Journal of Colloid and Interface Science 335 (2009) 94–104

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Journal of Colloid and Interface Science

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Effects of temperature on water-in-oil emulsions stabilised solely by wax

microparticles
Bernard P. Binks *, Anaïs Rocher
Surfactant & Colloid Group, Department of Chemistry, University of Hull, Hull HU6 7RX, UK

a r t i c l e i n f o a b s t r a c t

Article history: The possibility of stabilising oil–water mixtures using wax particles alone is reported. As judged from
Received 17 November 2008 contact angle measurements, wax particles are hydrophobic and act as effective emulsifiers of water-
Accepted 7 March 2009 in-squalane emulsions. Specific differences exist depending on the chemical composition of the particles.
Available online 10 April 2009
The effect of temperature on emulsion stability has been explored in detail. If particles are pre-adsorbed
to water drop interfaces by emulsification at room temperature, subsequent increase of temperature
Keywords: leads to a progressive increase in sedimentation and coalescence as particles melt and desorb from inter-
Wax
faces. The temperature range over which this occurs is similar to that of the melting range of the particles
Emulsions
Melting
alone. If however the particles are melted prior to emulsification, surface-active long chain ester or acid
Hydrophobic molecules adsorb to freshly created interfaces giving rise to excellent stability to coalescence at high tem-
peratures. Rapid cooling of these latter emulsions enhances their long-term stability as solidification of
the molten wax leads to a thickening of the continuous oil phase.
Ó 2009 Elsevier Inc. All rights reserved.

1. Introduction
Wax has been an ingredient in a variety of industries for many
years, having been used in e.g. polishes, candles, cosmetics, con-
tainer coatings and on paper. Waxes can be both natural, e.g. bees-
wax and those in petroleum, and synthetic, e.g. polyethylene-
based. A wax may contain a wide variety of long chain alkanes, es-
ters, polyesters and hydroxyl esters of long chain alcohols and fatty
acids. Waxes are insoluble in water and are very hydrophobic,
hence their use to waterproof fabrics. In the oil industry, while
wax is useful after separation from the crude oil, it can cause a
number of problems before separation [1,2]. Since the wax precip-
itates at low temperatures, it causes plugging in the drilling equip-
ment and in pipelines. Particulate waxes are thought to be partly
responsible for the extremely high stability to coalescence of
water-in-crude oil emulsions [2], since such particles (either bare
or coated) can adsorb to the oil–water interface providing a steric
barrier to drop fusion [3]. However, their precise role in such sta-
bilisation is difficult to ascertain since other surface-active materi-
als are always present, e.g. indigenous surfactants, resins and
asphaltenes [1,2]. We are not aware of any report on the use of
wax particles alone as emulsifiers of oil and water, although stud-
ies exist in which their influence on the properties of surfactant-
stabilised emulsions has been established [4–6] and a very recent
paper shows that Shellac wax particles are good stabilisers of aque-
* Corresponding author. Fax: +44 1 482 466410.
E-mail address: b.p.binks@hull.ac.uk (B.P. Binks).
ous foams [7]. It is also known that emulsions can be stabilised
partly by triglyceride [8] or fat particles [9,10], although these
are not strictly classified as waxes.
Paraffin wax crystals can aid in the stabilisation of water-in-oil
emulsions stabilised primarily by an oil-soluble surfactant [4–6].
Rousseau and Hodge [5] found that both the flocculation and coa-
lescence of the water drops were dependent on whether wax crys-
tals were present in the continuous oil phase prior to
emulsification at room temperature or whether they were formed
in situ by emulsification at high temperature followed by quench-
cooling. Emulsions made with post-crystallised wax were more
stable and it was shown that the crystals formed were smaller than
in the pre-crystallised wax case. In both cases, crystals appeared to
be associated with the drop interfaces and formed a network in the
continuous phase immobilising the drops and preventing sedimen-
tation. The presence of wax particles at liquid surfaces is also
implicated in their behaviour as antifoam agents in surfactant-sta-
bilised aqueous foams [11]. Aronson [11] showed clearly that the
physical state of the wax was crucial in determining their effective-
ness as antifoams. Thus, for paraffin wax, antifoaming was high be-
low the melting point of the particles but decreased substantially
at and above it. An argument based on the larger roughness of solid
particles compared with liquid drops was put forward to explain
this trend, with the asperities on solid particles being capable of
puncturing the aqueous foam films. In this work, we report the re-
sults of a study aimed at investigating if wax particles can act as
sole emulsifiers of oil–water mixtures and describe in detail the
influence of temperature in these systems in relation to the melt-

