Langmuir 2004, 20, 2069-2074 2069

Evaporation Rates of Water from Concentrated

Oil-in-Water Emulsions
I. Aranberri, B. P. Binks, J. H. Clint, and P. D. I. Fletcher*
Surfactant & Colloid Group, Department of Chemistry, University of Hull,
Hull HU6 7RX, United Kingdom

Received June 12, 2003. In Final Form: January 8, 2004

We have investigated the rate of water evaporation from concentrated oil-in-water (o/w) emulsions
containing an involatile oil. Evaporation of the water continuous phase causes compression of the emulsion
with progressive distortion of the oil drops and thinning of the water films separating them. Theoretically,
the vapor pressure of water is sensitive to the interdroplet interactions, which are a function of the film
thickness. Three main possible situations are considered. First, under conditions when the evaporation
rate is controlled by mass transfer across the stagnant vapor phase, model calculations show that evaporation
can, in principle, be slowed by repulsive interdroplet interactions. However, significant retardation requires
very strong repulsive forces acting over large separations for typical emulsion drop sizes. Second, water
evaporation may be limited by diffusion in the network of water films within the emulsion. In this situation,
water loss by evaporation from the emulsion surface leads to a gradient in the water concentration (and
in the water film thickness). Third, compression of the drops may lead to coalescence of the emulsion drops
and the formation of a macroscopic oil film at the emulsion surface, which serves to prevent further water
evaporation. Water mass-loss curves have been measured for silicone o/w emulsions stabilized by the
anionic surfactant SDS as a function of the water content, the thickness of the stagnant vapor-phase layer,
and the concentration of electrolyte in the aqueous phase, and the results are discussed in terms of the
three possible scenarios just described. In systems with added salt, water evaporation virtually ceases
before all the water present is lost, probably as a result of oil-drop coalescence resulting in the formation
of a water-impermeable oil film at the emulsion surface.

Introduction evaporation rates of o/w emulsions containing relatively

low oil-drop volume fractions.5 During evaporation, the
Evaporation rates are of interest from many viewpoints
dispersed oil drops cream under gravity to the emulsion
including assessment of hazards arising from the spillage
surface but remain separated from the vapor phase by a
of volatile chemicals, drying processes, and the release of
thin water film. Oil mass transfer from the drops to the
volatile active species such as perfumes and flavors from
vapor phase occurs via dissolution and diffusion across
commercial products. In many systems of practical inter-
the water film, not by entry of the oil drops into the air-
est, evaporation occurs from liquid mixtures that may be
water surface. As a result of this mechanism, the rates of
multiphase and possess microstructure. As part of a
evaporation of oils from o/w emulsions are retarded relative
