significant works on
the interactions between hydroxy-propylmethylcellulose
and alkylsulfonate surfactants, and they found that the
chain length of the anionic surfactant influences the
polymer adsorption at the interface. Dubin et al .[16] proposed the direct role of the cation in the stabilization
of the complex in which the cation interacts simultaneously with the micelle (through electrostatic forces) and
with the polymer (via coordination complexation). This
type of association may occur simultaneously with other
interaction forces. Minatti and Zanette[17] showed the
variation of CAC and polymer saturation point (PSP) of
polyethylene oxide and sodium dodecyl sulfate (SDS)
system at different NaCl concentrations.
Various aspects of the polymersurfactants interactions have been reported by analyzing viscosity,[18 22]
electric conductivity,[19,23,24] and surface tension.[25,26]
In the present work, a number of experiments have
been conducted to characterize the interaction between
different polymers [polyacrylamide (PAA), partially

M. Y. KHAN ET AL.

hydrolyzed polyacrylamide (PHPA), and xanthan gum]

and anionic surfactants [SDS and sodium dodecylbenzene sulfonate (SDBS)] at various concentrations by
measuring the conductivity and surface tension of the
solution. The effect of salts (Na2 CO3 and NaCl) and
alkali (NaOH) on the interaction between the polymer
and surfactant system has also been investigated.

EXPERIMENTAL
Materials
Two anionic surfactants, viz. SDS(approximately 99%
purity) and SDBS(approximately 98% pure quality)
were used for the present study. SDS (C12 H24 SO4 Na,
MW = 288.38) was purchased from Central Drug
House (P) Ltd., India and SDBS (C18 H29 NaO3 S, MW =
348.48) was procured from LOBA Chemie Pvt Ltd.,
India. Reagent grade Sodium Hydroxide (96% purity)
from Sd Fine-Chem Ltd., was used as alkali. Na2 CO3
and NaCl were purchased from Ranbaxy and Qualigens
Fine Chemicals, respectively. Three different polymers,
viz. PAA [(CH2 CHCONH2 )x , MW = 5 000 000, Made:
National Chemicals, India], commercial grade PHPA
(avg. mol. wt. = 3 000 000, SNF Floerger, France), and
xanthan gum (avg. mol. wt. = 250 000, Otto Kemi,
Mumbai) were used for the present study. These products were used because of their wide application in
industry.[27 30]

Preparation of solutions
The aqueous solutions with different concentrations of
surfactant and polymer were always freshly prepared
using a magnetic stirrer for 810 h to form a consistent
homogeneous solution at a low rotation per minute to
avoid any mechanical degradation. Appropriate quantity of anionic surfactant and polymer were dissolved
carefully in distilled water for about 15 min. A wide
range of concentrations approximating the CMC of SDS
(0.010.4 wt%) and SDBS (0.00010.4 wt%) were
chosen for the present study. The polymers (i.e. PAA,
PHPA, and xanthan gum) were used at 250, 500, 1000,
1500, 2000, and 2500 ppm concentrations. These ranges
of compounds were chosen to correspond with those
used for industrial applications.[17,28,31 34]

Asia-Pacific Journal of Chemical Engineering

thoroughly cleaned and flame-dried before each measurement. To determine the surface tension, the vertically hung ring was dipped into the liquid and then
subsequently pulled out. The maximum force required
to pull the ring through the interface was taken as the
surface tension, (mN/m). The tensiometer was calibrated with pure water at 298 K. In all cases, more than
three successive measurements were carried out, and
the standard deviation did not exceed 0.1 mN/m. The
conductivity data of the solutions were obtained by digital conductivity meter (Century Instruments Pvt. Ltd.,
Model: CC601). The instrument was properly calibrated
with KCl solutions of known concentration prior to taking the readings. The conductivity data were recorded
by placing the conductivity probe in the solution until
stable values were obtained. All the measurements were
carried out at a temperature of 25 C.

