Colloid Polym Sci (2014) 292:12971306

DOI 10.1007/s00396-014-3185-0

ORIGINAL CONTRIBUTION

Modification of the stability of oil-in-water nano-emulsions

by polymers with different structures
Qiao Yang & Xia Xin & Lin Wang & Hang Lu &
Huaying Ren & Yebang Tan & Guiying Xu

Received: 7 June 2013 / Revised: 16 February 2014 / Accepted: 19 February 2014 / Published online: 13 March 2014
# Springer-Verlag Berlin Heidelberg 2014

Abstract The effect of polymers (hydrolyzed polyacrylamide

(HPAM) and hydrophobically modified polyacrylamide
(HMPAM)) on the stability of oil-in-water nano-emulsions
has been studied in paraffin oil/Span 20-Tween 20/water
systems by method of phase inversion composition (PIC).
The stabilization of nano-emulsions was investigated by visual observation and the change of water content induced by
centrifugation. Droplet size distributions of nano-emulsions
were obtained by a laser-scanner particle size distribution
analyzer. The interfacial tension and charge of nanoemulsions were obtained by interfacial tension and zeta potential measurements. All the results indicate that the droplet
size can be decreased by the addition of HMPAM, while
almost no change could be observed when the HPAM was
added. Meanwhile, HMPAM has a better effect on the stabilization of nano-emulsions than HPAM. It may conclude that
the HMPAM molecules adsorbed at the oil/water interface of
the nano-emulsion droplets. Therefore, the stability of nanoemulsion with the addition of HMPAM is based on both an
associative thickening mechanism caused by the alkyl chains
of HMPAM molecules and the adsorption of HMPAM at the
oil/water interface, which can form a solid film to prevent the
Ostwald ripening of nano-emulsion droplets.
Keywords Nano-emulsion . HPAM . HMPAM . Stability .
Zeta potential . Interfacial tension
Q. Yang : X. Xin (*) : Y. Tan : G. Xu
National Engineering Technology Research Center for Colloidal
Materials, Shandong University, Jinan 250100, Peoples Republic
of China
e-mail: xinx@sdu.edu.cn
Q. Yang : X. Xin : L. Wang : H. Lu : H. Ren : Y. Tan : G. Xu (*)
Key Laboratory of Colloid and Interface Chemistry (Shandong
University), Ministry of Education, Jinan 250100, Peoples Republic
of China
e-mail: xuguiying@sdu.edu.cn

Introduction
With a droplet size of 50500 nm, nano-emulsion has aroused
a continuous and growing interest due to its characteristic
properties such as small size, high interfacial area, and transparent optical properties [13]. It has advantages in many
aspects of application field, for example, pharmaceutics [4,
5], cosmetics [6, 7], and food [8, 9] and chemical [10, 11]
industries. Especially, nano-emulsion can be used to effectively displace residual oil from the reservoir rocks, and monodisperse nano-emulsions with a small droplet size and a high
kinetic stability are attractive from the viewpoint of both
fundamental study and practical application. However, the
main mechanism responsible for the destabilization of nanoemulsions is attributed to Ostwald ripening, which can lead to
the growth of small droplets to larger ones and ultimately
coarsening of the nano-emulsion [12]. Consequently, its practical applications are limited.
Since Ostwald ripening is the main mechanism for nanoemulsion coarsening, the stability of the nano-emulsion thus
depends on the factors which can influence the rate of Ostwald
ripening. These factors include the preparation methodology,
the order of component addition, and the nature of the phases
generated during the emulsification process [1317]. For example, the compositions, ambient temperature, and concentration of emulsifiers have a significant effect on the initial
droplet size of the formed oil-in-water (O/W) nano-emulsion
and then can affect the rate of Ostwald ripening [13, 16, 17]. In
addition, the incorporation of some amphiphilic molecules
into the oil phase can decrease the droplet size, strengthen
the interfacial film, slow emulsion breaking processes such as
creaming and coalescences, and change the rate of Ostwald
ripening. In our previous study, we have investigated the
influence of the addition of small amounts of ionic surfactants
sodium dodecyl sulfate (SDS) and cetyltrimethylammonium
bromide (CTAB) on properties of O/W nano-emulsion with