program to study evaporation rates in different types of
to those for pure oils by factors of up to 20-fold, with greater
nonstructured and structured liquid systems, we have
retardation for those oils that have a low solubility in
previously investigated rates for pure liquids,1 water
water. In a gravity-creamed o/w emulsion containing a
contained within porous solids,2 water-in-oil microemul-
low volume fraction of mutually repulsive oil drops, the
sions,3 different liquid mixtures including water/surfac-
drops remain virtually spherical (ignoring minor distor-
tant systems showing a variety of microstructured liquid
tions due to gravity) and are widely separated by thick
crystalline phases,4 and creamed emulsions.5 Evaporation
water films. The evaporation rates of the continuous-phase
from a range of related surfactant colloidal mixtures has
water contained within the relatively thick films in such
also been studied by the group of Friberg.6-8
creamed emulsions are found to be identical to that for
Oil-in-water (o/w) emulsions are thermodynamically
pure water.5
unstable dispersions of micrometer-sized oil drops in
water. In a previous study, we used a mass-loss method In the present study, we have investigated the evapo-
under controlled gas flow conditions to investigate the ration of water from o/w emulsions containing high volume
fractions of involatile oil droplets. In emulsions with an
* To whom correspondence should be addressed. E-mail:
oil-drop volume fraction above the close-packing limit for
[email protected]. spheres, evaporation of the water continuous phase leads
(1) Beverley, K. J.; Clint, J. H.; Fletcher, P. D. I. Phys. Chem. Chem. to increased oil-droplet distortion and progressive thinning
Phys. 1999, 1, 149. of the nanometer water films separating them. As
(2) Beverley, K. J.; Clint, J. H.; Fletcher, P. D. I.; Thubron, S. Phys. discussed theoretically in the following, such thinning by
Chem. Chem. Phys. 1999, 1, 909.
(3) Clint, J. H.; Fletcher, P. D. I.; Todorov, I. T. Phys. Chem. Chem. evaporation is resisted by repulsive colloidal forces
Phys. 1999, 1, 5005. between the oil-drop surfaces, which increase in magnitude
(4) Beverley, K. J.; Clint, J. H.; Fletcher, P. D. I. Phys. Chem. Chem. as the films thin. Under these circumstances, the water
Phys. 2000, 2, 4173.
(5) Aranberri, I.; Beverley, K. J.; Binks, B. P.; Clint, J. H.; Fletcher, evaporation rate is slowed relative to pure water and is
P. D. I. Langmuir 2002, 18, 3471. sensitive to the variation of the colloidal forces with the
(6) Friberg, S. E.; Kayali, I. J. Pharm. Sci. 1989, 78, 639. water film thickness. Therefore, the rate of water evapo-
(7) Friberg, S. E.; Langlois, B. J. Dispersion Sci. Technol. 1992, 13, ration from concentrated o/w emulsions is expected to differ
223.
(8) Langlois, B. R. C.; Friberg, S. E. J. Soc. Cosmet. Chem. 1993, 44, from that for dilute o/w emulsions containing widely
23. separated, undistorted oil drops for which, as noted
10.1021/la035031x CCC: $27.50 © 2004 American Chemical Society
Published on Web 02/06/2004
2070 Langmuir, Vol. 20, No. 6, 2004 Aranberri et al.

