Article

pubs.acs.org/Langmuir

Highly Stable Concentrated Nanoemulsions by the Phase Inversion

Composition Method at Elevated Temperature
Lijie Yu, Chao Li, Jian Xu, Jingcheng Hao, and Dejun Sun*
Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan, Shandong, 250100, P. R.
China
ABSTRACT: Oil-in-water nanoemulsions were produced in
the system water/Span 80Tween 80/paran oil via the
phase inversion composition (PIC) method at elevated
temperature. With the increase of preparation temperature
from 20 to 70 C, we found that the emulsion droplet
diameter decreases from 10.3 m to 51 nm, proving the
formation of nanoemulsions. The viscosity of nanoemulsions
clearly increases with droplet volume fraction, , but the
droplet size changes less. Signicantly, at 0.5, the size
distribution of nanoemulsions can be kept unchangeable more
than 5 months. These results proved that the highly viscous paran oil can hardly be dispersed by the PIC method at 25 C, but
the increase in preparation temperature makes it possible for producing monodisperse nanoemulsions. Once the nanoemulsion is
produced, the stability against Ostwald ripening is outstanding due to the extremely low solubility of the paran oil in the
continuous phase. The highly stable nanoemulsions are of great importance in practical applications.

INTRODUCTION
Emulsions with droplet diameter in the nanometer scale are
often referred to as nanoemulsions.1 Since emulsions are
thermodynamically unstable systems, energy input is required
for the formation of emulsions. Two main approaches are
currently used for the preparation of nanoemulsions: high
energy and low energy. For the high-energy method, intense
mechanical energy input is carried out by extreme shear stirring,
high-pressure homogenizers, or ultrasounds.25 One important
advantage of these methods is the emulsication of the highly
viscous oil phase such as silicon oil and long-chain
triglycerides.6,7 The size distribution of these nanoemulsions
has not changed over months due to the insolubility of the oil
phase in water.8 In addition, concentrated nanoemulsions could
be produced by the combination of high-pressure homogenization and repeated ultracentrifugal fractionation. The
disadvantage of the these methods is the high energy intensity
required to generate nanoemulsions with small droplets,
making this approach unfavorable for industrial applications.8
For the low-energy method, the chemical energy stored in
the components is used by changing the spontaneous curvature
of the surfactants. For nonionic surfactant systems, this can be
achieved by changing the temperature at constant composition,
i.e., phase inversion temperature, PIT method, or changing the
composition at constant temperature, i.e., phase inversion
composition, PIC method.9,10 The PIC method has a great
potential for scale-up applications because of the ease of
formation and relatively low energy costs. A phase transition is
produced by stepwise addition of water to a mixture of the
surfactant and oil for the formation of oil-in-water (O/W)
nanoemulsions. 11 This process is well-known for the
emulsication of short-chain alkanes prepared at 25 C.12
2012 American Chemical Society

However, the Ostwald ripening, i.e., the oil diusion in the

aqueous phase, causes nanoemulsions to break down in
relatively short time periods, which is the main limitation for
developing practical applications.13
Generally speaking, the production of monodisperse nanoemulsions with small droplet size and high kinetic stability is
attractive for both a theoretical and practical point of view. In
our previous work, the liquid paran-in-water nanoemulsions
were prepared via the PIC method at low temperature.14 The
emulsion droplet diameter grows slowly and remains less than
300 nm after 5 months of storage at room temperature.
Afterward, nanoemulsions were prepared via the PIT method
using a more viscous paran oil. The size distribution has not
changed more than 6 months.15,16 In this report we present a
complete study on the formation and stability of nanoemulsions made via the PIC method using the viscous paran
oil. This study explored the inuence of emulsication
temperature, HLB value, and droplet volume fraction. These
results demonstrate that the PIC method at elevated temperature is of great signicance in nanoemulsion formation and
long-term stability.