RESULTS AND DISCUSSION

Surface tension of surfactants
It is well known that surfactants reduce the surface
tension of water by getting adsorbed on the liquidgas
interface. The CMC, one of the main parameters for
surfactants, is the concentration at which surfactant
solutions begin to form micelles in large amounts.[18]
Surface tensions of the surfactant (SDS and SDBS)
solutions at different concentrations were measured and
plotted as a function of concentration (Fig. 1). The
concentration at the turning point of the curve is CMC.
Reduction of surface tension with increase in surfactant
concentration is more prominent for SDBS compared
with SDS as observed from Fig. 1. The CMC value of
75

Surface Tension, mN/m

580

70

SDS

65

SDBS

60
55
50
45
40
CMC

35
CMC

30

Methods
Surface tension of different solutions was measured
under atmospheric pressure by the ring method[21] using
an Auto tensiometer (Rigosha & Co. Ltd., Model:
6801ES with platinum ring). The platinum ring was
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

25
0.00

0.05

0.10

0.15

0.20

0.25

0.30

Concentration of Surfactants (wt. %)

Figure 1. Variations of interfacial tensions with surfactant

concentrations. This figure is available in colour online at
www.apjChemEng.com.
Asia-Pac. J. Chem. Eng. 2008; 3: 579585
DOI: 10.1002/apj

Asia-Pacific Journal of Chemical Engineering

INTERACTION OF POLYMERSURFACTANT AQUEOUS SOLUTIONS

SDBS (0.075 wt%) is also lower than that of SDS (0.1

wt%) due to the difference in their head groups.

80
75

Different techniques are used to examine the watersoluble polymersurfactant aggregates formed in
solution.[3,4,17] The interaction of water-soluble polymers with anionic surfactants has been studied by surface tension and conductivity measurements. The main
characteristic of surfactants is to lower the interfacial
tension between an aqueous solution and some other
phases. But for ionic surfactant, these properties are
modified by the presence of polymer in aqueous solution. Figures 2 and 3 show the variations in surface
tension in the aqueous solutions of SDS and SDBS in
the presence of PAA polymer at different concentrations. Surface tension of surfactant solutions increases
in the presence of polymers. Surface tension vs surfactant concentration plots in the presence of polymer
show three distinct zones as shown in the Figs 2 and
3. Above the CAC, the interaction between the watersoluble polymer and surfactants is started. Dynamic
equilibrium between surfactant-saturated polymer and
the regular aqueous micelles coexist just above the PSP.
Thus with further increase in surfactant concentration,
surface tension remains constant and normal surfactant
micelles start to form.
With increase in the concentration of polymer, the
surface tension of the combined system gradually
increases. Though different authors[17,35] reported that
CAC and PSP slightly increase with an increase in
concentration of polymer, the variations in the above

0 ppm PAA
250 ppm PAA
500 ppm PAA
1000 ppm PAA
2000 ppm PAA

CAC

65
60
55
50
PSP

45
40
35
30

CMC

25
0.0

0.1

0.2

0.3

0.4

Concentration of SDBS (wt. %)

Figure 3. Effect of polyacrylamide on surface tension

of SDBS. This figure is available in colour online at
www.apjChemEng.com.

75
70
Surface Tension, mN/m

Surface tension of surfactantpolymer

mixtures

Surface Tension, mN/m

70

0 ppm Xanthan Gum

500 ppm Xanthan Gum
1000 ppm Xanthan Gum
1500 ppm Xanthan Gum

65
60
55
CAC

50

PSP

45
40
35
30

CMC

0.0

0.1

0.2

0.3

0.4

0.5

Concentration of SDS (wt. %)

80

Surface Tension, mN/m

70

60

Figure 4. Effect of xanthan gum on surface tension

of SDS. This figure is available in colour online at
www.apjChemEng.com.