0021-9797/$ - see front matter Ó 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.03.089
 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104
ing of the particles. The latter effect may provide a means to con-
trol the coalescence tendency of such emulsions.
2. Experimental
2.1. Materials
Four different types of commercial wax particles were used in
this work, and microscopy images of them are given in Fig. 1. Flo-
rabeads (200 lm mean diameter) and Floraspheres (500 lm mean
diameter) were supplied by Chesham Specialty Ingredients, UK,
and are used in, for example, facial scrubs. They are both saturated
esters of Jojoba oil (C38–C44), with the former being a hard wax and
the latter a soft wax. Their melting points are approximately 68
and 52 °C, respectively. Microklear 418 and Aquawax 114 samples
(Micro Powders, USA) are composed of much smaller, irregularly
shaped particles with densities between 940 and 990 kg m 3.
Microklear 418 with a mean particle size of 7 lm is derived from
the natural yellow Carnauba wax, being a mixture of esters of fatty
acids, alcohols and hydrocarbons. Its visual melting point is 83 °C.
Aquawax 114 with a mean particle size of 10 lm is synthetic and,
according to the manufacturer, is composed of saturated straight
chain hydrocarbon molecules, visually melting at 108 °C. The oil
used was squalane, a saturated branched C30 alkane of density
equal to 810 kg m 3, and was purchased from Aldrich (>99%). It
was columned twice through basic alumina to remove polar impu-
rities. It was chosen as a long chain alkane, liquid at room temper-
ature, so as to prevent any dissolution of the solid wax particles.
This was verified since no change in particle shape or size occurred
after dispersing the particles in squalane at room temperature.
Water was first passed through an Elga reverse osmosis unit and
Fig. 1. Optical microscopy images of dry (a) Florabeads and (b) Floraspheres, scale bars = 400 lm, and SEM images of (c) Microklear 418 and (d) Aquawax 114 particles, scale
bars = 10 lm.
95
then a Milli-Q reagent water system. Its natural pH was equal to
5.8 for all experiments.
2.2. Methods
2.2.1. Characterisation of waxes
Both optical (see later) and scanning electron microscopy (SEM)
were used to image the dry wax particle samples. For the latter,
samples were coated with a Au/Pd (82:18) film of 1.5 nm thickness
using a Polaron SC7640 sputter coater, and micrographs were ta-
ken with a Zeiss EVO 60 SEM instrument at a voltage of 22 kV
and a probe current of 20 pA. As discussed recently by Buchwald
et al. [12], melting point determination of waxes in standard cap-
illary tubes only partially describes the thermal properties of the
wax. We have also used differential scanning calorimetry, DSC, to
investigate the two micro-waxes since this enables determination
of the range of temperatures over which melting occurs as well as
the amount of energy associated with the melting transition. Ther-
mal analyses of the waxes were carried out using a Mettler Toledo
DSC-822e instrument, calibrated for temperature and heat flow
using an indium standard. Dry nitrogen was used as the purge
gas. Powdered wax samples (5 mg) were placed in sealed alumin-
ium pans which were run alongside an empty pan. Temperature
scans began with the samples held for 10 min at 25 °C followed
by heating at a particular rate (2 or 10 °C/min) to a temperature
of either 100 or 120 °C. This was immediately followed by cooling
at the same rate, with a second heating–cooling cycle subse-
quently. The results were plotted with heat flow as a function of
temperature, and the system software was used to obtain the on-
set, major peak and end of the melting/solidification transitions,
while the associated heats were calculated by standard methods.
96 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104