EXPERIMENTAL SECTION

Materials. The paran oil (d25 = 0.86, chemically pure grade),

Sorbitan monooleate (Span 80, chemically pure grade), and
polyoxyethylene (20) sorbitan monooleate (Tween 80, chemically
pure grade) were obtained from Sinopharm Chemical Reagent Co.,
Ltd. The components of this paran oil are mainly isoalkenes with

Received: July 24, 2012

Revised: September 14, 2012
Published: September 18, 2012
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2033 carbon atoms, as measured with an Agilent 7890 GC (Agilent

Co.). All reagents were used as received without further purication.
Water used in this work was deionized water.
Preparation of Nanoemulsions. Before emulsication, the
surfactants (Span 80 and Tween 80) were dissolved into the oil
phase under magnetic stirring. The surfactantoil mixture and water
were placed separately in a water bath at the desired temperature.
Then the water phase was added dropwise to the oil solution. After the
emulsication, the samples were immediately poured into colorimetric
cylinders and cooled at ambient temperature (20 C). The inuence
of composition parameters, including the oil-to-surfactant weight ratio
(O/S) and the droplet volume fraction (), was investigated
systematically. Moreover, the formation of nanoemulsions depends
not only on composition variations but also on preparation
conditions.17,18 So the experimental parameters were maintained
constant at a stirring rate of 600 rpm and an addition rate of 2 mL/
min.
Droplet Size Determination. Nanoemulsion droplet size and
distribution were determined by dynamic light scattering (DLS,
using a Brookhaven BI-200SM instrument). A 200 mW green laser (
= 532 nm) with variable intensity was used, and measurements were
carried out at room temperature with a scattering angle of 90. The
emulsion was diluted about 1000 times with deionized water just
before the measurements. The average radius and polydispersity index
were calculated from the intensity autocorrelation data with the
cumulants method. The intensityintensity time correlation functions
were analyzed by the CONTIN method.19
The morphology of macroemulsion droplets was observed with an
Axioskop 40 optical microscope (ZEISS, Germany). The size
distribution was obtained by processing the picture using the
microscopic image analysis software.
Long-Term Stability Test. The long-term stability of nanoemulsions
was assessed by measuring the change of droplet size with time of
storage. The samples were kept sealed at room temperature.
Interfacial Tension Measurements. The interfacial tension
between water and surfactant-in-oil solution was measured by the
spinning drop interfacial tension meter of Model TX500C, which can
be used in a wide range of measurements, 105102 mN m1.
Experiments were carried out with special care to avoid water
evaporation.
Rheological Measurements. Rheological measurements were
carried out on a HAAKE RS 6000 rheometer with a coneplate
geometry at 25 C. The diameter and the cone angle of the cone
plate were 35 mm and 1, respectively. In a steady shear experiments,
the shear rate was typically increased form 1 to 1000 s1 within 5 min.
Electrical Conductivity. Appropriate amounts of oil, surfactants,
and water (0.01 mol/L NaCl was added for the conductivity
determinations) were mixed at room temperature using a magnetic
stirrer. The specic conductivity of samples was measured as a
function of temperature by means of a DDS-307 conductometer with a
Pt/platinized electrode.

Figure 1. Eect of emulsication temperature on emulsion droplet

diameter and interfacial tension for samples with O/S = 1:1 and =
0.1. The dashed lines are used as a guide to the eye.

preparation temperature, the interfacial tension decreases and

the amount of surfactant molecules adsorbed at the O/W
interface increases gradually. At elevated temperatures (70
C), the surfactant adsorption reaches saturation.
Eect of Composition at Elevated Temperature. As
stated above, the droplet size distributions remain unchanged
when the emulsions are prepared at 70, 80, and 90 C. The
temperature of preparation is xed at 70 C for further
investigations. In this section, we examined the inuence of
HLB value and O/S on nanoemulsion formation.
When the emulsion is stabilized by a mixture of nonionic
surfactants, the mixed HLB value is considered to be the
algebraic average of the HLB value of the individual surfactants.
In other words, the variation in the mixed HLB values was
calculated according to the relationship
HLBmix = HLBA A% + HLBB B%

(1)

where HLBmix is the HLB value of the mixed surfactants,

HLBA/B is the HLB value of surfactant A or B, and A% and B%
are the weight percentages of A and B, respectively. All the
HLB values used are obtained at 25 C.
The HLBmix has little eect on the size distributions of
nanoemulsions obtained by the PIT method.20,21 In contrast,
the droplet diameter prepared by the PIC method depends on
both the surfactant mixing ratio and the preparation temperature.22,23 Figure 2 shows the inuence of HLB value on
emulsion droplet size. Corresponding to the minimum droplet
size, there is an optimum HLB region around 10 to 11. In the
following work the eect of O/S was investigated and the
HLBmix of Span 80 and Tween 80 was xed at 10.3 for
simplication. Furthermore, when the emulsions are produced