1298

paraffin oil as the oil phase and Span 20/Tween 20 as the

surfactant mixture [18]. The results indicated that the addition
of both SDS and CTAB induces a decreased mean droplet
size; however, the anionic surfactant SDS enhances the stability of the nano-emulsion, while the cationic surfactant
CTAB leads to a decrease of nano-emulsion stability. It is thus
inferred that the electrostatic repulsion between droplets is
responsible for the stability of the nano-emulsions.
The use of polymeric surfactants as emulsifiers and stabilizers in emulsions has attracted much attention in recent years
[19, 20]. Among the polymeric surfactants, hydrophobically
modified water-soluble polymers have been a target of extensive studies because of their potential industrial applications
such as cosmetics, foodstuff, drug delivery systems, oil recovery, and water treatment [21, 22]. Sun et al. [23] investigated
the stability of oil-in-water emulsions stabilized by
hydrophobically modified hydroxyethyl cellulose
(HMHEC). It was found that HMHEC shows much better
thickening ability than unmodified hydroxyethyl cellulose
(HEC). It is caused by the association of hydrophobic alkyl
chains of HMHEC molecules which is absent between HEC
molecules. Perrin and Lafuma [24] pointed out that the properties of emulsion are closely dependent on molecular weight,
hydrophobic modification of hydrophobically grafted poly
(sodium acrylates) and emulsifier concentration and all factors
lead to the variation of the viscosity of polymer aqueous
solutions. Akiyama et al. [25] indicated that the good thickening ability of the polymer, the elastic gel formed by it, and
the adsorption of polymer molecules at the oilwater interface
are all important for the stability of the oil-in-water emulsions.
Hydrophobically modified polyacrylamide (HMPAM) is a
typical example of hydrophobically modified water-soluble
polymers [26, 27], and it is found that the performance of the
polymer can be drastically changed even less than 1 mol% of
hydrophobic groups are incorporated on the unmodified hydrolyzed polyacrylamide (HPAM). In this paper, the influence
of HMPAM on the properties of an O/W nano-emulsion
system with a composition of water/Span 20-Tween 20/
paraffin oil which was obtained by the phase inversion composition (PIC) method at 25 C was investigated by visual
observation, droplet size distributions, interfacial tension, zeta
potential, and rheological measurements. The purpose of this
research is to compare the effect of polymers with different
structures on the stability of O/W nano-emulsions.

Experimental section
Materials
Paraffin oil ( = 0.845 g cm 3 , CP) is a product of
Shuangshuang Chemical Reagent Co. Ltd., China. Sorbitan
monolaurate (Span 20; hydrophile-lipophile balance, HLB=