2.2.2. Preparation of wax particle dispersions
Oil dispersions of all four particle types were prepared by add-
ing a known mass of particles to a volume of squalane followed by
vigorous hand shaking for 10 s at room temperature. It was also at-
tempted to disperse Florabeads and Floraspheres in oil using a
magnetic bar stirrer (Heidolph MP3001) operating at 1000 rpm
for 1 min at room temperature. A third method for the Flora parti-
cles employed a high intensity ultrasonic vibra-cell processor
(VC100 Sonics & Materials) with a 20 kV CV18 probe of 3 mm
diameter operating at 10 W for 2 min while immersing the vessel
in an ice bath. A second method for the Microklear 418 and Aqua-
wax 114 particles involved the use of a VXR Vibrax basic shaker
(IKA) at 500 rpm for 1 min at room temperature.
2.2.3. Preparation and characterisation of emulsions
Emulsions of 10 cm3 contained equal volumes of water and a
wax particle dispersion in squalane. They were prepared in foil-
lined screw capped glass vessels (i.d. 1.5 cm, height 9 cm) by either
hand shaking the mixture vigorously for 2 min or by using an Ultra
Turrax T25 rotor–stator homogenizer (IKA) with a 0.8 cm head
operating at 11,000 rpm for 30 s. Each set of emulsions was pre-
pared at least twice with good reproducibility and their results
are combined. Since the temperature history is important in
wax-containing systems, we devised different protocols to investi-
gate the effect of temperature. More explicit details will be given
when discussing the results but, in summary, they were:
(a) hand shaking, prepared and stored at room temperature,
(b) hand shaking, prepared at room temperature and subse-
quently heated (Grant LTD6G),
(c) homogenisation, prepared at room temperature and subse-
quently heated,
(d) homogenisation, prepared at different temperatures and
stored at these temperatures,
(e) homogenisation, prepared at different temperatures and
stored at room temperature.
Immediately after emulsification, the emulsion type was deter-
mined by the drop test and by conductivity using a Jenway 4510
conductivity meter with Pt/Pt black electrodes. The stability of
emulsions to coalescence and sedimentation was assessed by mon-
itoring the heights of resolved water and oil, respectively, from the
emulsion phase over time. The stability is recorded in terms of the
fraction of water, fw, or oil, fo, resolved compared with that existing
before emulsification. Thus, fw(o) = hw(o)/0.5 ht, where hw(o) are the
heights of the water (oil) phase resolved at any time and ht is the
5
(a)
4
3