depth, that is, the concentration of the volatile species at

the liquid surface is reduced relative to the depth-averaged
composition. Clearly, whether one of these limiting cases
is achieved experimentally depends not only on the
physical properties of the system (e.g., vapor pressures,
vapor- and liquid-phase diffusion coefficients, viscosities,
etc.) but also on the geometrical dimensions of the vessel,
in particular the depth of liquid in the sample and the
thickness h of the stagnant vapor space. For the sample
tube used here (with an internal depth of approximately
40 mm), h can be adjusted (by control of the depth of the
emulsion sample) over the range 3-37 mm.
We first consider the rate of water evaporation from a
concentrated o/w emulsion containing an involatile oil
under conditions of vapor diffusion control; that is, we
Figure 1. Schematic diagram of the gravimetric apparatus assume that the water volume fraction at the liquid surface
used to determine evaporation rates. Under the controlled gas
flow conditions used here, the stagnant vapor-phase thickness is identical to the overall average water volume fraction.
h is equal to the separation between the liquid surface and the Under conditions of high gas flow rate, the steady-state
sample tube mouth. water evaporation rate E, expressed as the rate of mass
loss, is independent of the gas flow rate and is given by1
previously, the rate of water evaporation is equal to that
for pure water. One motivation for this study is to gain dm MADVPz
a better understanding of the relationship between the E)- ) (1)
dt hRT
water evaporation rate from concentrated emulsions and
the colloidal forces between emulsion drops. where m is the sample mass at time t, M is the molar mass
of water, A is the liquid surface area of the sample, DV is
Experimental Section the diffusion coefficient of water vapor in the stagnant
Water was purified by reverse osmosis followed by passage vapor space of thickness h, P is the equilibrium water
through a Milli-Q reagent water system. Poly(dimethylsiloxane) vapor pressure, R is the gas constant, and T is the absolute
oil (PDMS, Dow Corning) had a kinematic viscosity of 300 cS and temperature. The parameter z is a correction factor that
was found to be completely involatile over the experimental time allows for additional convection resulting from the con-
scales used here. Sodium dodecyl sulfate (SDS, BDH, specially
pure grade) and NaBr (BDH, >99%) were used as received.
centration gradient of the second gas component (nitrogen)
PDMS-in-water emulsions were prepared using an Ultra within the stagnant layer and is given by

