Angewandte

Chemie

Nanoparticles hydrophilic particles preferentially forming o/w emulsions

and hydrophobic particles forming w/o emulsions. Although
Temperature-Induced Inversion of the influence of temperature on the stability of either w/o[13]
Nanoparticle-Stabilized Emulsions** or o/w[14] emulsions stabilized solely by nanoparticles has been
reported, the ability to phase invert such emulsions with
temperature has not been demonstrated.
Bernard P. Binks,* Ryo Murakami, Steven P. Armes,
The particulate emulsifier employed in this study was a
and Syuji Fujii
sterically stabilized polystyrene (PS) latex of 152 nm diame-
ter. The steric stabilizer was a near-monodisperse diblock
Emulsions are mixtures of immiscible liquids where one copolymer, poly[2-(dimethylamino)ethyl methacrylate-
liquid is dispersed as micrometer-sized drops in the contin- block-methyl methacrylate], PDMA-b-PMMA.[15] The hydro-
uous phase of the other. They occur as end products in a wide phobic PMMA block is designed to adsorb onto the latex
range of areas including the food, cosmetic, and pharmaceut- surface and the solvated PDMA block acts as the hydrophilic
ical industries. To prevent phase separation, surfactants or steric stabilizer. As reported earlier,[16] the cationic charge
proteins are usually added to cover the liquid–liquid inter- density of the PDMA block can be adjusted by controlling the
faces.[1] It has been shown recently that certain solid nano- solution pH value and this dictates the emulsification perfor-
particles act as excellent emulsifiers alone[2–5] and novel mance of these PS latex particles. At 25 8C, batch emulsions
materials can be made from them.[6, 7] Inversion of such containing equal volumes of n-hexadecane and 2 wt %
emulsions from oil-in-water (o/w) to water-in-oil (w/o) or aqueous PS latex are o/w at all pH values above 3, and the
vice versa can be effected by changes in the oil:water ratio,[8] stability of these emulsions towards coalescence increases
pH value,[9] or oil type.[10] Herein we describe for the first time progressively on increasing the pH from 3 to 8. It was argued
temperature-modulated emulsion inversion using sterically that this effect was due to progressive deprotonation of the
stabilized polystyrene latex particles as the sole emulsifier. PDMA-based stabilizer chains with increasing pH, causing
The steric stabilizer is a diblock copolymer in which one block the sterically stabilized PS latex particles to become less
is thermo-responsive, exhibiting inverse temperature solubil- hydrophilic and hence better emulsifiers.[16]
ity behavior. Thus the particle surface becomes less hydro- In this work, we investigate the effect of temperature on
philic at higher temperature, causing inversion from o/w to emulsions stabilized by the same particles as above, prepared
w/o to occur in batch emulsions. at pH 8.1, which are completely stable to coalescence at 25 8C.
Emulsions stabilized by ionic surfactant invert from w/o to In one series of experiments, an n-hexadecane/water (1:1)
o/w with increasing temperature as a result of the increased emulsion stabilized by 2 wt % particles was prepared at room
dissociation of counterions bound to surfactant head groups, temperature and heated progressively up to 70 8C with gentle
making the surfactant more hydrophilic.[11] In contrast, non- shaking. Although the emulsion remained o/w at all temper-
ionic surfactant-stabilized emulsions invert the other way atures, substantial coalescence occurred at and above 60 8C.
around; increasing temperature causes dehydration of head In a second series, an emulsion was prepared at each
groups, making them more hydrophobic.[11] Inversion with temperature after pre-equilibration of the two phases at
respect to temperature is important industrially and is that temperature. The difference between the two is that
exploited to prepare fine emulsions of increased stability.[12] particles are already adsorbed at oil–water interfaces in the
Small solid particles act in many ways like surfactant first series, whereas they are free to become adsorbed at
molecules in that they adsorb at fluid–fluid interfaces, different temperatures in the second series. Importantly in the
allowing stabilization of droplets in emulsions and bubbles second series, phase inversion of the emulsions occurs from o/
in foams.[3] However, it is only recently that their precise role w at low temperatures to w/o at higher temperatures. This
has begun to be elucidated in surfactant-free systems. The result is shown in Figure 1, which summarizes the emulsion
wettability of the particles at the oil–water interface is crucial conductivities (k) and the drop test findings obtained at
in determining which type of emulsion is formed, with various temperatures. At temperatures below 52 8C, the
conductivities are relatively high (kaq = 25, koil =
0.1 mS cm 1), the emulsions disperse in water and not in oil
[*] Prof. B. P. Binks, Dr. R. Murakami
Surfactant & Colloid Group and are therefore water continuous. At and above 65 8C, the
Department of Chemistry emulsions exhibit low conductivities, disperse in oil rather
University of Hull than in water, and are therefore oil continuous. At inter-
Hull HU6 7RX (UK) mediate temperatures indicated by the dotted lines (53–
Fax: (+ 44) 1482-466-410 64 8C), emulsions can be either of the two types, which may
E-mail: [email protected] co-exist.
Prof. S. P. Armes, Dr. S. Fujii Optical micrographs of the emulsions of the second series
Department of Chemistry
are shown in Figure 2. At 25 8C (Figure 2 a) oil drops in an o/w
Dainton Building, University of Sheffield
Sheffield S3 7HF (UK) emulsion are discrete and some appear non-spherical. At
55 8C (Figure 2 b) in addition to simple emulsions, there is
[**] This work was funded by the EPSRC (UK) (GR/S69283 and GR/
S69276). S.P.A. is the recipient of a Royal Society/Wolfson Research some evidence for multiple emulsions, in this case of water-in-
Merit award. We thank Dr. J. I. Amalvy for the synthesis of the oil-in-water (w/o/w), in which water drops are present within
sterically-stabilized polystyrene latex used in this study. oil globules themselves dispersed in water. The appearance of