Colloid Polym Sci (2014) 292:12971306

8.6; CP) and polyoxyethylene sorbitan monolaurate (Tween

20, HLB=16.7, CP) were purchased from Tianjin Kermel
Chemical Reagent Development Centre, China. Water used
in this work was deionized water. The hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were supplied by China National Offshore
Oil Corporation and used as received. The average molecular
weight of HPAM is 1.2107 g mol1, and the degree of
hydrolysis is 18 %. And, the average molecular weight of
HMPAM is 1.7106 g mol1, the degree of hydrolysis is
18.2 %, and the content of the hydrophobic group is <1 %.
The structures of both HPAM and HMPAM are shown in
Fig. 1.
Methods
Preparation of nano-emulsions
Firstly, energy input is needed for the production of nanoemulsions. The chemical energy stored in the components is
used to change the spontaneous curvature of the interfacial
films, which can be achieved by changing the composition at a
constant temperature (phase inversion composition, PIC) and
during this process low energy is adopted. In the PIC method
of an oil-in-water (O/W) nano-emulsion production, usually, a
phase transition is produced by the stepwise addition of water
to a mixture of the surfactant and oil. The detail is below: a
mixture of Span 20/Tween 20 with a weight ratio of 48.8/51.2
was dissolved in paraffin oil, and then water was slowly added
(1.0 mL min1) under gentle magnetic stirring at 25 C. It is a
suitable ratio (HLB=12.75) to prepare stable nano-emulsions
according to ref [13]. At last, the content of oil is 20 wt%, the
content of a mixture of Span 20/Tween 20 is 10 wt%, and the
content of water or polymer solution added was fixed at
70 wt% of the total system. After preparation, the nanoemulsions were divided into small portions and stored at
25 C for further characterizations. Compositions which were
considered as nano-emulsions were transparent, translucent,
or opaque, showing a bluish or reddish shine when observed
through a spotlight [28]. The photos of the samples were taken
at fixed time interval to evaluate the long-term stability of
nano-emulsion.
Stability tests
To determine the acceleration at which a thin continuous oil
layer is released on top of the emulsion cream as a result of
coalescence and the critical osmotic pressure at which a continuous oil layer is released as a quantitative measure of
emulsion coalescence stability, the creaming stability of
nano-emulsion was investigated by inferring from the change
of the water content induced by centrifugation (10 min at
12,000 rpm; Anke TGL-16G; Shanghai). This method has

Colloid Polym Sci (2014) 292:12971306

1299

Fig. 1 Structures of HPAM and

HMPAM

been widely used in the stability analysis of nano-emulsion

and concentrated emulsions [29]. The nano-emulsion can be
separated into different layers under centrifugation. After the
centrifugation, about 1 mL of sample was taken from a depth
of 1 cm below the surface. The water contents of the samples
before and after the centrifugation were determined by Karl
Fischer titration (787 KF Titrino, Metrohm). The creaming
stability was measured using the percentage of water removed
(defined as K, %) from the samples, which is calculated as
below (Eq. 1):
K C t0 C t =C t0  100 %

to fabricate the oil/water interface. The image of the Laplacian

profile of the bubble or drop formed at a needle tip was
captured by a CCD camera, digitized, and analyzed by a
computer according to the Laplace equation to obtain the
interface tension.
Zeta potential
Zeta potential was measured using a micro-electrophoresis
meter (JS94H, Zhongchen Ltd. Co., Shanghai). Each sample
was measured three times, and the values were averaged.
Rheological measurement

where Ct0 and Ct is the water content before and after centrifugation, respectively. The smaller the water removal, the
more stable the nano-emulsion is. The long-term stability of
the nano-emulsion was estimated by visual observation of the
photos taken at fixed time intervals for the samples stored at
25 C.

The rheological measurements were carried out on a HAAKE

RS75 rheometer (Germany) with a coaxial cylinder sensor
system (Z41 Ti) at 25 C. For the shear-dependent behavior,
the viscosity measurements were carried out at shear rates
ranging from 0 to 1,000 s1.

Droplet size
Results and discussion
The size distribution of the nano-emulsion droplets was measured using a laser scattering particle size distribution analyzer
(Beckman-Coulter, LS. 230, USA). Measurements were carried out after appropriate dilution of the sample emulsion with
water. It was confirmed in advance that the dilution process
did not significantly change the particle size. The measurement errors were less than 0.5 %.
Interfacial tension measurement
The interfacial tension between polymer-containing solutions
and paraffin oil was measured on the PROCESSOR K12
processor tensiometer (Krss Co., Germany) with ring method. The measurements were carried out for 30 min, and the
interfacial tension values were the average of readings from
three times. All experiments are performed at 25.00.1 C.
Interfacial dilational viscoelasticity measurements
The interfacial dilational viscoelasticities at the oil/water interfaces were measured using an oscillating bubble rheometer
(Tracker, Teclis Co., France). A paraffin oil drop was formed