RESULTS AND DISCUSSION

Eect of Emulsication Temperatures at Fixed
Composition. The droplet diameter of the nanoemulsions
as a function of the preparation temperature is shown in Figure
1. Droplet diameter decreases from 10.3 m to 51 nm with the
increase of emulsication temperature at a constant composition (O/S = 1:1, = 0.1). Macroemulsions with high
polydispersities were obtained when the emulsions were
prepared at 20 or 30 C. The droplet size and polydispersity
decrease dramatically with the increase of emulsication
temperature from 20 to 70 C and remain unchanged with a
further increase in the temperature. Figure 1 also shows the
curve of interfacial tension, which is similar to that of droplet
size. This means that nanoemulsions cannot be obtained at low
temperature due to the relatively high interfacial tension and
the high viscous resistance of the oil phase. With the increase of

Figure 2. Droplet size as a function of the HLB value for samples with
O/S = 1:1 and = 0.1. The dashed lines are used as a guide to the eye.
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dispersed phase (0 < 0.25). The eect of on the droplet

size distribution has been studied less frequently because of the
disadvantage on storage stability especially when the droplets
are concentrated.
In this system, the concentrated nanoemulsions were
produced by simply reducing the amount of water addition
during the emulsication process. The droplet volume fraction,
given by the oil volume fraction plus the surfactant volume
fraction, was varied from 0.1 to 0.62 (Figure 4). The droplet

below 30 C macroemulsions are obtained, yet at 70 C the

droplet diameter remains less than 150 nm over the entire HLB
range investigated. These results prove that the PIC method at
elevated temperature is a meaningful way to produce
nanoemulsions.
We examined the inuence of O/S on emulsion diameter
and polydispersity index of nanoemulsions, as presented in
Figure 3. The droplet diameter increases from 51 to 191 nm as

Figure 3. Evolution of the droplet diameter () and polydispersity

index () of nanoemulsions as a function of oil/surfactant weight
ratio. The dashed lines are used as a guide to the eye.

Figure 4. Variations of droplet diameter () and polydispersity index

() of emulsions as a function of . The dashed lines are used as a
guide to the eye. The solid line indicates the maximally random
jammed volume (MRJ) for monodisperse spheres.

the O/S increases from 1:1 to 4:1. This variation tendency

agrees with those reported earlier by the PIC method prepared
at 25 C.10,18,22 At low O/S the polydispersity index is less than
0.2, which reects a good monodispersity of the nanoemulsions.
Studies on nanoemulsion preparation by low-energy
methods have shown that the key to nanoemulsion formation
could be attributed to the phase transitions occurred during the
emulsication process.11,24,25 The droplet size is governed by
the surfactant phase structure (bicontinuous microemulsion or
liquid crystal phase) at the inversion point induced by either
temperature or composition.1,26,27 However, as is shown in
many literatures,9,28 the purity of all the components is
extremely important in the phase behavior investigation. The
response to temperature in systems with technical grade
surfactants could be completely dierent from that of the pure
system because the partition of surfactant homologues between
water and oil is distinct from each other. The technical grade
surfactants and oil phase used in this system makes it less
meaningful to investigate the phase behavior at dierent
temperatures. So we observed the appearance change with
water addition at 20 and 70 C. When the samples are
equilibrated at 70 C within the experimental O/S region, an
inverse microemulsion phase gradually transforms to an
isotropic bluish bicontinuous microemulsion as water concentration increases. In contrast, when the samples are kept at 20
C, the isotropic microemulsion gradually transforms to a white
gel phase. The change in the natural curvature of the surfactants
during the emulsication process is responsible for the uniform
nanoemulsion formation at elevated temperatures.
Formation of Concentrated Nanoemulsions. In highenergy methods, monodisperse nanoemulsions can be formed
over a wide range of droplet volume fraction (0 < 0.6) by
the combination of high-pressure homogenization and repeated
ultracentrifugal fractionation at 18 000 rpm for 3 h.3,4 The size
distribution of these emulsions has not changed over months.
However, using low-energy methods,10,28,29 most nanoemulsions are prepared at relatively low volume fractions of the