[ )]
Turrax rotor-stator homogenizer fitted with a T25 shaft. Samples

(
(10 mL) were homogenized at 11 000 rpm for 1 min. Emulsion Patm 1
drop size distributions were measured using a Malvern Mas- z) ln (2)
tersizer MS20 instrument. Optical micrographs of emulsion
P 1 - (P/Patm)
samples were obtained using a Nikon Labophot transmission
microscope equipped with a digital camera. where Patm is atmospheric pressure. For this study, the
Evaporation rates were determined gravimetrically using the flow rate of nitrogen was kept constant at 1710 mL min-1,
apparatus fully described in ref 1 and shown schematically in sufficiently high that eq 1 is valid within 2% or so. The
Figure 1. Briefly, a weighed sample of emulsion was placed in same sized sample tube was used for all measurements,
a cylindrical, open-topped glass tube suspended from a balance.
and, thus, the area A was constant (258.4 mm2). The initial
The sample was mounted within a thermostatted chamber, and
nitrogen gas was flowed vertically around the sample tube. For value of h was either 26.7 mm (when 3.0 g of the emulsion
this experimental geometry and gas flow configuration, the sample was used) or 36.5 mm (when 0.5 g of the emulsion
thickness of the stagnant vapor layer above the liquid surface was used).
(h) has been demonstrated to be equal to the distance between The vapor pressure P of water confined in the thin water
the liquid surface and the mouth of the sample tube.1 The films separating the oil drops is affected by the disjoining
knowledge of h from the experimental configuration is important pressure (repulsive force per unit area of film) Π operating
because it enables a full quantitative analysis of the measured between the drop surfaces according to9
evaporation rates. All measurements were made at 25.0 °C.
Πv
Theoretical Considerations
Two possible limiting situations can arise in considering
P ) P0 exp - ( kT ) (3)

the rate of evaporation of a volatile species from a where P0 is the vapor pressure of bulk water, v is the
multicomponent liquid mixture across a stagnant vapor molecular volume of water, and k is Boltzmann’s constant.
layer of thickness h. The first case arises when the rate From eq 3, it can be seen that a positive disjoining pressure
of vapor diffusion from the liquid surface across the (i.e., a repulsive force between oil drops) causes a decrease
stagnant vapor space is slow relative to diffusion of the in the water vapor pressure and, from eq 1, a corresponding
volatile species within the liquid mixture to the surface. decrease in the evaporation rate. For the purposes of
In this case, denoted here as “vapor-diffusion controlled”, estimating the magnitude and range of the disjoining
the liquid composition remains uniform throughout the pressure necessary to produce measurable changes in the
liquid as evaporation proceeds because the volatile species mass-loss rates for emulsions under conditions similar to
is depleted only slowly relative to diffusion within the those used here, we assume that the total disjoining
liquid. The second case (“liquid-diffusion controlled”) arises pressure decays exponentially with film thickness d
when the diffusion rate in the liquid is slow relative to according to
that in the vapor space. Under these circumstances,
depletion of one component by evaporation leads to the (9) Derjaguin, B. V.; Churaev, N. V.; Muller, V. M. Surface Forces;
development of a concentration gradient through the liquid Plenum Press (Consultants Bureau): New York, 1987.
Evaporation Rates of Water from o/w Emulsions Langmuir, Vol. 20, No. 6, 2004 2071