Stability of nano-emulsions
The stability of nano-emulsion was visually inspected after
stored for 2 months at 25 C. The results of the stability of
HMPAM-containing nano-emulsion with varying HMPAM
concentration from 10 to 600 mg L1 were investigated (the
picture is not shown here). It can be concluded that all of the
samples remained stable even after 2 months and no obvious
phase separation was observed. Coalescence process between
the droplets did not occur significantly, and the droplet size
was still below 500 nm. Besides, the HPAM-containing nanoemulsion with an HPAM concentration ranging from 10 to
200 mg L1 has a similar phenomenon.
As indicated above and according to Tcholakovas work
[30], coalescence stability is evaluated by the critical osmotic
pressure at which a continuous oil layer is released and can be
measured by centrifugation immediately when the sample
was prepared. By this way, the long-term stability of the
nano-emulsion stabilized by HPAM or HMPAM can be inferred in a relatively short time. The coalescence stability of
the nano-emulsions is usually evaluated by the water removal

1300

Colloid Polym Sci (2014) 292:12971306

Droplet sizes of nano-emulsions

(K) after centrifugation. In case of HPAM-containing nanoemulsion, the water content decreased obviously after centrifugation (Fig. 2a) and it was found that K calculated from
Eq. (1) decreases with the increase of HPAM concentration
first and then increases a little when the concentration of
HPAM exceeds 20 mg L1 (Fig. 2c), indicating that the best
concentration of HPAM to stabilize the nano-emulsions is at
20 mg L1. For HMPAM-containing nano-emulsion, the water content is nearly unchanged before and after centrifugation at 12,000 rpm for 10 min (Fig. 2b) and it was found that
K remains nearly constant with the increase of HMPAM
concentration first and then increases obviously when the
concentration of HMPAM exceeds 40 mg L1 (Fig. 2c),
indicating that below 40 mg L1, all the concentrations of
HMPAM we observed can stabilize the nano-emulsions.
Moreover, it also can be seen that the values of K for
HMPAM-containing nano-emulsion are much lower than
those of HPAM, indicating higher stability of the former
compared with the later. It is well known that centrifugation
can accelerate the collision and promote the rupture of the
interfacial film, which causes the coalescence of the droplets.
The high coalescence stability of HMPAM-containing nanoemulsion compared to that of polymer-free (K=4.18 %) or
HPAM-containing nano-emulsion can be explained by the
increased thickness and strength of the interfacial film and
the decreased dehydration rate caused by the polymer
addition.

b
Before centrifugaltion
After centrifugaltion

The water content %

Before centrifugaltion
After centrifugaltion

78

75

72

10

10

10

75

70

65

10

-1

CHMPAM (mg L )

4
HPAM
HMPAM

0
10

10
-1

CHPAM (mg L )

K%

The water content %

Fig. 2 The water contents of

nano-emulsions (a, b) and the
variation of water removal (K) of
nano-emulsions (c) as a function
of the concentration of HPAM or
HMPAM, respectively

The size distribution of the droplets is one of the important

characteristics of nano-emulsion. The dependence of droplet
size of the nano-emulsion on the concentration of HPAM or
HMPAM was given in Fig. 3. It can be seen that the addition
of HMPAM decreases the droplet size while HPAM nearly has
no change on the droplet sizes (the droplet size of polymerfree nano-emulsion is 168.3 nm). When the concentration of
HMPAM was increased from 10 to 600 mg L1, a decrease in
droplet size from about 140 to 80 nm was observed. This
phenomenon reveals the role of the polymers on the formation
of the nano-emulsion. Generally speaking, the polymer possesses three functions in the system. First, the polymer has
surface activity and can adsorb on the oil/water interface,
which can increase the flexural modulus of the interfacial film
and inhibit the variation of spontaneous curvature of the
interface. Second, under a certain stirring intensity, the viscosities of nano-emulsions increase with the increase of polymer
concentrations, which is not suitable for the shear dispersion
of droplets. Third, the adsorbed polymer molecules on the oil/
water interface can reduce the interfacial tension [31]. Among
them, the third function helps to form small droplets, and the
first two functions are not conducive to the formation of new
droplets. The small variation of the size distribution of HPAM
system also reveals that it has little effect on the stability of oil/
water nano-emulsion compared with HMPAM system.