Angew. Chem. Int. Ed. 2005, 44, 4795 –4798 DOI: 10.1002/anie.200501073  2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4795
Communications

Figure 1. Conductivity k of batch emulsions (second series, see text

for details) comprising equal volumes of n-hexadecane and 2 wt %
Figure 3. Average drop diameter d versus temperature for batch emul-
aqueous PDMA-b-PMMA-stabilized PS latex (152 nm diameter, pH 8.1)
sions prepared as in Figure 1 immediately after preparation. Sizes
as a function of temperature. Emulsions are only o/w (~) to the left of
determined by optical microscopy (& o/w, ~ w/o) and using light dif-
the first dotted line and only w/o (~) to the right of the second dotted
fraction (& o/w) are shown.
line, but can be either type or multiple at intermediate temperatures.
The labels for emulsion type are based on drop test results.

o/w emulsions, the number-average mean determined by

optical microscopy (40 drops) is shown, as is the median
diameter measured using light diffraction. For w/o emulsions,
only the mean by microscopy has been determined. The
average oil-drop size increases with temperature on
approaching inversion and the size of water drops is less
than that of oil drops. Assuming that particles form a
hexagonally close-packed monolayer around oil drops, we
calculate that at 25 8C approximately 35 % of the particles
originally in water become adsorbed around drops of average
diameter 76 mm. This number falls to 24 % for the larger drops
of 113 mm at 50 8C. On this basis, there is thus a distribution of
particles between interface and bulk, although no exchange is
likely because of the high energies of particle attachment to
interfaces.[3]
The stabilities of these latex-stabilized emulsions six
months after preparation are summarized in Figure 4. The
Figure 2. Optical micrographs of emulsions prepared as in Figure 1 at parameters f(oil) (and f(water)) are defined as the volumes of
a) 25 (o/w), b) 55 (w/o/w), and c) 65 8C (w/o). Also shown is micro- oil (or water) resolved relative to the initial volumes of oil (or
graph of the 2 wt % aqueous PS latex (pH 8.1) held at 70 8C for 30 min water). At temperatures prior to inversion, the oil drops in
on a glass slide (d). The scale bar refers to all images. o/w emulsions cream within 1–2 h at all temperatures with no
further change subsequently. The oil volume fraction in the
multiple emulsions around conditions of phase inversion in cream is now increased beyond 0.5 and, apart from the stable
surfactant-stabilized systems is common; the balanced sur- emulsion at 25 8C, a low degree of coalescence occurs in
factant satisfies the preference for both types of emulsion emulsions approaching 50 8C. At intermediate temperatures
simultaneously.[12] Such emulsions are notoriously unstable to (between the dotted lines), the creaming of o/w emulsions is
coalescence (of both drops and globules), whereas these solid- reduced and w/o emulsions sediment but are stable to
particle-stabilized emulsions are stable. The stabilization of coalescence. At temperatures above inversion, sedimentation
multiple emulsions by only one type of particle has been of water drops occurs gradually in the first 24 h followed by
reported for silica.[17] At 65 8C, water drops in a w/o emulsion their coalescence. Eventually, virtually complete phase sep-
are characteristically flocculated (Figure 2 c), since any repul- aration ensues as indicated by near unity values of both f(oil)
sion between particle surfaces on neighboring drops is and f(water).
mediated through the oil phase, which has a low dielectric We seek to understand the origin of emulsion phase
constant, and little steric stabilization is provided by the inversion with temperature, which occurs in the same sense as
PDMA chains in this oil. that for non-ionic surfactants. Some clues to this can be found
A measure of the average diameter of drops in both types in the behavior of the aqueous PS latex particle dispersions in
of emulsion is plotted against temperature in Figure 3. For the absence of oil. Dynamic light-scattering studies indicate