2
Heat flow / mW

0
25 40 55 70 85 100
-1

-2

-3

-4

-5
Temperature / oC

1.5
(b)
1.0

0.5
Heat flow / mW

0.0
25 40 55 70 85 100 115
-0.5

-1.0

-1.5

Fig. 2. (a) Optical microscopy image of a water-in-squalane emulsion stabilised by
2 wt% Floraspheres after homogenisation for 30 s at 11,000 rpm. Scale
bar = 100 lm. (b) Vessel in (a) 1 min after emulsification; white phase is emulsion
with oil and water above and below.
-2.0
Temperature / oC
Fig. 3. DSC traces for the melting and solidification of (a) Microklear 418 and (b)
Aquawax 114 powders. Two heating/cooling cycles are shown at a rate of 2 °C/min.
 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104
total height of the liquid mixture (oil, residual emulsion, water).
Complete coalescence (sedimentation) corresponds to fw(o) equal
to 1, whereas complete stability corresponds to values of 0. Photo-
graphs of vessels were taken using a Canon IXUS55 digital camera.
Drops of diluted emulsions were placed on a single cavity glass
slide with or without a coverslip. They were imaged with a Nikon
Labophot microscope fitted with a digital camera QICAM 12-bit
mono Fast 1394 (QImaging), using Image-Pro Plus 5.1 software
(Media Cybernetics). The average diameter of approximately 100
drops per image was calculated using this software. For experi-
ments in which emulsions were heated to different temperatures,
glass slides were also heated to these temperatures for rapid
microscopic imaging.
For contact angle measurements, hydrophilic microscope glass
slides were first prepared by immersing them in aqueous KOH
solution followed by rinsing with purified water and drying. Pow-
dered wax was then gently poured onto the heated slides; on fur-
ther heating the wax melted and a second slide was used to flatten
the wax layer forming a coating of uniform thickness on cooling.
The advancing contact angles of sessile water drops (20 lL,
pH = 5.8) under squalane were determined using a thermostatted
Krüss DSA10 instrument. The average value of three drops was ta-
ken and oil contacted the solid first. The temperature of the cell
was increased progressively with a water drop in place.
3. Results and discussion
3.1. Emulsions stabilised by Flora-particles
Being hydrophobic, Florabeads and Floraspheres remain on the
surface of water after vigorous mixing with it (hand shaking, stir-
ring and ultrasound). By contrast, dispersions in oil can be pre-
pared using the first two methods but, due to their large size, the
particles sediment to the bottom of the vessel in under 1 min. Son-
Fig. 4. Photographs of the vessels containing water-in-squalane emulsions (1:1) stabilised by (a) Microklear 418 and (b) Aquawax 114 wax particles as a function of initial
particle concentration in oil (given in wt%), 1 month after emulsification. Emulsions were prepared and stored at room temperature, by hand shaking.
97
ication however is not a safe method with such particles since, as a
result of localised heating near the probe, we saw evidence of a
portion of the sample having been melted. Oil dispersions contain-
ing 2 wt% particles were emulsified with water in three ways. If
hand shaken for 2 min or magnetically stirred for 2 min at
2000 rpm, the oil and water phases were completely separated
10 s after mixing, with particles resting in oil at the planar oil–
water interface. If homogenised for 1 min at 11,000 rpm, particles
were broken into smaller ones and, with Floraspheres, fibres ca.
20 lm in length were also formed. Though the oil and water
phases also completely separated after 2 min, a water-in-oil (w/
o) emulsion formed transiently which is stabilised by the wax fi-
bres. A mean diameter of 40 ± 10 lm was measured for the water
drops, Fig. 2. We conclude from this that these wax particles prefer
to stabilise w/o emulsions but, due to their large size, cannot re-
main at the interface around drops [3].
The complete analysis of the forces acting on particles held at
liquid interfaces is very complex, due partly to the deformation
of the surface caused by the presence of the particle [13]. However,
a rough approximation for a spherical particle takes the buoyancy
force as counteracting the interfacial tension force. The former
scales with the cube of the particle radius (via its volume), whereas
the latter varies with radius to the power unity (via its circumfer-
ence). For typical interfaces of alkane–water (as here) and particles
with densities between 1000 and several thousand kg m 3, the
buoyancy term exceeds the tension term, and hence prevents the
particle remaining in the interface, for particle diameters in the
millimetre size range.
3.2. DSC of micro-wax powders
The DSC traces for powdered samples of Microklear 418 and
Aquawax 114 are given in Fig. 3 in which the heat flow is plotted
versus temperature. Two heating and cooling cycles are shown
98 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104

for each. Although the cycles were determined at a high (10 °C/
min) and low rate of temperature change, only that at 2 °C/min
is plotted since there was very little difference between the two
and this rate corresponds more or less to the rate of temperature
rise set in subsequent emulsion studies. For Microklear 418 wax
which melts visually at 83 °C, Fig. 3(a) shows that the reproducibil-
ity of the heating and cooling curves is good and that there is a
small degree of hysteresis in the heating/cooling cycles. More
importantly, on heating, melting is seen to occur gradually over a
13 °C range between 72 (onset) and 85 °C (end), with two peaks
appearing at 77 and 82 °C. On cooling, solidification commences
at 81 until 65 °C. The average enthalpy change on melting is
+173 ± 7 J g 1, while that on solidification is 146 ± 5 J g 1. These
can be compared with that for pure hexacosane (C26 hydrocarbon)
of ±143 J g 1 [14].
By contrast, for Aquawax 114 which melts visually at 108 °C,
the curves are not as reproducible and it melts over a larger range
(60 °C) from 55 to 115 °C, solidifying between 102 and 50 °C and
exhibiting a number of peaks (Fig. 3(b)). The corresponding enthal-
py changes are +170 ± 10 J g 1 on melting and 178 ± 8 J g 1 on
solidification. It is thus clear that due to the large variety of com-
pounds in each wax, melting occurs in stages and that for Aquawax
114 is much more extensive with respect to temperature than that
for Microklear 418.
3.3. Emulsions stabilised by micro-wax particles
We have investigated several routes to study the influence of
particle concentration and temperature in emulsions stabilised so-
lely by the micro-wax particles, and these are discussed
sequentially.
3.3.1. Effect of particle concentration in hand shaken emulsions at
room temperature
Since particles act in many ways like surfactant molecules [3], it
is expected that emulsions will become more stable on increasing
the particle concentration. The wettability of particles at the oil–
water interface is crucial in determining both the preferred emul-
sion type and emulsion stability [15]. The contact angle of water on