10

10
-1

C (mg L )

Colloid Polym Sci (2014) 292:12971306

b
-1

-1

CHMPAM/mg L

CHPAM/mg L
2
4
20
60
80
200

10
20
40
80
200
400
600

40

Intensity/a.u.

20

Intensity/a.u.

Fig. 3 Droplet size distributions

of nano-emulsion at different
concentrations of HPAM (a) and
HMPAM (b). Variation of the
droplet diameter for HPAM- and
HMPAM-containing nanoemulsions as a function of HPAM
(c) and HMPAM (d)
concentration

1301

10

30
20
10
0

10

10

10

d (nm)

d (nm)

180

160

140

Diameter/nm

160

Diameter/nm

140

120

120

100

80

100
10

10

10
-1

CHPAM (mg L )

Moreover, it can be observed that the droplet size of

HMPAM-containing nano-emulsion is smaller than that of
HPAM-containing nano-emulsion. It can be ascribed to the
difference between the molecular structure of HPAM and
HMPAM. The molecular weight of HMPAM is smaller and
more compact than that of HPAM, and the viscosity of HPAM
is larger than that of HMPAM; thus, at the same concentration,
the amounts of HMPAM molecules adsorbed at the oilwater
interface are more than that of HPAM [32].
The changes in droplet size as a function of the storage time
for nano-emulsions with different concentrations of emulsifiers were also investigated, and the results are not shown
here. The droplet size keeps nearly unchanged at all HPAM
and HMPAM content in 2 months, indicating samples with
different emulsifier concentrations all have good stability. It
has been known that the main unstable mechanism for nanoemulsion is the Ostwald ripening due to the different solubility
of droplets with various sizes. The results indicate that the
Ostwald ripening rate during the study is very little.
Interfacial tensions of different mixed systems
In order to confirm whether HPAM or HMPAM molecules
adsorbed at oil/water interfaces, interfacial tension experiments were performed and the results are shown in Fig. 4. It
can be seen that HMPAM itself can lower the interfacial
tension of the paraffin oil/water interface. This indicates that

10

10

10
-1

CHMPAM(mg L )

HMPAM can adsorb at the oil/water interface and can form

a polymer layer to stabilize the nano-emulsion. In comparison, only tiny changes of the interfacial tension have been
observed for HPAM-containing system (Fig. 4a). This indicates that HPAM molecules cannot effectively adsorb at
paraffin oil/water interface, which is consistent with a literature report [33].
It is common to see the synergistic effect in a polymer/
surfactant mixture [34], which can influence the stability of
the nano-emulsions. When 2105 mol L1 Span20/Tween20
with a weight ratio of 48.8/51.2 was added to the aqueous
solution of HMPAM, a continuous decrease of the interfacial
tension was observed (Fig. 4b). Over the whole investigated
HMPAM concentration, the interfacial tensions are lower than
those without Span20/Tween20 due to the intrinsic surface
activity of the surfactant mixture. When the same amount of
surfactant mixture was added to the aqueous solution of
HPAM, however, an increase in the interfacial tension was
noticed. It revealed that HMPAM, with the side hydrophobic
chains, can interact with the surfactant mixture of Span20/
Tween20 to form a mixed layer at the paraffin oil/water
interfaces. This makes the interface close-packed and improves the stability of the nano-emulsion [18]. But, it is not
the case for HPAM due to its low surface activity and better
water solubility. Moreover, it may pull part of surfactant
molecules from the interface into the solution, accounting
for the increase of the interfacial tensions.

