Journal of Colloid and Interface Science 314 (2007) 230235

www.elsevier.com/locate/jcis

Oil-in-water nanoemulsions for pesticide formulations

Lijuan Wang a , Xuefeng Li a , Gaoyong Zhang a , Jinfeng Dong a, , Julian Eastoe b
a College of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, China
b School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK

Received 3 March 2007; accepted 15 April 2007

Available online 13 May 2007

Abstract
A two-step process for formation of nanoemulsions in the system water/poly(oxyethylene) nonionic surfactant/methyl decanoate at 25 C
is described. First, all the components were mixed at a certain composition to prepare a microemulsion concentrate, which was rapidly subjected into a large dilution into water to generate an emulsion. Bluish transparent oil-in-water (O/W) nanoemulsions were formed only when
the concentrate was located in the bicontinuous microemulsion (BC) or oil-in-water microemulsion (Wm) region. The existence of an optimum
oil-to-surfactant ratio (Ros ) in the BC or Wm region indicates that both the phase behavior and the composition of the concentrate are important
factors in nanoemulsion formation. To demonstrate potential applications of these systems, they were employed to formulate a water-insoluble
pesticide, -cypermethrin (-CP). The nanoemulsion was compared with a commercial -CP microemulsion in terms of the stability of sprayed
formulations.
2007 Elsevier Inc. All rights reserved.
Keywords: Nanoemulsion; Equilibrium phase behavior; Pesticide formulation

1. Introduction
Nanoemulsions [1] have uniform and extremely small droplet sizes, typically in the range of 20200 nm. In addition, high
kinetic stability, low viscosity and optical transparency make
them very attractive systems for many industrial applications;
for example, in the pharmaceutical field as drug delivery systems [2,3], in cosmetics as personal care formulations [4], in
agrochemicals for pesticide delivery [5], and in the chemical
industry as polymerization reaction media [6]. The use of nanoemulsions as colloidal drug carriers is well-documented [3,
79]. The bioavailability of drugs was reported to be strongly
enhanced by solubilization in small droplets (below 0.2 m);
for example, submicronic emulsions were found to increase the
bioavailability of cefpodoxime proxetil from 50 to 98%, compared to other oral formulations [9].
Unlike microemulsions, nanoemulsions are metastable systems, and stability depends on the method of preparation. The
most common approach is high-energy emulsification [10], using high-shear stirring, high-pressure homogenizers and ultra* Corresponding author.

E-mail address: colloid@whu.edu.cn (J. Dong).

0021-9797/$ see front matter 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.04.079

sound generators. More recently a neat low-energy emulsification method [11] has been developed, by taking advantage
of phase behavior and properties, to promote the formation of
ultra-small droplets. These low energy techniques include selfemulsification [1214], phase transition [1,15,16] and phase
inversion temperature methods (PIT) [1722]. To make use
of these approaches, it is necessary to study the relationship
between the equilibrium phase behavior of the initial system
and the resulting nanoemulsions. For example, with the PIT
method, emulsions are obtained by increasing or lowering the
temperature quickly to pass through the HLB (hydrophile
lipophile balance) temperature in a system containing nonionic
surfactant. In particular, if the initial system is located in a
bicontinuous microemulsion region (D phase) or a two phase
(W + D) system at the HLB temperature, nanoemulsions can
be readily generated [20]. In the phase transition method, water
is added dropwise to a mixture of surfactants and oil at constant
temperature. The formation of nanoemulsions is generally attributed to phase instabilities during emulsification, where the
presence of lamellar liquid crystallites and/or bicontinuous microemulsions are thought to play critical roles [1,23,24]. However, no direct evidence has yet been put forward to clarify these
issues. Further effort is required in order to fully understand the