(a) 1.0

(a) 3.5

0.8
3.0
Mean water drop diameter / mm

2.5
0.6
fo or fw

2.0

0.4 1.5

1.0
0.2
0.5

0.0 0.0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Microklear 418 / wt.%
Microklear 418 / wt.%

3.0
(b) 1.0 (b)

2.5
0.8
Mean water drop diameter / mm

2.0

0.6
fo or fw

1.5

0.4
1.0

0.2 0.5

0.0
0.0 0 2 4 6 8 10 12 14 16
0 2 4 6 8 10 12 14 16 Aquawax 114 / wt.%
Aquawax 114 / wt.%
Fig. 6. Variation of the mean water drop diameter and size distribution with
Fig. 5. Water-in-squalane emulsion stability for the systems in Fig. 4 for (a) particle concentration for w/o emulsions stabilised by (a) Microklear 418 and (b)
Microklear 418 and (b) Aquawax 114 particles. Filled points refer to fo (sedimen- Aquawax 114 particles prepared and stored as in Fig. 4. The very small drops at the
tation), open points to fw (coalescence) after 1 day. lowest concentrations rapidly grow by coalescence.
 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104
wax-coated surfaces under non-polar oils, measured through
water, is in the range 135–145°, depending on the source of wax
[16], and so it is expected that wax particles will stabilise water-
in-oil emulsions. For glass slides coated with Microklear 418, we
determined the contact angle through water under squalane as
171° between 20 and 50 °C, and equal to 165° for Aquawax 114
over the same temperature range. Above 50 °C in both systems,
the measurement was unreliable since the drop began to enter
the softer, partially melted substrate. The appearance of the vessels
1 month after emulsification of a mixture (1:1) of pure water and a
squalane dispersion of particles is shown in Fig. 4 for both Micro-
klear 418 (a) and Aquawax 114 (b) systems. The particles were dis-
persed in oil by hand shaking for 10 s and then hand shaken with
water for 2 min at room temperature and stored at this
temperature.
For both series, emulsions are w/o as expected and their stabil-
ity to coalescence increases initially with particle concentration
reaching a limit around 8 wt% particles. Their stability is quantified
Fig. 7. Optical microscopy images of w/o emulsions (as in Fig. 4) stabilised by Microklear 418 particles at (a) 2, (b) 7 and (c) 15 wt% and by Aquawax 114 particles at (d) 1, (e)
5 and (f) 13 wt%. Scale bars = 100 lm.
99
in terms of fw or fo which are plotted as a function of particle con-
centration in Fig. 5. For both series, complete phase separation oc-
curs rapidly at and below 1 wt% of particles, with stability to
sedimentation and coalescence increasing progressively above
this. By 10 wt% of particles, w/o emulsions exhibiting very little
coalescence can be formed. The variation of the average water drop
sizes and size distributions with particle concentration is shown in
Fig. 6, with representative optical microscopy images of the emul-
sions being given in Fig. 7. Below 1 or 2 wt% of particles, only small
drops exist initially which coalesce rapidly yielding bulk oil. At
intermediate concentrations, emulsions consist of a population of
small drops (tens of lm measured microscopically) and one of
much larger drops (up to mm measured by eye). Given the polydis-
persity in the size of the wax particles, it is likely that the smaller
drops are stabilised by the smaller size fraction of the particles and
the opposite for the larger drops, as observed previously for latex
particle-stabilised drops [17]. If this is the case, preparing parti-
cle-stabilised emulsions and separating the different drop popula-
100 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104

1.0 1

0.8 0.8

0.6 0.6
fo or fw

fw
0.4 0.4

0.2
0.2

0.0
10 30 50 70 90 110
0
o 10 30 50 70 90 110
Temperature / C
Temperature / oC
Fig. 8. Stability after 1 h of w/o emulsions prepared at room temperature and
Fig. 10. Stability to coalescence after 1 h of w/o emulsions stabilised by 10 wt%
stabilised by 10 wt% Microklear 418 (circles) or Aquawax 114 (triangles) particles
Microklear 418 (circles) and Aquawax 114 (triangles) particles prepared by
as a function of temperature after preparation. Filled points refer to fo (sedimen-
homogenisation at room temperature and subsequently heated.
tation), open points to fw (coalescence). Inset shows the vessels at 95 °C with
Microklear 418 (left) and Aquawax 114 (right).