diameter remains less than 58 nm when O/S is xed at 1:1. In

addition, similar patterns were obtained at other O/S ratios.
For instance, the droplet size remains less than 197 nm when
O/S is xed at 4:1. These results demonstrate that the
individual oil droplets do not depend on the dilution of water
once they have been formed. The droplet size is mainly
governed by the structure of the bicontinuous phase during the
phase inversion. Excess water acts only as a dilution medium.
This is in agreement with the literature data28 showing that for
emulsions produced by the PIT method. The slight increase of
the polydispersity index might be attributed to the weak
interactions between oil droplets.
The droplet diameter of the emulsion with = 0.62 is
slightly larger than those of emulsions with lower internal phase
volume fractions. The solid line in Figure 4 marks the
maximally random jammed (MRJ) state for monodisperse
spheres with a packing fraction of MRJ 0.64.30 Mason et al.7
proposed that at high the deform droplets are packed into
foam-like structures. Wilking et al. 8 demonstrated the
disruption of droplet aggregates of concentrated nanoemulsions
into individual droplets by high shear ows using rheological
small-angle neutron scattering. In this case, the increase in
droplet size of the emulsion with = 0.62 might be due to the
droplet deformation and/or the formation of tumbling clusters.
When 0.7, a white gel instead of the translucent
nanoemulsion was observed, which was an indication of
phase inversion.
Figure 5 shows the shear rate dependence of the viscosities of
nanoemulsions with dierent droplet volume fractions.
Emulsions with 0.4 exhibit strong shear-thinning behavior.
With the increase of shear rate, the structure of the
nanoemulsions (i.e., the arrangement of droplets) is gradually
destroyed and locally dense clusters are disrupted into
individual droplets.8 Samples with 0.3 behave like the
Newtonian ows. This result indicates that the cluster
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advantages of the PIC method are as follows: (i) Nanoemulsions could be obtained over a wide range of preparation
temperature. The droplet diameter is below 100 nm when the
temperature is above 50 C in the PIC method, as shown in
Figure 1. But the emulsication in the PIT method should be
xed to a temperature close to THLB. (ii) The temperature
quench after preparation is not necessary in the PIC method.
As stated above, nanoemulsions were poured into colorimetric
cylinders and cooled at ambient temperature. In contrast, using
the PIT method, the samples should be quickly transferred to
an ice bath, and a constant stirring is necessary in many
systems.15,16,32,33 (iii) The eciency of emulsication is
improved by the PIC method. When the emulsion with a
volume of 20 mL was prepared by the PIC method at elevated
temperature, the total emulsication process was carried out
within less than 10 min, whereas the same sample should be
equilibrated at THLB for more than 30 min before the
temperature quench in this system using the PIT method.
High Stability. Ostwald ripening is usually considered to be
the major destabilization mechanism of nanoemulsions. It arises
from the fact that oil solubility increases with decreasing droplet
size. Large droplets grow at the expense of small ones in
polydisperse emulsions due to molecular diusion of the oil
through the continuous phase. The rate of Ostwald ripening
can be obtained by LSW (LifshitzSlezovWagner) theory:34

Figure 5. Shear viscosity as a function of shear rate for emulsions with

dierent dispersed phase volume fractions.

aggregations and interdroplet attractions are weak in the highly

diluted nanoemulsions.
Figure 6 shows the variation of conductivity with temperature for samples with O/S of 1:1 and dierent droplet volume

dr 3
8 CVmD
=
dt
9 RT

(2)

where r is the average droplet radius, t is the storage time, C is

the bulk phase solubility, is the interfacial tension, Vm is the
molar volume of the oil, D is the diusion coecient of the oil
phase in the continuous phase, R is the gas constant, and T is
the absolute temperature. Equation 2 predicts a linear
relationship between the cube of the radius and time.
The main limitation for developing nanoemulsion applications is the relatively low stability. When the emulsication was
produced by high-energy methods, the stability of nanoemulsions could be improved by increasing the oil viscosity,
corresponding to the decrease in C. The size distributions of
these nanoemulsions have not changed over months.6,8 But the
disadvantages of these methods are the high energy cost and
viscous heating.35 For instance, the high-pressure homogenizers
generally work in the pressure range between 50 and 100 MPa.1
When nanoemulsions were prepared using low-energy
methods, the eect of carbon number of various n-alkanes on
nanoemulsion formation and stability has been investigated.31,36,37 The Ostwald ripening is suppressed by the
increase in carbon chain length owing to the decrease of oil
solubility in water.37 Nevertheless, the initial droplet size
increases with the increase in hydrocarbon alkyl chain length
due to the increase in the interfacial tension and oil viscosity. In
brief, it is dicult to obtain highly kinetically stable
nanoemulsions with remarkably small droplet sizes by lowenergy methods.
In our previous work,14 nanoemulsions could be obtained by
the PIC method below 50 C because the liquid paran is
mainly constituted of short-chain isoalkanes (C15 to C26). In
this paper the paran oil is mainly constituted of long-chain
isoalkanes (C20 to C33), which makes the dispersed phase hard
to be emulsied by the PIC method at low temperatures
(Figure 1). Further increase in preparation temperature makes
it possible to produce monodisperse nanoemulsions. The
stability of these nanoemulsions was assessed by following the

