Factors Affecting Emulsion Stability, and the HLB Concept

J. BOYD, C. P A R K I N S O N , 1 AND P. S H E R M A N 1

Unilever Research Laboratory Colworth/Welwyn,

Welwyn, Hertfordshire, England
Received October 11, 1971; accepted December 14, 1971

INTRODUCTION the rate of separation of dispersed phase

The H L B system for selecting suitable from emulsions stored in closed glass con-
emulsifiers to stabilize emulsions has been in tainers. This is a very unsatisfactory method
use now for about two decades. I t developed for evaluating emulsion stability since the
initially from observations by Griffin (1-3) globules undergo substantial coalescence
that the efficiency of blends of hydrophilic before there is any visible dispersed phase
and lipophilic non-ionic surfactants as separation. As far as the authors are aware
emulsifiers for a particular oil was at a max- there has been no systematic quantitative
imum when the blends contained similar evaluation of the influence of H L B on emul-
weight percentages of hydrophilic material. sion stability. The present paper describes
It was concluded that " . . . H L B value is a such a study and reexamines some of the
function of the weight percentage of the factors which influence emulsion stability.
hydrophilic portion of the molecule of a non-
ionic surfactant" (2). EXPERIMENTAL METHODS
Several analytical procedures have been 1. Preparation of Emulsions. O / W and
proposed (4) for determining the HLB of W / O emulsions were prepared containing
emulsifiers, or emulsifier blends. However, 50.0 % (v/v) dispersed phase. The emulsifiers
they all suffer from the disadvantage that used were commercial grade Spans and
the emulsifiers are examined in isolation Tweens (Honeywill-Atlas, London), and the
from the practical environment so that the oil was Nujol. The emulsifiers used to pre-
data are of dubious value. Shinoda (5) high- pare the O / W emulsions were mixtures of
lighted the difficulties in evaluating meaning- Spans and Tweens blended together so as to
ful HLB's when he pointed out that this give H L B values within the range 8.5-16.5;
concept depends upon the balance of tile mixtures of Spans were used to prepare W / O
emulsifier at the oil-water interface, and emulsions with H L B values from 2.0 to 6.5.
that HLB would also depend on the nature Prior to emulsification the Spans were always
of the oil phase and on the additives in the dissolved in the oil phase and the Tweens in
aqueous and oil phases. Temperature would the aqueous phase. The total emulsifier con-
also be important since it would influence centration in each emulsion was held con-
the interaction between the aqueous phase stant at 10-5 mole/liter.
and the hydrophilic groups of the emulsi- Following slow dropwise addition of the
fiers, and between the oil phase and the dispersed phase to the continuous phase
lipophilie groups. with vigorous manual agitation each coarse
One of the ways used to characterize emulsion was passed twice through a lab-
emulsifier blend efficiency was to determine oratory size valve homogenizer. The O/W
1 Present address: Department of Food Sci- emulsions were then allowed to age at 5,
enee and Nutrition, (~ueen Elizabeth College 25, and 40°C. Tests on the W/O emulsions
(University of London), Campden Itill Road, were restricted to aging at 25°C.
London W.8., England. 2. Particle Size Analyses. These were made
Copyrightc@1972by AcademicPress,Inc. Journal of Colloid~nd InterfaceScience,Vol.41, No. 2, November1972
All rights of reproductionin any formreserved.
359
360 BOYD, PARKINSON, AND SHERMAN
with a Coulter centrifugal photosedimen-
tometer (6, 7). Analyses were speeded up by
linking a data logger to the equipment, and
recording the data directly on punched tape.
A computer program was devised to facili-
tate the calculations. Mean volume diam-
eters were calculated from the data, and
these values led to the number of globules/
ml (Nt).
3. Rheological Characterization of Emulsi-
tier Films at the Oil-Water Interface. Detailed
studies were made on Tween 20-Span 20
blends. The Tween 20 was dissolved in the
aqueous phase and the Span 20 in the Nujol.
A total emulsifier concentration of 10%
(w/w) was used, and the Tween/Span con-
centration ratio was varied so as to provide
five different HLB values. These were 8.7,
10.75, 12.75, 14.75, and 16.7, and they were
derived by moving from 10.0 % (w/w) Span
20 in the oil phase, through various concen-
trations of Span 20 in the oil phase with
appropriate concentrations of Tween 20 in
the aqueous phase, to 10.0 % (w/w) Tween
20 in the aqueous phase.
After the oil phase had been carefully
added above the aqueous phase the emul-
sifter film was allowed to form at the oil--
water interface by adsorption from the two
bulk phases. The rheometer employed to
study the rheological properties of the inter-
facial films has been described elsewhere (8).
Each creep compliance-time study took
about 10 rain. As the properties of the inter-
face change more rapidly soon after the
interface has been formed than at longer