and a coating of wax particles on their surfaces is evident. Above

tions, e.g. by centrifugation, offers a means to separate particles of a particular concentration, the average drop size (and width of
the same type but different in size. At higher concentrations, a sin- the distribution) decreases with concentration reaching a plateau
gle small drop population exists again. All the drops are spherical value of around 100 lm for Microklear 418 and 500 lm for Aqua-

Fig. 9. Optical microscopy images of some of the emulsions treated as in Fig. 8. Microklear 418 systems at (a) 20 and (b) 60 °C, Aquawax systems at (c) 30 and (d) 70 °C. Scale
bars = 400 lm.
 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104 101

wax 114 systems, in line with the changes in emulsion stability.
Excess wax particles are visible in the continuous oil phase at high-
er concentrations.
3.3.2. Effect of temperature on hand shaken emulsions prepared at
room temperature
Based on the above results, we decided to choose a particle con-
centration which yields stable emulsions at room temperature and
investigate what happens to their stability upon increasing the
temperature gradually. The question we wanted to address was
whether the coalescence stability was sensitive to the physical
state of the adsorbed particles below and above the melting point
range. Two emulsions were prepared from a dispersion of 10 wt%
of Microklear 418 or Aquawax 114 particles in oil and an equal vol-
ume of water by hand shaking for 2 min at room temperature.
Using a water bath, the temperature was increased in 10° steps
to 95 °C, with the vessels being hand shaken gently and then held
for 1 h. at each temperature. Between each temperature, the rate of
temperature increase was close to 2 °C/min, comparable to that in
DSC studies.
Emulsion stabilities are plotted versus temperature in Fig. 8 for
both wax–stabilised systems. The overall trend in both is that the
sedimentation (fo) and coalescence (fw) extents increase with tem-
perature as particles are transformed from solid to liquid. The in-
crease in sedimentation may be due in part to the decrease in
the viscosity of the continuous oil phase with temperature, which
falls by over a factor of three between 20 and 60 °C [18]. This may
be coupled to the increase in coalescence as drops become more
concentrated. As the stabilising wax particles begin to melt, molec-
ular species desorb from the oil–water interface and dissolve in the