1302

45

-1

Interfacial tension (mN m )

pure HPAM

-1

Interfacial tension (mN m )

Fig. 4 Variations of the

interfacial tensions (a, b) at oil/
water interface of pure HPAM,
HMPAM, Span20/Tween20/
HPAM, and Span20/Tween20/
HMPAM solutions as a function
of the concentrations of HPAM
and HMPAM; Variations of the
dilational viscoelasticities (c) of
HPAM and HMPAM at the oil/
water interfaces at various
oscillation frequencies

Colloid Polym Sci (2014) 292:12971306

-5

2 10 mol/L Span20/Tween20 +HPAM

40

35

30

25
0

10

10

10

pure HMPAM

40

-5

2 0 mol/L Span20/Tween20 +HMPAM

30

20

10
1

10

10

10
-1

-1

CHMPAM (mg L )

CHPAM (mg L )

(mN m-1)

30

HMPAM 10
HMPAM 100
HPAM 10
HPAM 100

25

20

0.01

0.1

(Hz)

Zeta potential
The zeta potentials of HMPAM- and HPAM-containing nanoemulsions were measured, and the results were given in Fig. 5.
It can be seen that the zeta potential of the nano-emulsion
increases with the concentration of HMPAM or HPAM, indicating that both of them can enhance the stability of the nanoemulsions through the improvement of electrostatic repulsion

HPAM
HMPAM

Zeta Potential(mV)

Because the main reason of the stability of the nanoemulsions is attributed to the associative thickening mechanism of the film, thus, the interfacial rheology would provide
more direct information on the film properties, and the
dilational viscoelasticities of HPAM and HMPAM at the oil/
water interfaces have been measured at various oscillation
frequencies (as shown in Fig. 4c). It can be seen that the
dilational modulus increases with the increasing oscillation
frequency, which coincides with the previous results of traditional surfactants with long chains [18]. Comparing the curves
of HPAM and HMPAM, the dilational modulus of HPAM is
found to be low in comparison with HMPAM, suggesting that
the strength against perturbation of surface layer of HMPAM
is higher than that of HPAM, which makes the interfacial film
of HMPAM more stable.
Combined with the O/W interfacial tension results mentioned above, it can be seen that a low value of the interfacial
tension for the interface of nano-emulsions favors the emulsification. Besides, from the results of the interfacial
dilational moduli of nano-emulsions, it can be seen that the
dilational moduli of the interface is also expected to be
important for the emulsion stability because it is responsible
for the dampening of area fluctuations, which are instead
needed for breaking droplets. The overall results demonstrate
the great importance of the interface dilational moduli in
emulsion stability.

-20

-30

-40

10

10

10

10

-1

C(mg L )
Fig. 5 Variations of zeta potential of O/W nano-emulsions as a function
of the concentrations of HPAM and HMPAM

Colloid Polym Sci (2014) 292:12971306

1303

between oil droplets. It is in agreement with the results reported in the literatures [35, 36]. The zeta potential of nanoemulsion with HMPAM is larger than that of system with
HPAM, presumably due to the adsorption of HMPAM molecules at the paraffin oil/water interface, which is consistent
with the results of the interfacial tension measurements. It is
well known that flocculation may contribute to the instability
of the nano-emulsions during storage, especially for the samples with a low polymer concentration. Generally, the flocculation can be restrained by steric or electrostatic stabilization
[17]. In our system, it can be seen that the stabilization of
nano-emulsions can be achieved by increasing HPAM or
HMPAM concentration. An alternative is to supply enough
electrostatic energy barriers between droplets, since the electrostatic repulsive effect of the adsorbed layer is an important
mechanism to prevent the coalescence of droplets.