aging times, the creep compliance-time data
for the longer aging times are the most re-
liable. The theological properties of the
interfaces were studied at temperatures of
25.0 4- 0.5 and 49.0 4- 0.1°C, so as to paral-
lel some of the emulsion stability studies.
The linear dependence of compliance on
stress was checked so as to ensure that anal-
ysis of the data could be based on linear
viscoelasticity theory; also, to ensure that
it was permissible to adjust the shear stress
by a small, but measurable, amount as re-
quired so as to counteract the changes in
film properties during aging.
RESULTS
1. Emulsion Stability. The influence of
HLB on the rate of globule coalescence at
Journal of Colloid and Interface Science, Vol. 4I, No. 2, November 1972
25°C is shown in Fig. 1 for W/O emulsions
stabilized by Span 80-Tween 20 or Span
85-Span 20, and for O/W emulsions sta-
bilized by Span 20-Tween 20, Span 80-
Tween 20, Span 85-Tween 20, Span 80-
Tween 40, or Span 20-Tween 40. The rate
of globule coalescence, which is the only
quantitative criterion of emulsion stability,
was calculated from the rate of change in
In Nt with time during the slow phase of
coalescence (9).
It is readily apparent that both HLB and
chemical constitution of the emulsifiers
exert a large influence on the rate of coales-
cence of emulsions containing blends of Span
and Tween emulsifiers. Both the O/W and
W/O emulsions show regions of minimal
coalescence at characteristic HLB values,
viz, ~12.0 for the O/W emulsions and ~--3.5
for the W/O emulsions. The stability of the
O/W emulsions falls away rather sharply on
either side of the optimum HLB; but, for
the W/O emulsions, the effect is less marked,
probably because of the much narrower
HLB range over which the latter emulsions
could be made. For the O/W emulsions, the
order of decreasing stability is Span 80-
Tween 40 > Span 80-Tween 20 > Span
20-Tween 40 > Span 85-Tween 20 > Span
20-Tween 20, while W/O emulsions pre-
pared with Span 80-Span 20 were more
.<__% ~
E 05
,OZ
9
~.~
~\\'~\\~/~ / t ~
\ 1
/ SPAN20/TWEEN20
SPANSS/TWEEN20
SPANSO/TWEEN20
]1 '~, ~ /] SPAN80/TWEEN40
SPAN20/TWEEN40
2 5 LSPAN85/TWEEN20
.ff
; 4'0 1~ 2'0
H.L.B
F I G . 1. I n f l u e n c e of H L B on emulsion stability.
 EMULSION STABILITY
stable than emulsions prepared with Span
85-Span 20.
Other pertinent facts revealed by Fig. 1
are as follows:
a. Almost equal stabilities are obtained
when O / W emulsions are prepared with
Span 20 dissolved in the oil phase or with
Tween 20 dissolved in the aqueous phase.
b. O / W emulsions prepared with Span
80 or Span 85 dissolved in the oil phase are
not very stable.
c. O / W emulsions prepared with Span-
Tween blends are more stable when Tween
40 is used in preference to Tween 20.
d. O / W emulsions prepared with Span-
Tween blends are more stable than O / W
emulsions prepared with either a Span or a
Tween alone. Optimu m stability is achieved
at a critical molar ratio of the two emul-
sifters. This is ~ 1 : 1 for Span 80 or Span
85-Tween 20 or Tween 40 blends, and ~ 3 : 1
for Span 20-Tween 20 blends.
The rates of globule coalescence in O / W
emulsions aged at 5 and 40°C show a similar
dependence on H L B during the early days
to that observed at 25°C. Figure 2 shows
some typical data for O / W emulsions sta-
bilized with Span 20-Tween 20. The data
derived at 25°C are included for comparison
purposes, and the rates of coalescence are
2
'o
~5
2
1() 115
H.LB.
FIG. 2. Influence of HLB on the stability of
Tween 20-Span 20 stabilized O/W emulsions at
different temperatures.
Journal of Colloid and Interface Science, V o l . 41, N o . 2, N o v e m b e r 1972
36I
plotted on a logarithmic scale so that all
data can be fitted into a single graph. The
40°C data relate to stability studies for a
maximum aging period of 15 days, since the
emulsions broke down very rapidly after
this. Emulsions aged at 55°C (data not
quoted) broke down completely after 7-8
days.
Figure 3 illustrates the semilogarithmie
dependence of coalescence rate on tempera-
ture at four different H L B values. I t appears
that temperature influences coalescence to a
lesser extent as the H L B increases.
2. Rheological Properties of Span 20-Tween
20 Emulsifier Films at Oil-Water Interface.
Preliminary studies indicated that the emul-
sifter films broke down very readily and ex-
hibited viscous flow, so that it was necessary
to keep the strain extremely low to identify
viscoelastic behavior. This requirement was
met by restricting the strain to about 10-a.
Furthermore, tests indicated that the stress-
strain relationship became nonlinear when
the applied stress exceeded a value repre-
sented by 14 v, so the stress was kept below
this level. Compliance-time curves obtained
in the linear region were "normalized" to
one intermediate shear stress so that the
various sets of data could be compared more
readily.
v
S
"6
.Ol
~ ~'o ~'o 5 ~'o ~'o
T~mp~ratur¢ °C
FIG. 3. Influence of temperature at selected
HLB values on the stability of Tween 20-Span 20
stabilized O/W emulsions.
362 BOYD, PARKINSON, AND SHERMAN