Π ) Π0 exp(-d/d0) (4)

where Π0 is the disjoining pressure corresponding to

virtually zero thickness of the water film between opposing
emulsion drop surfaces (i.e., d ) 0) and d0 is the decay
length. This exponential force law corresponds to solely
electrostatic repulsive forces for which the decay distance
d0 is equal to the Debye length.10 This very crude approach
neglects contributions to the overall disjoining pressure
between compressed drops arising from van der Waals,
steric, hydration, and oscillatory forces associated with
micelle stratification but has the advantage of involving
only two unknown parameters (Π0 and d0). It is adopted
here solely to estimate the approximate magnitude and
range of the disjoining pressure required to significantly
affect the shapes of the mass-loss curves.
For an emulsion containing monodisperse drops with
a mean undistorted spherical radius r and volume fraction
of water φw, the drop surface area per unit volume of
emulsion (neglecting the distortion of the drops from
sphericity) is 3(1 - φw)/r. Noting that the network of films
separating the drops has an area equal to 1/2 that of the
drops and a volume fraction equal to φw, it follows that the
average water film thickness d is approximately

2φwr
d≈ (5)
3(1 - φw)

Equations 1-5 can be used to make an approximate

estimation of the sensitivity of the evaporative mass-loss
versus time curves for concentrated emulsions to the
strength and range of repulsive interdroplet forces (i.e.,
through variation of Π0 and d0) and emulsion drop radius
r. Figure 2 shows a series of simulated mass-loss curves
corresponding to water evaporation at 25 °C from 3.0 g
of o/w emulsion samples initially containing 20 vol %
water. Figure 2a shows the effect of changing the
magnitude of repulsive disjoining pressure through varia-
tion of Π0. When repulsive forces are weak (i.e., when Π0
is low), the mass-loss curves show a sharp kink corre-
sponding to the point at which all the water initially
present is lost. Stronger repulsion acts to reduce the water
vapor pressure and slow the evaporation before all the
water is lost, that is, the kink is “smoothed”. A repulsive
disjoining pressure on the order of 107 Pa is required to Figure 2. Simulated water loss curves for o/w emulsions
produce a measurable reduction in the vapor pressure containing 80 vol % dispersed drops of an involatile oil. Unless
stated otherwise, r ) 4 µm, Π0 ) 3 × 108 Pa, and d0 ) 50 nm.
(and, hence, evaporation rate) of about 10%. For this In Figure 2a, the right-hand scale shows the film thickness
magnitude of repulsive interaction to give an observable corresponding to the mass loss indicated on the left-hand scale.
“smoothing” of the sharply kinked mass-loss curve, the
disjoining pressure must operate over a film thickness of forces give smoother curves. Figure 2c shows the influence
at least 20 nm (see right-hand scale of Figure 2a). Both of the emulsion oil-drop radius. When all other parameters
the magnitude and the range of the repulsion required to are kept constant, the largest drop size produces the lowest
significantly affect the evaporative mass-loss curves are film surface area and, hence, the thickest film, weakest
much higher than the experimentally measured values. interdroplet repulsion, and most kinked mass-loss curve.
For o/w emulsions stabilized by SDS at a concentration Overall, comparison of the calculated curves and the
equal to the critical micelle concentration, the disjoining disjoining pressure isotherms of ref 11 shows that emul-
pressure decays exponentially from approximately 4 × sions stabilized by SDS possess interactions of too low a
106 Pa at d ) 2.5 nm to 2 × 105 Pa at d ) 5 nm.11 Figure magnitude and range to produce a significant smoothing
2b shows the influence of the range d0 of the electrostatic of the mass-loss curves from the limiting kinked shape
repulsive forces. Short-range forces (e.g., d0 ) 5 nm) give corresponding to negligible interactions.
a strongly kinked mass-loss curve because virtually all The simulated mass-loss curves of Figure 2 correspond
the available water must be lost before the films are thin to a hypothetical situation in which mass transport across
enough to be affected by the colloidal forces. Longer-range the stagnant vapor phase is rate limiting and the water
volume fraction is virtually uniform throughout the
(10) See, for example, Hunter, R. J. Foundations of Colloid Science; emulsion. It is also assumed that the oil drops remain
Clarendon Press: Oxford, 1991; Vol. 1, p 406. intact as they are compressed together by progressive
(11) Sonneville-Aubrun, O.; Bergeron, V.; Gulik-Krzywicki, T.; Jon-
sson, B.; Wennerstom, H.; Lindner, P.; Cabane, B. Langmuir 2000, 16, evaporation of the water continuous phase. In fact, two
1566. additional scenarios are possible. First, when water mass
2072 Langmuir, Vol. 20, No. 6, 2004 Aranberri et al.