4796  2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org Angew. Chem. Int. Ed. 2005, 44, 4795 –4798
 Angewandte
Chemie

Two competing effects caused by increasing temperature may

cause this change. The first is the disruption of hydrogen
bonds surrounding the PDMA chains, leading to an increase
in their hydrophobicity. The second is an increase in the
degree of protonation of tertiary amine groups resulting in
increased particle hydrophilicity. For trimethylamine in
water, this has been measured as an increase in Kb (equilib-
rium constant) with temperature, taking into account the
increase in the dissociation constant of pure water.[19] It is
therefore clear that for these sterically stabilized PS latex
particles, the dominant influence of temperature is in
reducing the degree of hydration of the PDMA chains to
such an extent that these particles become preferentially
wetted by oil.
Nanoparticles are effective emulsifiers of oil and water.
Appropriate design of the latex surface allows the particle
wettability to be controlled by adjusting the temperature,
Figure 4. Stability of batch emulsions after six months at different tem- which in turn allows the preparation of either o/w or w/o
peratures. For o/w, f(water) (&) relates to creaming and f(oil) (&)
emulsions. The emulsions described herein are temperature-
relates to coalescence. For w/o, f(oil) (~) relates to sedimentation and
f(water) (~) relates to coalescence. dependent but not temperature-responsive. Manipulating the
behavior of particles adsorbed at fluid interfaces in this way
augurs well for the development of a novel range of simple
and multiple emulsions for use in cosmetic, food, and drug
that the mean hydrodynamic diameter remains constant at and formulations.
152 nm between 20 and 50 8C and increases to 173 nm at
53 8C, above which significant flocculation is apparent.
Optical microscopy investigations of a drop of dispersion on
a glass slide shows no features above 1 mm up to 50 8C but Experimental Section
particle aggregates of increasing size above this critical The synthesis and characterization of the PDMA-b-PMMA-stabi-
temperature (Figure 2 d). Since PDMA homopolymer in lized PS particles (diameter = 152 nm, Mn = 38 400 g mol 1, Mw/Mn =
water at pH 8.1 exhibits a lower consolute solution temper- 1.14) was described earlier.[15, 16b] Dynamic light scattering of 2 wt %
aqueous PS latex at pH 8.1 was measured using a Malvern Nano ZS
ature between 32 and 46 8C (depending on its mean degree of
ZEN3600 instrument under a N2 atmosphere at a scattering angle of
polymerization),[18] it is likely that the temperature-induced 1738. Three measurements were made at each temperature, with
flocculation of the latex particles reflects the thermo-respon- 30 min being allowed for equilibration. Batch emulsions of equal
sive character of the PDMA block in the stabilizer chains. volumes (2 mL) of n-hexadecane and aqueous PS latex (pH 8.1),
This hypothesis was verified by performing contact-angle equilibrated at the appropriate temperature, were prepared at that
measurements of water drops under n-hexadecane on spin- temperature using an Ultra Turrax T25 homogenizer (1 cm head)
coated films of PDMA homopolymer at different temper- operating at 11 000 rpm for 2 min. Emulsion type was determined by
conductivity measurements and the drop test. Their stabilities at
atures. As shown in Table 1, the contact-angle measured
different temperatures were measured by monitoring the movement
through water increases with temperature from near-wetting of the oil–emulsion and water–emulsion interfaces. Drop size
(hydrophilic) at 25 8C to values that are characteristic of distributions of o/w emulsions were measured using a Malvern
hydrophobic surfaces above 60 8C. They are also in line with MasterSizer 2000 instrument using either cold or hot water as diluting
the predicted change in the wettability of the particles in phase. For microscopy, a dilute sample of emulsion/dispersion was
emulsions, from predominantly hydrophilic at low temper- placed in a haemocytometer cell (Weber Scientific) and viewed with a
atures (o/w) to more hydrophobic at high temperatures (w/o). Nikon Labophot microscope fitted with a DIC-U camera (World
Precision Instruments). Images were processed using Adobe Photo-
shop 5.0 software. The contact angles of water drops (10 mL, pH 8.1)
under n-hexadecane on films of PDMA homopolymer (Mn =
Table 1: Effect of temperature on the contact angle q of a water drop.[a] 21 300 g mol 1) spin-coated onto glass slides from a 5 wt % solution
in methanol (Speciality Coating Systems model P6700, 2000 rpm for
T [8C] q (w/o) [8] q (o/w) [8]
1 min) were determined using a KrEss DSA10 apparatus with a
25 4 3 thermostatted cell. At least five separate drops were used at each
35 6 6 temperature.
45 11 12
55 28 28 Received: March 24, 2005
60 34 32 Published online: June 29, 2005
65 33 30
75 58  10 65  10
[a] At pH 8.1 under n-hexadecane, measured through water, on a glass
slide coated with a film of PDMA homopolymer. Data given for water
(w/o) or oil (o/w) contacting the substrate first.
.
Keywords: emulsions · inversion · latex · nanoparticles ·
wettability