The compliance-time data (Figs. 4-7) in- ~o

dicate that the compliance decreases at 25°C

with increasing film age at all the HLB
values selected. The influence of HLB on
the compliance exhibited 30 sec after apply-
ing the stress is summarized in Fig. 8 for
five different aging times. All the curves
show minimum compliance in the HLB re- ~0
gion where maximum emulsion stability is

10 Film age (hr)

/ o 74
~1Y2
A4
* 23
a46

4[.S 1273 25'C

01 I
0-i 1~,0 1o
Time (rains)
j 7
Y
FIG. 6. Creep compliance-time response of
~ IO
v Tween 20-Span 20 mixed films at ttLB 12.73 at
an oil-water interface.
.2

Flolrr~Age (hi')
1~h
A3
20
o 22
• 23'&
f
HLB 87 25~
01
01 i'0 i'o
Time (mins) ==
Fro. 4. Creep compliance-time response of
Tween 20-Span 20 mixed films of HLB 8.7 at an
oil-water interface. ~ I£ j J

oE
u
Film age (hr)
o~
~1~
,L3
x 2Z,.
/ D 24~

/
{n 4LB 14.75 25°C
I
J / 0.~).1 110 10
/ Time (rains)
u
.~1.(
y / FIG. 7. Creep compliance-time response of
Tween 20-Span 20 mixed films at HLB 14.75 at
uoE
an oil-water interface.

observed (Fig. 1). The minima in Fig. 8

are better defined than in Fig. 1 because in
~2~
,4 the latter case less data was acquired over
x18Y2
HLB 10.75 25°C
D20
,24
HLB 9-13. It is interesting to note that the
01 I minimum compliance appears to shift to a
01 1!0 10
Time (mins) somewhat lower HLB as the film age in-
F r o . 5 . Creep compliance-time response of creases.
Tween 20-Span 20 mixed films of HLB 10.75 at Compliance-time data at 40°C follow the
an oil-water interface. same trend as at 25°C, with the compliance
Journal of Colloid and Interface Science, Vol. 41, No. 2, November 1972
 EMULSION STABILITY 363