0 ppm PAA
1000 ppm PAA
1500 ppm PAA
2000 ppm PAA
2500 ppm PAA

CAC
PSP

50

40
CMC

30
0.0

0.1

0.2

0.3

0.4

0.5

Concentration of SDS (wt. %)

Figure 2. Effect of polyacrylamide on surface tension

of SDS. This figure is available in colour online at
www.apjChemEng.com.
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

parameters within the concentration range of the present

study are quite negligible.
Figures 4 and 5 show the effect of xanthan gum and
PHPA polymer respectively on the surface tension of an
aqueous solution SDS. These combinations also show
similar types of interaction via CAC and PSP like the
previous combinations shown in Figs 2 and 3. However,
the surface tension of combined xanthan gum and
SDS system decreases with increasing concentration of
the polymer at the same concentration of surfactant.
This is due the fact that xanthan gum itself shows
lower surface tension in aqueous solution.[36] Nedjhioui
et al .[4] also found the same behavior of xanthan gum
solutions in the presence of other surfactant. The values
Asia-Pac. J. Chem. Eng. 2008; 3: 579585
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581

M. Y. KHAN ET AL.

Asia-Pacific Journal of Chemical Engineering

75

70
0 ppm PHPA
250 ppm PHPA
500 ppm PHPA
1000 ppm PHPA
1500 ppm PHPA
2000 ppm PHPA

65
60

CAC

60

55
PSP

50

Nil
0.005 % SDS
0.1 % SDS
0.1% SDS+1500ppm PAA

65
Surfac Tension, mN/m

70

Surface Tension, mN/m

45

55
50
45
40
35
30
25

40

20
35

15

CMC

30

10
-2
0.0

0.1

0.2

0.3

0.4

10

12

14

16

18

Concentration of NaOH (wt. %)

Concentration of SDS (wt. %)

Effect of partially hydrolyzed polyacrylamide

(PHPA) on surface tension of SDS. This figure is available
in colour online at www.apjChemEng.com.

Figure 5.

Figure 6.
Variations in surface tension with alkali
concentrations. This figure is available in colour online at
www.apjChemEng.com.

Table 1. Values of CMC, CAC, and PSP for different

surfactantpolymer combinations.

System

CMC

CAC

PSP

SDS
SDBS
SDS-PAA
SDBS-PAA
SDS-xanthan gum
SDS-PHPA

0.100
0.054

0.525
0.0155
0.0371
0.0215

0.1108
0.0959
0.1038
0.1033

at PSP
(mN/m)
(1000 ppm
polymer)

36.28
35.53
38.61
41.61

60
Surface Tension (mN/m)

582

Nil
1500 ppm PAA
1500 ppm PAA+1% NaOH

55
50
45
40
35
30

of CAC, PSP, and surface tension at PSP for different

surfactantpolymer combinations are shown in Table 1
along with the CMC of two surfactant solutions.

0.0

0.1

0.2

0.3

0.4

Concentration of SDS (wt. %)

Figure 7. Effect of alkali on surface tension of SDS in the

Surface tension of combined

AlkaliPolymerSurfactant
The presence of alkali in a solution significantly influences the surface and interfacial tensions.[4,30] Figure 6
represents the variation of surface tension with alkali
(NaOH) in the presence of SDS and polymer. It is
observed from the figure that surface tension of alkali
solution is decreasing with increase in NaOH concentration up to a certain limit; beyond which it again
starts to increase. An interesting observation of the
study was that addition of a minute quantity (0.005%)
of surfactant significantly reduces the surface tension,
which remains almost unchanged with further addition (0.1%) of the surfactant. The effect of NaOH on
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

presence of polyacrylamide. This figure is available in colour

online at www.apjChemEng.com.