L. Wang et al. / Journal of Colloid and Interface Science 314 (2007) 230235

mechanism of nanoemulsion formation, and therefore, optimize

nanoemulsification processes.
In this work, a new self-nanoemulsifying alcohol-free system was developed, where fatty acid methyl ester (methyl decanoate) was chosen as the oil phase. In order to gain a better
understanding of the isothermal formation of these nanoemulsions, a two-step process (method A), was compared with phase
transition methods (B and C); these experiments were designed
to clarify which equilibrium phase is responsible for the formation of nanoemulsions during the phase transition. The relationship between final droplet sizes and the equilibrium phase
behavior of the initial microemulsion concentrate was studied.
One reason for employing fatty acid methyl esters as oily component is due to their mild irritation to eyes and skin [25,26].
Indeed, fatty acid methyl esters derived from vegetable oils
have gained attention over recent years as solvents in a variety of applications [2729]; significantly they are also widely
used as economically viable solvents in pesticide delivery systems [30,31].
To investigate potential applications of the system developed
here, a water insoluble pesticide, -cypermethrin (-CP), was
incorporated into the precursor microemulsion concentrate. The
effect of this active pesticide on stabilities of the concentrate,
and the corresponding nanoemulsion, were also investigated.
The formulation process presented in this work consists of incorporating -CP in a bicontinuous microemulsion, which can
be converted into a nanoemulsion spontaneously upon water
dilution. This technique provides a new method to formulate
water insoluble pesticides for spraying applications.

231

Fig. 1. Schematic representation of the experimental path in method A.

(A) A two-step process: first, mixing all appropriate components to generate a concentrate; then, a certain amount of
concentrate was injected into a very much larger volume
of water under gentle stirring to achieve the final emulsion.
The water concentration in the initial concentrate was fixed
at 50 wt%. This could be termed a crash dilution method.
(B) Water was added dropwise to the surfactant and oil mixture. The addition rate was adjusted carefully, to ensure it
was slow enough that so the bicontinuous D phase or oil-inwater Wm phase was present, but not too slow to result in
an increase in droplet size due to emulsion destabilization.
(C) An appropriate amount of water was poured into a starting
solution of the surfactant and oil mixture. No obvious distinct stable phases were noted during the emulsification
procedure, except for the starting isotropic mixtures of oil
and surfactant and the final emulsion.
The final concentration of water was kept constant at
97.5 wt% and the temperature was held at 25 1 C (thermostat
bath K20, ThermoHaake, Germany).

2. Experimental
2.1. Materials
A technical grade poly(oxyethylene) lauryl ether, with an
average of 7 mol of ethylene oxide (EO) per surfactant molecule, was supplied by Xingtai Lantian Jingxi Chemical Co.
Lt. Methyl decanoate (purity 98.7%) was supplied by Wujiang
Tianhong Food Corporation. -Cypermethrin (-CP) (purity
97%) and a commercial -CP microemulsion were purchased
from Yetian Agrochemical Corporation. All products were used
without further purification. Water was twice distilled.
2.2. Methods
2.2.1. Phase diagrams
All components were weighed, sealed in ampoules, and homogenized with a vibromixer. The samples were kept at 25 C
to equilibrate. Optically anisotropic liquid crystalline phases
were identified by using polarizing light microscopy (PLM,
BX51, Olympus, Japan) through identification of characteristic
textures. The boundary lines were found by consecutive addition of one component to mixtures of the other components.
2.2.2. Nanoemulsion preparation
Emulsions were prepared using the following low-energy
emulsification methods (Fig. 1):