Figure 3. Water mass-loss curves for PDMS-in-water emul- Figure 4. Water mass-loss curves for PDMS-in-water emul-
sions containing 20 mM SDS and the vol % water indicated. sions containing 20 mM SDS and the vol % water indicated.
The initial mass of the emulsion was 3.0 g, corresponding to an The initial mass of the emulsion was 0.5 g, corresponding to an
initial h ) 26.7 mm. For each plot, the narrow line is a best-fit initial h ) 36.5 mm. For each plot, the narrow line is a best-fit
to the model described in the text. to the model described in the text.

transport within the network of emulsion films within measured in comparable systems11 and than the value of
the liquid emulsion is fully or partially rate limiting, water critical disjoining pressure required to induce droplet
evaporation causes a concentration gradient in water coalescence in similar emulsion systems.12 Second, the
throughout the depth of the emulsion. This gives thinner best-fit value of d0 (110 nm) is much larger than the Debye
emulsion films at the emulsion-vapor surface and pro- length estimated for the electrolyte concentration in the
duces slower water evaporation. Second, as shown by emulsion samples. SDS (20 mM) in the aqueous phase
Bibette,12 osmotic compression of monodisperse emulsion corresponds to an initial Debye length of less than 1 nm,
drops can commonly cause drop coalescence above a critical which will become even shorter as the water evaporates
disjoining pressure that is around 105 Pa for o/w emulsions and the ionic strength in the remaining water is increased.
stabilized by SDS, much less than the values of Π0 required Although crude, these comparisons strongly suggest that
to significantly affect the evaporation rate. Extensive oil- the smooth slowing down of evaporation rates observed
droplet coalescence to produce a water-impermeable oil in Figure 3 before all the water is lost is not due to vapor
film of macroscopic thickness at the emulsion surface pressure reduction within thinned water films in emul-
would act to strongly retard the further evaporation of sions of uniform composition. It is likely that water
water. This type of behavior has been observed in drying
diffusion within the film network of the emulsion is (at
studies of concentrated o/w emulsion films by Bouchama
least partly) rate-limiting and that this produces a gradient
et al.,13 albeit without the controlled gas flow and
in the water concentration and film thickness.
knowledge of the thickness of the stagnant vapor space
as used in this study. Further information on aspects of Further evidence that the limiting “vapor-diffusion-
evaporation from concentrated emulsions can be found in control” mechanism is not achieved in the systems of
the study of film formation from reactive silicone emulsions Figure 3 is provided by comparison with mass-loss curves
by Guigner at al.14 and references therein. measured at a smaller depth of emulsion sample corre-
sponding to a higher stagnant layer thickness h. Under
Results and Discussion these conditions, water diffusion times in the liquid will
Figure 3 shows experimental water mass-loss curves be shorter and those in the vapor will be longer, making
measured for a series of 3.0 g of emulsion samples with it more likely for vapor diffusion to be rate limiting. If
initial water volume fractions of 0.1, 0.2, and 0.3. The vapor diffusion were rate limiting under the conditions of
average oil-droplet radius (defined as the radius value at Figure 3, then the mass-loss curve shapes and best-fit
which the cumulative, volume-weighted distribution curve values of Π0 and d0 should be identical for different h
reaches 50%) was 4.0 µm for all samples. The experimental values. Figure 4 shows plots of water loss versus time
curves were globally fitted to the “vapor-diffusion-control” measured for a series of 0.5 g of emulsion samples with
model (eqs 1-5) to obtain an approximate estimate of the initial water volume fractions of 0.1, 0.2, and 0.3. For this
strength and range of repulsive interactions that would series, the initial value of h was 36.5 mm, compared with
be consistent with the data if the rate was limited solely 26.7 mm when 3.0 g of emulsion sample was used. The
by vapor diffusion. Because the crude model neglects emulsion sample depth was approximately 2 mm for 0.5
nonelectrostatic forces, droplet polydispersity, and the fact g of emulsion compared with 12 mm for 3.0 g. In comparing
that the ionic strength of the aqueous phase increases as corresponding plots in Figures 3 and 4, it can be seen that
the water evaporates and changes the range of the increasing h causes the mass-loss curves to become
electrostatic interactions, the apparent best-fit values of significantly more kinked, and this shape change is
Π0 ) 3.0 × 108 Pa and d0 ) 110 nm are order-of-magnitude reflected in the best-fit value of d0 of 12 nm, compared
estimates only. Despite this, the comparison still serves with 110 nm for the data of Figure 3. The best-fit value
to show that the assumptions inherent in the “vapor- of Π0 is virtually unchanged at 2.7 × 108 Pa. The observed
diffusion-control” model do not apply to our experimental change in the shape of the mass-loss curves at different
situation. First, the best-fit value of Π0 of 3.0 × 108 Pa h’s clearly confirms that liquid-phase transport is rate
corresponds to disjoining pressures much larger than those limiting (at least partially) and, hence, that a water
concentration gradient is generated during evaporation.
(12) Bibette, J.; Langmuir 1992, 8, 3178. The fact that virtually all the available water is lost by
(13) Bouchama, F.; Estramil, G.; Autin, A. J. E.; Koper, G. J. M.
Colloids Surf., A 2002, 210, 120. evaporation suggests that oil-droplet coalescence to pro-
(14) Guigner, D.; Fischer, C.; Holl, Y. Langmuir 2001, 17, 3598. duce a macroscopic oil film at the emulsion surface
Evaporation Rates of Water from o/w Emulsions Langmuir, Vol. 20, No. 6, 2004 2073