polymersurfactant interaction may be clearly understood from Fig. 7. Significantly lower values of surface tension are observed in alkalipolymersurfactant
system due to a synergistic effect of alkali on the
surfactant compared with surfactantpolymer system
without alkali. The decrease in surface tension of surfactantpolymer solution in the presence of alkali may also
be due to the charge-shielding mechanism and hydrolysis polymer. This reduced surface tension is one of
the most important criteria for enhanced recovery of
oil by increasing the capillary number of oilwater
system.
Asia-Pac. J. Chem. Eng. 2008; 3: 579585
DOI: 10.1002/apj

Asia-Pacific Journal of Chemical Engineering

INTERACTION OF POLYMERSURFACTANT AQUEOUS SOLUTIONS

Effect of salt on surfactantpolymer

interaction

60
55

Nil
1500 ppm PAA
1500 ppm PAA+1% Na2CO3
1500 ppm PAA+1% NaCl

Conductivity of surfactantpolymer system

The interaction of polymer and surfactant may also be
observed from the conductivity measurements. Conductivity of aqueous polymersurfactant solution is nothing but the dissociated cations and anions of polymer
and surfactant. Thus, conductivity of the solution is

50
45
40
35
30
25
0.0

0.1

0.2

0.3

0.4

Concentration of SDBS Surfactant (wt%)

Figure 9. Effect of salts on surfactantpolymer interaction. This figure is available in colour online at
www.apjChemEng.com.

2500

Specific conductivity (S/cm)

It has been reported

that addition of salt significantly reduces the CMC of ionic surfactants. For
surfactantpolymer system, CAC also decreases drastically in the presence of salt, indicating that association
starts at a much lower concentration of the surfactant.[2]
The effects of 1% Na2 CO3 and 1% NaCl on polymersurfactant interaction are shown in Fig. 8. It may
be seen that in the presence of salt, the surface tension
of the solution significantly decreases. This reduction in
surface tension is probably due to the increasing binding
ability between surfactant and polymer in the presence
of salt. Suksamranchit and Sirivat[35] also reported that
in salt solution with higher ionic strength, the formation of micelles and surfactantpolymer complexes is
promoted due to reduction in electrostatic repulsion
between the ionic surfactant head groups, which stabilizes the surfactant micelle structure. Figure 9 shows
the salt effects on PAA polymer and SDBS surfactant
system. This system also shows a similar trend as in
the case of SDS-PAA-salt systems. However, the effect
of salts is more prominent at lower concentration in the
case of SDBS.

Surface Tension (mN/m)

[37,38]

PSP

2000
CAC

1500

1000
0 ppm PAA
1500 ppm PAA
2000 ppm PAA
2500 ppm PAA

CMC

500

0
0.0

65

0.1

0.2

0.3

0.4

Concentration of SDS (wt. %)

Surface Tension (mN/m)

60

Nil
1500 ppm PAA
1500 ppm PAA+1% Na2CO3
1500 ppm PAA+1%NaCl

55
50

Effect of polyacrylamide on conductivity

of SDS. This figure is available in colour online at
www.apjChemEng.com.

Figure 10.

45
40
35
30
25
20
0.0

0.1

0.2

0.3

0.4

Concentration of SDS Surfactant (wt%)

Figure 8. Effect of salts on surfactantpolymer interaction. This figure is available in colour online at
www.apjChemEng.com.
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

related to dissociation and thus an interaction between

the polymer and surfactant. Figure 10 represents specific conductivity as a function of SDS concentration
in the absence and presence of polymer. The figure
shows that conductivity increases with increase in the
concentration of surfactant. The break point (CMC) is
also clearly identified in the conductivity plot in the
absence of polymer as shown in the Fig. 10. Above this
concentration, the slope of conductivity vs surfactant
concentration decreases, since the free SDS ions contribute more to the solution conductivity as compared
with the same ions in micelles.[39] In the presence of
polymer, the plots are shifted upward showing higher
Asia-Pac. J. Chem. Eng. 2008; 3: 579585
DOI: 10.1002/apj