2.2.3. Droplet size measurement

The mean droplet size and distribution of the nanoemulsions
were determined by dynamic light scattering (DLS) at a scattering angle of 173 (Zetasizer Nano-ZS, Malvern, UK) at 25 C,
employing an argon laser ( = 633 nm).
2.2.4. Pesticide-loaded formulations
The solubility of -CP is much higher in methyl decanoate
(468 mg/ml) compared to in water (1.13 104 mg/ml) at
25 C. -CP was incorporated to oil/surfactant mixtures prior
to the addition of water to form the active-loaded concentrate
at 25 C. The concentrate was then injected into water under
gentle stirring to generate nanoemulsions. Dispersions were
sprayed onto glass slides which were examined visually 24 h
after spraying. The appearance of crystals observed by polarizing light microscopy (PLM) indicated that the sprayed solution
was unstable.
3. Results and discussion
3.1. Equilibrium phase behavior of three-component systems:
water/nonionic surfactant/methyl decanoate
The phase diagram of the water/nonionic surfactant/methyl
decanoate at 25 C is shown in Fig. 2. Four distinct one-phase
regions are observed, consistent with a micellar solution of

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L. Wang et al. / Journal of Colloid and Interface Science 314 (2007) 230235

Fig. 2. Phase behavior of the water/poly(oxyethylene) nonionic surfactant/

methyl decanoate system at 25 C. II, two-liquid isotropic phases; Om,
isotropic liquid phase (inverse micellar solution or W/O microemulsion); Wm,
isotropic liquid colorless phase (micellar solution of O/W microemulsion); L,
optically anisotropic phase; D, isotropic liquid phase (bicontinuous microemulsion); M, multiphase region (phases not determined).

an O/W microemulsion (Wm), an inverse micellar solution or

W/O microemulsion (Om), a bicontinuous microemulsion or
O/W microemulsion (D or Wm) and lamellar liquid crystalline
phases (L). The phases Wm, D and Om are isotropic, colorless fluids. The rest of the diagram consists of several two- and
multiple-phase regions. Along the oilsurfactant axis, a twophase region (II) extends between oilsurfactant ratios of 70/30
to 88/12. At higher water concentrations, the two-phase region
denoted as (L + Om) consists of a lower liquid crystalline
phase with an upper colorless liquid phase. The region M denotes a multiphase region, where phase equilibria were not determined.
3.2. Effect of initial concentrate phase behavior on the final
diluted nanoemulsion
The final emulsions were prepared according to method A
(the two-step process) which was described in Section 2. The
droplet sizes of the resulting nanoemulsions as a function of initial water concentration in the concentrate are shown in Fig. 3
for different oilsurfactant weight ratios (Ros ). Broadly, this
figure can be divided into three regions. In regions I and III,
emulsions with large droplet sizes and high polydispersity indices were obtained, which appeared milky white or translucent. Whereas, in region II, for which the concentrate is the D
or Wm phase, the resulting emulsion is of very small droplet
size (30 nm) and narrow distribution (polydispersity index
<0.2). These results illustrate a close relationship between the
equilibrium phase behavior of the initial concentrate and the
droplet sizes and polydispersities of the resulting emulsions.
Nanoemulsions, with small droplet sizes and narrow distributions, are formed only when the concentrate starts off as a
bicontinuous D phase or Wm microemulsion. Similar results
have been observed by employing the PIT method [1,16,21,
22,32]. Bluish transparent O/W nanoemulsions were obtained