Angew. Chem. Int. Ed. 2005, 44, 4795 –4798 www.angewandte.org  2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4797
Communications

[1] Modern Aspects of Emulsion Science (Ed.: B. P. Binks, The

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[2] N. X. Yan, M. R. Gray, J. H. Masliyah, Colloids Surf. A 2001, 193,
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[3] B. P. Binks, Curr. Opin. Colloid Interface Sci. 2002, 7, 21 – 41.
[4] E. Vignati, R. Piazza, T. P. Lockhart, Langmuir 2003, 19, 6650 –
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[5] S. Stiller, H. Gers-Barlag, M. Lergenmueller, F. PflEcker, J.
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[6] A. D. Dinsmore, M. F. Hsu, M. G. Nikolaides, M. Marquez,
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[9] B. P. Binks, J. A. Rodrigues, Angew. Chem. 2005, 117, 445 – 448;
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[11] See Chapter 7 by A. S. Kabalnov in ref. [1].
[12] K. Shinoda, H. Saito, J. Colloid Interface Sci. 1969, 30, 258 – 266.
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[15] F. L. Baines, S. Dionisio, N. C. Billingham, S. P. Armes, Macro-
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[16] a) J. I. Amalvy, S. P. Armes, B. P. Binks, J. A. Rodrigues, G.-F.
Unali, Chem. Commun. 2003, 1826 – 1827; b) J. I. Amalvy, G.-F.
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Rodrigues, C. P. Whitby, Langmuir 2004, 20, 4345 – 4354.
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[18] V. BEtEn, S. P. Armes, N. C. Billingham, Polymer 2001, 42, 5993 –
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[19] D. H. Everett, W. F. K. Wynne-Jones, Proc. R. Soc. London Ser.
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4798  2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org Angew. Chem. Int. Ed. 2005, 44, 4795 –4798