583

M. Y. KHAN ET AL.

Asia-Pacific Journal of Chemical Engineering

2200
2000
Specific conductivity (S/cm)

values of conductivity. The higher conductivity of the

surfactant solutions in the presence of polymer is probably due to a higher mobility of the sodium ion of
the surfactant under complexation with polymer compared with its relatively strong ion-pairing with SDS
micelles in the absence of polymer.[40] In addition, the
polymersurfactant complex may consist of surfactant
micelles bound to the polymer, enabling higher mobility
of the sodium ions from one micelle to another.[41] Evidence of formation of polymer-surfactant complexes[42]
may be observed from the characteristic behavior of
the conductivity plots within the concentration range
of CAC-PSP. Figures 11 and 12 show conductivity vs
SDS concentration in the presence of xanthan gum and
PHPA, respectively, which also show similar trends.

PSP

1800
1600

CAC

1400
1200
1000
800
0 PPM PHPA
1000 PPM PHPA
1500 PPM PHPA
2000 PPM PHPA

600
400

CMC

200
0
0.0

0.1

0.2

0.3

0.4

Concentration of SDS (wt. %)

Effect of PHPA on conductivity of SDS

solution. This figure is available in colour online at
www.apjChemEng.com.

Figure 12.

CONCLUSIONS
On the basis of the results of the experiments which
were conducted to examine the interaction between
anionic surfactants and polymers by measuring the
surface tension and conductivity of the solutions, the
following conclusions can be drawn.
1. The lowering of surface tension with increase in
concentration of surfactants is higher in the case of
SDBS, and also the CMC value of SDBS (0.075
wt%) is lower than that of SDS (0.1 wt%) due to the
difference in their head groups.
2. Surface tension of the surfactant solutions increases
in the presence of polymers. However, the surface tension of xanthan gum and SDS system taken
together was found to decrease with increasing concentration of the polymer for the same concentration

3.

4.

5.

9000
0 ppm Xanthan gum
1000 ppm Xanthan gum
2000 ppm Xanthan gum
2500 ppm Xanthan gum

8000
Specific conductivity (S/cm)

584

7000

6.

6000
5000
4000

PSP

CAC

3000

of surfactant, as xanthan gum itself shows lower surface tension in aqueous solution.
The surface tension vs surfactant concentration plots
in the presence of polymer shows three distinct zones
and the interaction between surfactant and polymer is
strongly dependent on the surface tension concentration. The maximum interaction occurs between CAC
and PSP of the surfactant.
It has also been seen that alkali (NaOH) has significant influence on the polymersurfactant interaction.
The presence of a very minute quantity of alkali
in aqueous surfactant solution shows a substantial
effect on the surface properties. The surface tension of the aqueous solution of NaOH first decreases
with an increase in concentration of NaOH and then
slowly increases after passing through minima.
The presence of salt significantly reduces the surface
tension of surfactantpolymer system due to increasing binding ability between surfactant and polymer
in the presence of salt.
The interaction between polymer and surfactant
observed by surface tension measurement was found
to be supported by the conductivity measurements
also.

2000
CMC

Acknowledgements

1000
0
0.0

0.1

0.2

0.3

0.4

Concentrationof SDS (wt. %)

Figure 11.
Effect of xanthan gum on SDS conductivity. This figure is available in colour online at
www.apjChemEng.com.
2008 Curtin University of Technology and John Wiley & Sons, Ltd.

We gratefully acknowledge the financial assistance

provided by the Council of Scientific and Industrial Research (CSIR, 424/07) to the Department of
Petroleum Engineering, Indian School of Mines University, Dhanbad, India. Thanks are also extended to
all individuals associated with the project.
Asia-Pac. J. Chem. Eng. 2008; 3: 579585
DOI: 10.1002/apj

Asia-Pacific Journal of Chemical Engineering

INTERACTION OF POLYMERSURFACTANT AQUEOUS SOLUTIONS

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