when the equilibrium phases at the HLB temperature were D

or W + D phases (no excess oil had separated at the HLB temperature). It is well known that hydration of the ethylene oxide
groups is dramatically increased by reducing temperature, and
hence promoting a preferred curvature change of the surfactant
monolayer and consequently the tendency for oil droplet formation.
The results in Fig. 3 can also be explained by inversion of
the interfacial monolayer curvature. In region I, the concentrate
begins as an W/O microemulsion, the formation of O/W emulsions by dilution with water requires the inversion of surfactant
film curvature, which will demand more curvature free energy
to generate small droplets. This effect would contribute towards
an increase of droplet size and polydispersity [33]. When the
initial concentrate was located in region II, the oil phase is
completely solubilized in a bicontinuous (D phase) or oil-inwater (Wm) microemulsion. The dilution of this concentrate
with excess water decreases the surfactant concentration in the
system, which inevitably leads to a decrease in oil solubilization. Subsequently, the system becomes supersaturated in oil,
which may lead to homogeneous nucleation of oil in the form
of small monodisperse droplets [13]. When the concentrate was
located in region III, the simple dilution by water produced
highly polydisperse emulsions, likely because of heterogeneous
nucleation [33].
3.3. Effect of the emulsification method on the nanoemulsion
droplet sizes
In order to investigate the effect of the emulsification
process, related systems were prepared by three different methods as described in Section 2. The droplet sizes of the emulsions
as a function of oilsurfactant weight ratio (Ros ) obtained by
different approaches are shown in Fig. 4. A U-shape curve is
evident, showing nanoemulsions obtained by both methods A
and B, with low polydispersity (<0.2) for Ros values between
0.8 and 1.2. Highly polydisperse emulsions, characterized by
indices of about 0.4 were obtained for Ros outside this range.
Considering the equilibrium phase behavior of the concentrate
used in method A, it can be observed that smaller droplet sizes
are obtained when the initial concentrate was a D phase bicontinuous microemulsion or an oil-in-water microemulsion
(Wm). Increasing Ros causes the separation of an excess oil
phase, resulting in higher droplet sizes. On the other hand,
a decrease in Ros produced the separation of a lamellar liquid crystalline phase, which also resulted in higher droplet
sizes. The same results were obtained by method B, because
the same phase evolution was experienced during the emulsification process. However, emulsions obtained by method C
were highly polydisperse and with large droplet sizes irrespective of Ros . The reason is that no D phase or Wm was
present during the emulsification process. This agrees with
the aforementioned results and shows clearly that the existence of D or Wm phases is crucial to nanoemulsion formation.
The slight increase of droplet size, as Ros increases from 0.8
to 1.2, can be explained by following three points:

L. Wang et al. / Journal of Colloid and Interface Science 314 (2007) 230235

233

3.4. Nanoemulsion formation at constant oilsurfactant

weight ratio (Ros )

Fig. 3. Droplet size of the nanoemulsions at 25 C as a function of water content in the concentrate with various oil-to-surfactant weight ratios Ros : 0.9 (1),
1 (!), and 1.1 (P). The dotted lines indicate the range of D or Wm phase for
the corresponding system.

It was also of interest to study the nanoemulsion droplet sizes

prepared by method A as a function of water concentration in
the final emulsion. Note when Ros = 1 and the water content of
the concentrate is fixed at 50 wt%, the systems are in the D or
Wm phase range. Bluish transparent O/W nanoemulsions with
droplet sizes on the order of 28 nm were obtained, independent
of the water content (data shown in Supplementary material); in
addition, polydispersity indices were lower than 0.2. These results show that nanoemulsions form when the D or Wm phase
range microemulsion contacts with extra water; most likely the
excess water acts as a dilution medium resulting in oil nucleation. The droplet sizes are mainly controlled by the structure
of the D or Wm phase, independent of the volume of water in
the final emulsion.
3.5. Stability of nanoemulsions
The nanoemulsions prepared displayed good stability; although there was no phase separation after several weeks, an
increase in droplet size was noted with time. The two most
probable breakdown processes in dispersed systems are coalescence and Ostwald ripening. The LifshitzSlezov and Wagner
(LSW) theory [34] gives the following expression for the rate
of Ostwald ripening:


= dr 3 /dt = (8/9) (C VmD)/RT ,
(1)

Fig. 4. Droplet sizes at 25 C as a function of Ros by method A (1), method B

(!), and method C (P). The dotted lines indicate the range of D or Wm phase
for the concentrate used in method A.