Figure 6. Conductivity as a function of temperature for samples with

dierent droplet volume fractions. The dashed lines are used as a guide
to the eye.

fractions. Independent of , with the increase of temperature

the conductivity initially increases slightly and after a certain
point decreases suddenly, reaching very low values. This
indicates that the inversion from an O/W to a W/O emulsion
takes place. The HLB temperature, THLB, was taken as the
average value between the maximum and the minimum values
of conductivity. The reduction of THLB with may be
attributed to the impurity of the surfactants.11,12,21
In nonionic surfactant systems, when nanoemulsions are
prepared by the PIC method at 25 C, the THLB of the systems
is usually lower than 50 C.9,12,20 It is well-known that near the
THLB the interfacial tension reaches a minimum.31 In this way
the PIC process can make use of the low interfacial tension.
However, coalescence rate is extremely fast around the THLB. So
the droplet size of these emulsions grows fast and the
nanoemulsions break down in days. In our system nanoemulsions cannot be obtained at 25 C because the interfacial
tension is relatively high and the THLB is above 70 C. The
emulsication at elevated temperatures takes advantage of the
minimum interfacial tension and makes it possible to produce
nanoemulsions. Moreover, the storage stability of emulsions at
room temperature is improved by avoiding coalescence around
the THLB. In brief, the THLB can be used to guide the
emulsication temperature of the PIC method.
Although the droplet diameters prepared by this method are
similar to those obtained using the PIT method,15,16 the
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applications. It is noteworthy that although the stability of our

nanoemulsions is similar to that of microemulsions, there is a
distinct dierence between them. Because the structure of these
nanoemulsions is highly dependent on the method used to
prepare them,38 consequently the PIC method at elevated
temperature is an excellent alternative for the formation of
stable nanoemulsions. Further eort is required to investigate
the emulsication of other highly viscous oil phases and the
application of these concentrated nanoemulsions.

change in droplet diameters with time of storage at room

temperature (20 C), as summarized in Figure 7. The size

CONCLUSIONS

AUTHOR INFORMATION

Paran oil-in-water nanoemulsions have been obtained by the

PIC method at elevated temperatures. The increase in
preparation temperature enhances the surfactant adsorption at
the O/W interface and reduces the viscous resistance of the oil
phase. As a result, the droplet diameter decreases dramatically
with the increase in emulsication temperature. The droplet
diameter is mainly governed by the structure of microemulsion
during the emulsication process, and excess water acts only as
a dilution medium. In brief, nanoemulsions could be obtained
over a wide range of temperature and droplet volume fractions.
Once formed, the size distributions of nanoemulsions have not
changed over 5 months. The insolubility of the oil phase in the
continuous phase prevented the Ostwald ripening process. The
PIC method at elevated temperature is an attractive alternative
for preparation of nanoemulsions since this method leads to
formation of concentrated nanoemulsions with long-term
stability.

Figure 7. Droplet size as a function of time for samples prepared at

dierent emulsication temperatures and stored at 20 C (O/S = 1:1
and = 0.1).

distributions of nanoemulsions prepared at elevated temperatures have not changed over 5 months. In addition,
nanoemulsions prepared within the experimental O/S region
(Figure 3) also remained stable during the same storage time
(data not shown). In recent literature it has been presented that
the Ostwald ripening rate could be reduced by the addition of a
second, less soluble, component to the dispersed phase.6,34 It is
deduced that the components with long-chain hydrocarbons
could help enhance the stability against Ostwald ripening.
Figure 8 shows the eect of droplet volume fraction on the
stability of nanoemulsions stored at ambient temperature. The

Corresponding Author

*E-mail djsun@sdu.edu.cn; Tel +86-531-88364749; Fax +86531-88364750.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was nancially supported by the Key Project of
Chinese National Programs for Fundamental Research and
Development (973 Program, No. 2009CB930103).

Figure 8. Droplet size as a function of time for samples with dierent

droplet volume fractions.

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dx.doi.org/10.1021/la302995a | Langmuir 2012, 28, 1454714552