Figure 6. Water mass-loss curves for PDMS-in-water emul-

sions with 20 mM SDS and 10 vol % water containing different
initial NaBr concentrations (shown on the curves). The initial
mass of each emulsion was 0.5 g, corresponding to an initial
h ) 36.5 mm. The horizontal dashed line corresponds to the
plateau value expected for complete water loss.

to an aliquot of an o/w emulsion prepared without NaBr.

For the emulsion containing zero added NaBr, the
evaporative mass-loss stops when virtually all of the water
Figure 5. Phase-inversion map for batch emulsions containing in the original emulsion is lost (approximately 0.15 g). As
PDMS and aqueous NaBr solutions and stabilized by 20 mM
SDS. Open circles correspond to o/w emulsions, whereas filled the NaBr concentration is increased, the evaporation slows
circles correspond to w/o emulsions. The line is a guide to the and stops well before all the water is lost. This behavior
eye for the locus of phase inversion. The micrographs show the is not expected if the only effect of NaBr addition is to
emulsion appearance at the compositions indicated by the reduce the range of the electrostatic repulsion between
arrows. droplets. As noted previously, this should enhance the
kinks in the curves but is not predicted to alter the final
apparently does not occur, except possibly in the final plateau values of mass loss. The most likely explanation,
stages of water loss. qualitatively consistent with the observation (Figure 5)
In a further series of experiments, we have investigated that NaBr promotes phase inversion, is that NaBr addition
the effect of electrolyte (NaBr) addition on the water induces oil-droplet coalescence and the formation of a
evaporation rates. Increased aqueous-phase electrolyte water-impermeable film of oil that strongly retards further
concentration is expected to reduce the range of the water loss.
interdroplet electrostatic repulsion. As seen in the simu-
lated plots of Figure 2b, reducing d0 is expected to enhance Conclusions
the sharpness of the kinks in the mass-loss curves. A We have investigated the rate of water evaporation from
second effect of the addition of NaBr is that it promotes concentrated o/w emulsions containing an involatile oil.
phase inversion of the emulsions from o/w to w/o, for which Evaporation of the water continuous phase causes com-
the first stage is coalescence of the oil drops. Figure 5 pression of the emulsion with progressive distortion of
shows the locus of the phase-inversion transitions for batch the oil drops and thinning of the water films separating
emulsions homogenized separately at each composition. them. Theoretically, the vapor pressure of water is
o/w emulsions are produced at low [NaBr] and φoil (open sensitive to the interdroplet interactions, which are a
points), whereas w/o emulsions are favored at high [NaBr] function of the film thickness. Three possible situations
and φoil (filled points). Illustrative micrograph images of are considered. First, under conditions when the evapora-
the emulsions are also shown. tion rate is controlled by mass transfer across the stagnant
For emulsions that are initially o/w, water loss by vapor-phase, model calculations show that evaporation
evaporation increases both [NaBr] and φoil (and [SDS]) can, in principle, be slowed by repulsive interdroplet
and is, therefore, expected to trigger phase inversion and interactions. However, significant retardation requires
production of an oil film, which serves to prevent further very strong repulsive forces acting over large separations
water evaporation. In the absence of added NaBr, the for typical emulsion drop sizes. Second, water evaporation
batch-homogenized emulsions of Figure 5 invert from o/w may be limited by diffusion in the network of water films
to w/o at φoil of 0.92, that is, at φwater of 0.08. From Figures within the emulsion. In this situation, water loss by
3 and 4, water evaporation ceases when φwater reduces to evaporation from the emulsion surface leads to a gradient
less than approximately 0.01. Clearly, water evaporation in the water concentration (and in the water film thick-
retardation does not occur at the same composition as ness). Third, compression of the drops together may lead
phase inversion in the batch-homogenized emulsions. This to coalescence and the formation of a macroscopic oil film
may be related to the difference in SDS concentration at the emulsion surface, which can serve to prevent or
induced by water evaporation or the lack of re-homog- strongly retard further water evaporation.
enization as the emulsion composition is altered by Water mass-loss curves have been measured for PDMS-
evaporation. in-water emulsions stabilized by the anionic surfactant
Figure 6 shows mass-loss curves for a series of o/w SDS with different water contents, stagnant vapor-phase
emulsions (0.5 g) initially containing 30 vol % water and layer thicknesses, and aqueous-phase electrolyte concen-
the NaBr concentrations indicated in the legend. The trations. Under conditions of slow vapor-phase transport
emulsion samples were prepared by addition of the (i.e., large stagnant layer thickness) and zero added
required volume of a concentrated aqueous NaBr solution electrolyte, virtually all the water is lost by evaporation
2074 Langmuir, Vol. 20, No. 6, 2004 Aranberri et al.

at a rate similar to that for pure water. This is consistent inversion in batch emulsions. Water evaporation from
with theoretical calculations that indicate that inter- emulsions containing added electrolyte is strongly re-
droplet repulsive forces are unlikely to be sufficiently tarded well before all the water is lost, probably as a result
strong to significantly retard the evaporation rate. Under of oil-drop coalescence and the formation of a macroscopic
conditions of faster vapor-phase transport (i.e., reduced oil film at the emulsion surface, which strongly retards
stagnant layer thickness) and zero added electrolyte, there further water evaporation.
is a significant reduction in the evaporation rate prior to
complete water loss. A likely explanation for this observa-
tion is that depletion of water by evaporation in the Acknowledgment. We thank Dr. Eric Paterson for
emulsion surface region has caused water films in the many helpful discussions and Dow AgroSciences for
surface region to be thinner than the values estimated financial support.
using an average water concentration. Addition of elec-
trolyte is shown to promote oil-drop coalescence and phase LA035031X