First, the structure of concentrate changes with increasing

Ros , which increases the size of the oil domains of the bicontinuous phase, leading to an increase in the droplet size.
Second, owing to the dynamic nature of surfactant adsorption at the oilwater interface, the newly formed interface
is more rapidly stabilized at higher surfactant concentrations;
therefore, smaller, more stable droplets are formed at lower Ros .
Furthermore, at low surfactant levels the interfacial tension
would decrease with increasing surfactant concentration, which
would also favor the formation of smaller droplets.
Lamaallam et al. [14] have reported similar results by varying surfactant concentration from 6 to 11 wt%.

where C is the bulk phase solubility (the solubility of the oil

in an infinitely large droplet), is the interfacial tension, Vm is
the molar volume of the oil, D is the diffusion coefficient of the
oil in the continuous phase, is the density of the oil, R is the
gas constant, and T is the absolute temperature.
To determine if the main breakdown process was Ostwald
ripening, the cube of the radius, r 3 , is plotted as a function
of time at different Ros in Fig. 5. The linear variation of r 3
as a function of time indicates that the mechanism of instability can be attributed to Ostwald ripening. It is shown that the
slope declines with the decreasing Ros , which means the more
stable nanoemulsions are obtained with higher surfactant concentration. This phenomenon is consistent with results reported
earlier [3537]. It was suggested that excess micelles formed
in the aqueous phase, which act a solubilization sites for added
oil. The oil solubilized in the micelles was not dispersed at the
molecular level in the continuous phase. As a result, the increase of the amount of micelles actually lowers the solubility
of oil in the bulk phase, viz. the term C in Eq. (1) and hence
the ripening rate. Besides, the interfacial tension reduced as the
increase of surfactant concentration, which is a factor to reduce
the Ostwald ripening according to in Eq. (1).
4. -Cypermethrin (-CP) incorporation
Nanoemulsions have shown to be advantageous for optimizing delivery of water-insoluble compounds in agrochemicals [5]. The small size of the droplets allows them to deposit

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L. Wang et al. / Journal of Colloid and Interface Science 314 (2007) 230235

Fig. 5. Droplet sizes at 25 C as a function of time at various Ros : 0.8 (1), 0.9
(!), 1 (P), 1.1 () and 1.2 (E).

uniformly on plant leaves. Wetting, spreading and penetration

may be also enhanced as a result of the low surface tension of
the whole system and the low interfacial tension of the O/W
droplets [38]. The utility of any given system for drug or pesticide delivery depends on whether it is likely to be diluted on
use, and whether the solubilization capacity is lost on dilution
[39]. In this work, the agrochemical active -CP was employed
as a model water insoluble compound to investigate the potential application of nanoemulsions prepared by this two-step
process for pesticide delivery.
The concentrate with oilsurfactant weight ratio (Ros ) = 1
and 50 wt% water was chosen as a self-nanoemulsified system to prepare nanoemulsions for active-loading studies. -CP
was dissolved in oil/surfactant mixtures prior formulation of
the concentrate. The droplet size and stability of the -CPloaded nanoemulsions were evaluated in the same way as for
the active-free system. Fig. 6 shows the droplet size of nanoemulsions as a function of concentration of -CP in methyl
decanoate. The droplet size of nanoemulsions prepared with
less than 12 wt% of -CP was around 30 nm (polydispersity
lower than 0.2). The droplet size and polydispersity with greater
than 12 wt% -CP increased dramatically, because of the appearance of multi-phase M systems in the initial formulations.
This observation confirms that nanoemulsions form only when
the phase of the concentrate is the bicontinuous D, or watercontinuous Wm phase. With a large amount of -CP, the phase
behavior of the concentrate changes from a D phase or Wm to
an M phase, thus leading to a sharp increase in droplet size. The
droplet sizes of nanoemulsions after 24 h of preparation show
no obvious difference compared to systems in the presence or
absence of the pesticide, which means pesticide has no noticeable effect on the stability/size of the final nanoemulsions.
The stability of sprayed solutions resulting from dilution of
the prepared formulation, and the corresponding commercial
-CP microemulsion, was compared in terms of droplet sizes
and their solubilization capacity on dilution (Figs. 7 and 8). Although the droplet size does not show significant differences
in the two systems, the precipitation of pesticide appeared in

Fig. 6. Droplet sizes at 25 C as a function of the -CP present in the oil phase
at 0 h (1) and 24 h (!), respectively. The corresponding phase behavior for the
initial system is shown above.