electrostatic attraction between HMPAM molecules, so the

viscosities of these two kinds of nano-emulsions have apparent differences even at low concentrations (10 mg L1) and at
higher concentrations, HPAM-containing nano-emulsions
showed much better thickening ability than HMPAM ones.
The thickening mechanism of HPAM can be illustrated as
follows: at low concentrations, it mainly exhibits intramolecular association and the polymer chains are curling,
accounting for the low viscosity. As the concentration is
increased, intermolecular aggregation occurs which leads to
the association of the hydrophobic groups between different
HPAM molecules, and a transient three-dimensional network
is formed. Hence, the viscosity of the solution drastically
increased.
Stabilization mechanism of nano-emulsion stabilized
by HPAM and HMPAM

Viscosity of nano-emulsions
Figure 6 illustrates the steady shear rate-viscosity curves for
the nano-emulsions at different HPAM or HMPAM concentrations. For the HPAM-containing nano-emulsion, a
Newtonian fluid behavior was observed at low concentrations.
When the concentration is above 100 mg L1, a shear thinning
behavior appears, and it has been taken as an evidence for the
formation of network which is due to the formation of intermolecular hydrogen bonding between the HPAM molecules
[37]. For HMPAM-containing nano-emulsion, all the samples
are approximately Newtonian fluids in the investigated shear
rates until 800 mg L1, indicating that higher stability of
HMPAM compared with HPAM on nano-emulsions, which
is in agreement with the experimental results shown above.
The zero-shear viscosity (0) can be obtained from Fig. 6,
and a comparison between 0 of HPAM- and HMPAMcontaining nano-emulsions is shown in Fig. 7. Although
HMPAM molecule has hydrophobic side chain, its molecular
weight is much lower than that of HPAM and there is


cr cexp

10


2

 



RT
c r 1
1 1

ln
:
2
Vm
c r 2
r1 r2

Equation (3) shows that the larger the difference between r1

and r2, the higher the rate of Ostwald ripening.

b
10

2V m
rRT

where c(r) is the solubility surrounding a particle of radius r,

c() is the bulk phase solubility, and Vm is the molar volume
of the dispersed phase.
For two droplets of radii r1 and r2 (where r1 <r2),

10

-1

10

-2

Viscosity (Pas)

Viscosity (Pas)

One of the main problems for nano-emulsions is Ostwald

ripening which results from the difference in solubility between small and large droplets. The difference in chemical
potential of dispersed phase droplets between droplets with
different sizes as given by Lord Kelvin [38],

CHPAM/mg L-1
2
4
8
20
40
80
100
200
600

10

10

Shear rate

10

(s-1)

10

-1

CHMPAM/mg L
10
40
80
200
600
800
1000

10

10

10

Shear rate (s-1)

Fig. 6 Viscosity () versus shear rate for nano-emulsions at different concentrations of HPAM (a) and HMPAM (b)

10

1304

Colloid Polym Sci (2014) 292:12971306

HPAM
HMPAM
2

Viscosity (Pas)

10

10

10

-2

10

10

10

C (mg L-1)
Fig. 7 The zero-shear viscosity (0) of nano-emulsions as a function of
HPAM and HMPAM concentrations

Ostwald ripening can be quantitatively assessed from plots

of the cube of the radius vs. time t (the Lifshitz-Slesov
Wagner, LSW, Theory) [39, 40],


8 cV m D
3
r
t
4
9
RT
where D is the diffusion coefficient of the disperse phase in the
continuous phase and is the density of the disperse phase.
According to Eq. (3), the reduction in results in the
reduction of Ostwald ripening. However, only one factor is
not sufficient since one has to reduce by several orders of
magnitude. Walstra [41] suggested that by using surfactants or