(a) 20 30 40 50 60 70 80 90 95oC

(b) 1.0

0.8

0.6
fw

0.4

0.2

0.0
10 20 30 40 50 60 70 80 90 100
o
Emulsification temperature / C
Fig. 11. (a) Photographs of vessels containing w/o emulsions stabilised by 10 wt% Microklear 418 (upper) and Aquawax 114 (lower) particles homogenised and stored at
different temperatures (given). (b) Variation of fw with emulsification temperature for emulsions in (a) for Microklear 418 (circles) and Aquawax 114 (triangles) particles.
102 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104
oil phase. The drops lose their protective armour and fusion be-
tween them proceeds. Phase separation is nearly complete at
95 °C for Microklear 418 emulsions (well above the melting range)
and 75% complete for those of Aquawax 114 (below the end of the
melting range). It can be seen in Fig. 8 that significant coalescence
occurs in a narrow temperature range above 80 °C for Microklear
418 emulsions, whereas it is more gradual between 50 and 95 °C
for Aquawax 114 emulsions. This difference is related to the rela-
tively narrow melting point range determined earlier for the for-
mer and the much wider range measured for the latter,
suggesting that the dominant influence of temperature in the
emulsions is on the properties of the wax particles themselves.
Microscope images of selected emulsions at low and high
temperature are given in Fig. 9. On warming the Microklear 418
emulsion, (a) and (b), we notice that some of the drops become
non-spherical. This is a characteristic of particle-stabilised emul-
sions subjected to coalescence [19] and is linked to the irreversible
nature of particle adsorption. In the Aquawax 114 case, (c) and (d),
although this shape change is less prominent, it is clear that parti-
cle aggregates at the surface of drops are more numerous at the
low temperature than at the high one. In other images not shown,
we also observe portions of the interfaces devoid of particles at
high temperatures.
3.3.3. Effect of temperature on homogenised emulsions prepared at
room temperature
We repeated the experiment just detailed above but where the
emulsion prepared at room temperature was made by homogeni-
sation at 11,000 rpm for 30 s. The findings are reported in Fig. 10.
It should be noted first that the emulsion stability at 20 °C is signif-
Fig. 12. Optical micrographs of w/o emulsions prepared and stored as in Fig. 11 stabilised by Microklear 418 particles at (a) 40 and (b) 60 °C and by Aquawax 114 particles at
(c) 40 and (d) 90 °C. Scale bars = 100 lm.
icantly lower than that for emulsions prepared by hand shaking for
both wax particle systems. This may be caused by partial melting
of the particles in the warmer regions close to the rotor–stator
homogeniser head. Again, the Microklear 418-stabilised emulsion
destabilises abruptly above 80 °C. However, although there is vir-
tually no change in the volume of separated water as a function
of temperature for the Aquawax 114 emulsion, the average drop
diameter observed visually increased with temperature due to
coalescence.
3.3.4. Emulsions homogenised and stored at different temperatures
In order to see if the state of the wax particles prior to emulsi-
fication is important, emulsions were prepared at different tem-
peratures and their stability assessed at the same temperatures.
After hand shaking the particles into oil (10 wt%), the oil phase
was heated to the appropriate temperature (from 20 to 90 °C)
and an equal volume of water at the same temperature was added
followed by homogenisation at 11,000 rpm for 30 s. All emulsions
were stored at the emulsification temperature for 8 h, after which
they were placed on the bench at room temperature. Fig. 11(a) is a
photograph of the vessels 8 h after emulsion formation for the
Microklear 418 (upper) and Aquawax 114 (lower) systems, and
Fig. 11(b) shows how the fraction of aqueous phase resolved after
8 h varies with emulsification temperature. No further changes
were evidenced after 4 h. however. On subsequent cooling of all
the emulsions to room temperature, no changes in the relative vol-
umes of oil, emulsion and water phases occurred. For Microklear
418-stabilised emulsions, the stability to coalescence increases
from 20 to 60 °C, above which it decreases significantly to 95 °C.
The oil phase prior to emulsification was a slightly turbid disper-
 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104 103

sion from 20 to 60 °C, whereas at 70 °C and above it became clearer
and more yellow with residual particles sedimenting very quickly.
The increase in the extent of coalescence above 70 °C is as observed
previously (Fig. 8) and starts at the onset of melting of a fraction of
the particles. The increase in stability approaching 60 °C is surpris-
ing however. If it is due to desorption of a small amount of surface-
active molecules (ester or acid) from particle surfaces which are
then available for adsorption at freshly created oil–water inter-
faces, then at high temperatures when all these molecules are des-
orbed emulsions should be as stable which they are not. However,
smaller chain length molecules which desorb at lower temperature
will be more effective emulsifiers than longer chain homologues
liberated at higher temperature, although we have not proved this.
The average drop sizes immediately after emulsification pass
through a minimum at 60 °C in line with the emulsion stability
maximum. Fig. 12(a) and (b) show micrographs of the emulsions
at 40 and 60 °C where non-spherical drops characteristic of parti-
cle-dominated interfaces are present at the lower temperature,
and mainly spherical drops typical of surfactant-stabilised inter-
faces are seen at the optimum temperature.
By contrast, emulsions stabilised by Aquawax 114 particles
show little change in coalescence stability up to 60 °C, are very
unstable at 70 and 80 °C and become re-stabilised above this
(Fig. 11(b)). In addition, the oil phase before emulsion formation
is slightly turbid between 20 and 60 °C, above which it becomes
clearer. Contrary to the brief description of the composition of this
wax given by the manufacturer, our own ATR-FTIR spectra of a
small sample revealed a band of significant intensity correspond-
ing to a AC@O stretch either from ester or carboxylic acid groups.
This same band was also present in the spectrum of Microklear
418, as expected. It thus appears that Aquawax 114 contains polar
molecules in addition to long chain hydrocarbons, the former being