Fig. 7. Droplet sizes obtained from dilution of nanoemulsion formulation (-2-)

and commercial microemulsion (-"-), at 25 C as a function of time.

the sprayed solution of the commercial -CP microemulsion

within 24 h of dilution, whereas no precipitation was observed
from the concentrate (Fig. 8). It has been shown that precipitated pesticides have lower bioavailability in spraying applications [40]. The results of Figs. 7 and 8 indicate the solubilization
capacity of the concentrate was maintained on dilution, which
shows this system is very suitable for agrochemical active delivery.
5. Conclusions
O/W nanoemulsions have been obtained at constant temperature by a two-step process (method A), which involves crash
dilution of a bicontinuous or oil-in-water microemulsion into
a large volume of water. A key factor for the formation of nanoemulsions at constant temperature has been identified as the
use of a bicontinuous D phase or oil-in-water microemulsion
(Wm) as the initial concentrate. The two-step process is easy to

L. Wang et al. / Journal of Colloid and Interface Science 314 (2007) 230235

235

Fig. 8. Polarizing light microscopy images taken of spray solution diluted from (a) the commercial -CP microemulsion; (b) the nanoemulsion formulation after
24 h.

scale up and with less energy consumption, which is of great

interest for practical applications.
The incorporation of -CP in the concentrate showed no effect on the phase behavior when present at less than 12 wt%.
Compared with the commercial -CP microemulsion, the excellent stability of sprayed solution diluted from the concentrate
makes this system an ideal candidate as a water-insoluble pesticide delivery system. Thus, the application of the new methodology in designing spray formulations of -CP may enable a
reduction in the applied amounts, relative to those formulated
as O/W microemulsions. These characteristics make the new
methodology promising from both environmental and economical points of view.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (NSFC 20573079) and Ministry of Science and Technology (2006 BAE01A07-5).
Supplementary material
The online version of this article contains additional supplementary material.
Please visit DOI: 10.1016/j.jcis.2007.04.079.
References
[1] A. Forgiarini, J. Esquena, C. Gonzalez, C. Solans, Langmuir 17 (2001)
2076.
[2] H.L. Wu, C. Ramachandran, N.D. Weiner, B.J. Roessler, Int. J. Pharm. 220
(2001) 63.
[3] E.I. Taha, S. Al-Saidan, A.M. Samy, M.A. Khan, Int. J. Pharm. 285 (2004)
109.
[4] O. Sonneville-Aubrun, J.-T. Simonnet, F. LAlloret, Adv. Colloid Interface
Sci. 108109 (2004) 145.
[5] G. Lee, T. Tadros, Colloids Surf. 5 (1982) 105.
[6] X. Liu, Y. Guan, Z. Ma, H. Liu, Langmuir 20 (2004) 10278.
[7] N. Sadurni, C. Solans, N. Azemar, M.J. Garcia-Celma, Eur. J. Pharm.
Sci. 26 (2005) 438.
[8] J.S. Schwarz, M.R. Weisspapir, D.I. Friedman, Pharm. Res. 12 (1995) 687.
[9] G. Nicolaos, S. Crauste-Manciet, R. Farinotti, D. Brossard, Int. J. Pharm.
263 (2003) 165.

[10] S. Tomomasa, M. Kochi, H. Nakajima, J. Jpn. Oil Chem. 37 (1988) 1012.