Scheme 1 Schematic
representation of the proposed
mechanism for polymer-stabled
nano-emulsions by adding
HPAM and HMPAM

polymers, which are strongly adsorbed at the O/W interface

and do not desorb during ripening, the rate could be significantly reduced. An increase in the surface dilational modulus
and decrease in would be observed for the shrinking drops.
The difference in between the droplets would balance the
difference in capillary pressure (i.e., curvature effects).
Thus, from the above results, we can summarize the stabilization mechanism of nano-emulsions containing HPAM and
HMPAM. At low concentration of HPAM, the molecules of
HPAM are spread, and the viscosity of Span 20-Tween 20/
paraffin oil/water nano-emulsions is enhanced by HPAM,
which can stabilize the nano-emulsion by reducing the settling
velocity. At intermediate concentration, HPAM molecules
cannot effectively adsorb at the oil/water interface due to its
low interfacial activity, leading to Ostwald ripening of the
nano-emulsion. And at higher concentration, flocculation of
HPAM results in the decline of stability of nano-emulsion.
In the case of HMPAM, at low concentration of
HMPAM, it has a strong interaction with Span 20/Tween
20 and can adsorb at the oil/water interface due to its
higher interfacial activity. The mixed adsorption layer can
effectively prevent the droplets from moving and
impacting with each other to form a bigger droplet through
three-dimensional interaction, thus preventing Ostwald
ripening of the droplets and stabilize the nano-emulsion
[23, 42, 43]. At higher concentration, however, flocculation of HMPAM plays the main role which disfavors the
stabilization of nano-emulsion. The sketch map of the
adsorption of HMPAM molecules at the oil/water interface
is shown in Scheme 1.

Colloid Polym Sci (2014) 292:12971306

When the concentration of HPAM or HMPAM is higher

than a critical value, the nano-emulsions will unstable and
make the flocculation of the systems. This is because the rate
of Ostwald ripening increases at higher polymer concentration, and in case of nano-emulsions, this was also reported
previously [44, 45]. It is well known that the emulsion drop
size evolution is first controlled by Ostwald ripening and
later on by drop coalescence which is quite short. The
overall emulsion lifetime is therefore dominated by ripening.
And for given oil, the overall emulsion lifetime appears well
correlated with the interfacial dilational moduli of adsorbed
layer, which is expected to control coalescence. When any
component of nano-emulsion which controls ripening is
changed, the stability of nano-emulsion is also changed.
The reasons for the Ostwald ripening may include [46] the
following: (i) the decrease in droplet size at higher polymer
concentration increases the Brownian diffusion; (ii) as the
droplet size decreases, the Laplace pressure inside the droplet becomes greater, leading to a greater tendency for the
components to diffuse between small and large droplets; and
(iii) the structure of the network is too strong at higher
polymer concentration which is unfavorable for the stability
of nano-emulsions, especially for HPAM-containing nanoemulsions.

Conclusions
The influences of HPAM and HMPAM on the stability of oilin-water nano-emulsions which is composed of water/Span
20-Tween 20/paraffin oil via the phase inversion composition
(PIC) method were investigated. From the experimental results, it is concluded that both the addition of HPAM and
HMPAM can stabilize the nano-emulsions and HMPAM is
more effective than HPAM. This is because HMPAM is an
amphoteric substance with hydrophobic and electrostatic attractive properties. It can form an intra-molecular salt, and it
is active at the interface. HMPAM also has an associative
thickening mechanism; thus, it can enhance the viscosity of
the nano-emulsions, adsorb at the oil/water interface, and
interact with surfactant to form a mixed solid adsorption
layers. Therefore, this enhances the strength of interfacial
film to prevent Ostwald ripening of the droplets. Moreover,
a more comprehensive knowledge on the influence of additives and mechanisms on nano-emulsion formation will allow
their optimization and consequently will expand their
applications.

Acknowledgment We graefully acknowledge the financial support from the Natural Science Foundation of China (21203109),
Independent Innovation Foundation of Shandong University
(IIFSDU), and the national science base of talent cultivation
(J1103314).

1305

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