Fig. 13. Photographs of vessels containing w/o emulsions stabilised by 10 wt% (a) Microklear 418 and (b) Aquawax 114 particles, homogenised at different temperatures
(given) and stored at room temperature. The photos were taken 1 day after emulsification.
104 B.P. Binks, A. Rocher / Journal of Colloid and Interface Science 335 (2009) 94–104
500
400
Average drop diameter / µm
300
200
100
0
10 20 30 40 50 60 70
Emulsification temperature / Co
Fig. 14. Variation of average drop diameter with emulsification temperature for w/
o emulsions prepared as in Fig. 13 and stabilised by either 10 wt% Microklear 418
(circles) or Aquawax 114 (triangles) particles.
capable of adsorbing to the squalane–water interface. Although not
easy to understand, the significant increase in instability occurring
above 60 °C is probably due to the partial melting of the wax par-
ticles (from DSC data, beginning at 55 °C) with a concomitant
change in their solid-like character and wettability. Towards the
upper end of the melting range, a significant proportion of the par-
ticles have melted and hydrophobic molecular species dissolved in
oil act as efficient stabilisers of water drops. As with the other wax
particles, the most stable emulsions are those comprised of the
smallest drops, Fig. 12(c) and (d). It is clear from the findings in
sections 3.3.3 and 3.3.4 that the temperature history in these
wax particle-stabilised emulsions is very important with regards
to their stability. Changing the temperature once particles are ad-
sorbed yields quite different stabilities to that of increasing the
temperature before emulsification; compare 60 °C for Microklear
418 and 95 °C for Aquawax 114.
3.3.5. Emulsions homogenised at different temperatures and stored at
room temperature
Finally, we investigated what happened to emulsions prepared
at different temperatures as described above but cooled within
5 min to room temperature. This is the basis of the method known
as emulsification by the phase inversion temperature (PIT) method
for non-ionic surfactant systems [20], in which the emulsion is
made around the PIT where the drop size is least and then cooled.
In this way, the minimum drop size produced at the PIT is ‘locked
in’ yielding very stable emulsions at the lower temperatures. For
our systems, any melted material formed at higher temperatures
should be solidified in oil on cooling, potentially enhancing the sta-
bility to sedimentation. The results of these experiments can be
seen in Fig. 13 for the two wax types. In (a) for Microklear 418 par-
ticles, the trend in stability with emulsification temperature is the
same as that for emulsions in section 3.3.4, but emulsions are
invariably more stable and the most stable emulsions are formed
at 60, 70 and 80 °C as opposed to at 60 °C only. Importantly, much
better emulsions persist if made at high temperatures (90, 95 °C)
probably due to reduced sedimentation of the drops in a semi-solid
oil phase which lowers the probability of drop coalescence. In (b)
for Aquawax 114 particles, coalescence stability initially increases
to 50 °C, decreases progressively to 80 °C and increases again sub-
stantially to 95 °C, similar to that seen for emulsions prepared in
section 3.3.4 but with higher stabilities. The extent of drop sedi-
mentation releasing free oil is reduced by immediate cooling after
formation. The variation in the average drop diameter with emul-
sification temperature is shown in Fig. 14 for both particle types.
Smaller drops are formed in the Microklear 418 system since these
wax particles are smaller than those of Aquawax 114. The marked
reduction in drop size at the highest temperature is noticeable.
4. Conclusions
Emulsions can be stabilised by micro-wax particles alone and,
since particles are hydrophobic at the oil–water interface, such
emulsions are water-in-oil. Different ways of dispersing the parti-
cles in oil and emulsifying the oil dispersion with water have been
80 90 100 investigated. The stability of these emulsions at different tempera-
tures to both sedimentation and coalescence depends markedly on
whether particles are adsorbed to drop interfaces or not prior to
the temperature change. If drops are formed at room temperature,
increasing the temperature of the emulsion subsequently leads to a
progressive increase in the extent of coalescence as particles melt
and cannot provide a barrier to drop fusion; the temperatures over
which this occurs are in the same range as that of the melting
range of the particles alone. By contrast, emulsions prepared and
stored at a range of temperatures within the melting point range
are particularly stable for the ester-containing wax and at high
temperatures for the predominantly hydrocarbon-containing
wax. It is likely that surface-active molecules adsorb to fresh inter-
faces in these emulsions.
Acknowledgments
We thank the University of Hull for a Ph.D. Scholarship to A.R.
and Dr. M. Hird (University of Hull) for allowing use of the DSC
instrument. We also thank Prof. P.D.I. Fletcher for useful
discussions.
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