[11] M.J. Rang, C.A. Miller, J. Colloid Interface Sci. 209 (1999) 179.
[12] R. Pons, I. Carrera, J. Caelles, J. Rouch, P. Panizza, Adv. Colloid Interface
Sci. 106 (2003) 129.
[13] H. Bataller, S. Lamaallam, J. Lachaise, A. Graciaa, C. Dicharry, J. Mater.
Process. Technol. 152 (2004) 215.
[14] S. Lamaallam, H. Bataller, C. Dicharry, J. Lachaise, Colloids Surf. A
Physicochem. Eng. Aspects 270271 (2005) 44.
[15] A. Forgiarini, J. Esquena, C. Gonzalez, C. Solans, Prog. Colloid Polym.
Sci. 115 (2000) 36.
[16] A. Forgiarini, J. Esquena, C. Gonzalez, C. Solans, Prog. Colloid Polym.
Sci. 118 (2001) 184.
[17] K. Shinoda, H. Saito, J. Colloid Interface Sci. 26 (1968) 70.
[18] T. Frster, W.V. Rybinski, A. Wadle, Adv. Colloid Interface Sci. 58 (1995)
119.
[19] P. Izquierdo, J. Esquena, Th.F. Tadros, C. Dederen, M.J. Garcia-Celma, N.
Azemar, C. Solans, Langmuir 18 (2002) 26.
[20] P. Izquierdo, J. Esquena, Th.F. Tadros, J.C. Dederen, J. Feng, M.J. GarciaCelma, N. Azemar, C. Solans, Langmuir 20 (2004) 6594.
[21] P. Izquierdo, J. Feng, J. Esquena, Th.F. Tadros, J.C. Dederen, M.J. Garcia,
N. Azemar, C. Solans, J. Colloid Interface Sci. 285 (2005) 388.
[22] D. Morales, J.M. Gutierrez, J.M. Garcia-Celma, C. Solans, Langmuir 19
(2003) 7196.
[23] A. Forgiarini, J. Esquena, C. Gonzalez, C. Solans, Prog. Colloid Polym.
Sci. 115 (2000) 36.
[24] A. Forgiarini, J. Esquena, C. Gonzalez, C. Solans, Prog. Colloid Polym.
Sci. 118 (2001) 184.
[25] US EPA Inert (other) Pesticide IngredientsList 3.
[26] US EPA Inert (other) Pesticide IngredientsList 4B.
[27] C.H. Wang, X.W. Tong, B. Xu, H.Z. Jin, H.M. Lei, Faming Zhuanli Shenqing Gongkai Shuomingshu (2003), CN 1431188.
[28] M.M. Azam, W. Amtul, N.M. Nahar, Biomass Bioenergy 29 (2005) 293.
[29] Y. Fang, Y.M. Xia, W.X. Jiang, Riyong Huaxue Gongye 5 (1991) 236.
[30] P.R. Skelton, ASTM STP 13 (1993) 114.
[31] P.R. Skelton, K.L. Turpin, ASTM STP 18 (1998) 185.
[32] D. Morales, C. Solans, J.M. Gutirrez, M.J. Garcia-Celma, U. Olsson,
Langmuir 22 (2006) 3014.
[33] J. Morris, U. Olsson, H. Wennerstrm, Langmuir 13 (1997) 606.
[34] A.S. Kabalnov, E.D. Shchuckin, Adv. Colloid Interface Sci. 38 (1992) 69.
[35] W.R. Liu, D.J. Sun, C.F. Li, Q. Liu, J. Xu, J. Colloid Interface Sci. 303
(2006) 577.
[36] Y.D. Smet, L. Deriemaeker, R. Finsy, Langmuir 15 (1999) 6745.
[37] K.N. Hoang, V.B. La, L. Deriemaekera, R. Finsy, Langmuir 17 (2001)
5166.
[38] T. Tadros, P. Izquierdo, J. Esquena, C. Solans, Adv. Colloid Interface
Sci. 108109 (2004) 303.
[39] C.W. Pouton, Adv. Drug Delivery Rev. 25 (1997) 47.
[40] W.L. Guo, Liquid Formulations, third ed., 2004, p. 144.