10 pared with either emulsifier separately, the

Span and Tween enter into some form of
molecular association at the oil-water inter-
face. The various forces which can be in-
volved are van der Waals' forces between
the hydrocarbon chains of the emulsifier
molecules, and ion-dipole or dipole-dipole
interactions between the head groups (10,
11). According to Derviehian (12) it is the
van der Waals' forces between the hydro-
carbon chains which are primarily respon-
~ 1.0 sible for the regular arrangement of emul-
sifier molecules in mixed monolayers. Fur-
¢2 thermore, it has been observed that emul-
sifier molecules cannot associate easily
unless the hydrocarbon chains contain at
Film age (hr) least 8 C atoms.
o 1~
Molecular association at an oil-water
• 3-4 interface between Span and Tween mole-
* 18~2-20
• 24 cules could follow a distinctive pattern. If
we select Span 80 and Tween 40 as our first
example then the Span 80 molecules will be
oriented so that each hydrocarbon chain
HLB
lies on the oil side of the interface and each
FIO. 8. Influence of HLB on creep compliance
at, 25°C of Tween 20 Span 20 mixed films 30 sec
after applying shear stress. 10

decreasing as the film age increases. The in-

fluence of H L B on the compliance exhibited
30 sec after applying the stress is summarized
in Fig. 9, and the minimum in each curve is
located at the H L B at which emulsion sta-
bility at 40°C is maximal. All the emulsifier
films showed viscoelastic behavior under the
stress conditions imposed, which could be v

represented satisfactorily by 6 element o

models consisting of two Kelvin-Voigt units ml(
in series with a Hookean spring and New-
tonian dashpot.
Compliance-time data for interracial films
at H L B 16.7, i.e., prepared from Tween 20 Film age (hr)
only, have not been quoted because these
3
films were very weak and the data could not 22
be shown on the scale used in Figs. 4-7.
DISCUSSION
1. Molecular Association of Spans and
Tweens. Since the stability of the O / W emul- 0.1 9 - l~D 111 II2 113 lt4 115 16 117
sions to coalescence is greater for Span- HLB

Tween blends than when using either emul- FIG. 9. Influence of I~LB on creep compliance
sifier on its o ~ , and it is not merely the at 40°C of Tween 20-Span 20 mixed films 30 sec
average of the stabilities of emulsions pre- after applying shear stress.
Journal of Colloid and Interface Science, V o l . 41, N o . 2, N o v e m b e r 1972
364 BOYD, PAP~KINSON, AND SHEP~MAN
sorbitan ring lies on the aqueous side. When
the interfacial tension falls during the emul-
sification stage, i.e., the surface pressure
increases, the hydrocarbon chains of the
Span 80 molecules are prevented from mov-
ing close together because of the width of
the sorbitan rings (Fig. 10). In the case of
Tween 40, because of the strong attraction
for water exhibited by the polyoxyethylene
chains, the molecules are oriented at the
oil-water interface in such a way that only
a part of each hydrocarbon chain lies within
the oil phase, the other part being located
in the aqueous phase on the other side of
the interface. When Span 80 and Tween 40
are used together those parts of the Tween
40 hydrocarbon chains that are located in
the oil phase penetrate between the ad-
sorbed Span 80 molecules (Fig. 10). The
S80
H~
cha ins
Oit
OH
Water
OH
OH q-OH
/ "S50
$80
FZG. 10. S c h e m a t i c r e p r e s e n t a t i o n of o r i e n t a t i o n of T w e e n 40 a n d S p a n 80 molecules in m i x e d films
a d s o r b e d at t h e o i l - w a t e r i n t e r f a c e .
Journal of Colloid and Interface Science, Vol. 41, No. 2, November 1972
distance between adjacent hydrocarbon
chains is thereby reduced, so that the prob-
ability of attraction between them is in-
creased.
When emulsions are allowed to age follow-
ing preparation the globules come together
and form floccules. With time these floccules
grow progressively larger, but this process
is partially offset by globule coalescence. It
can be readily shown that flocculation pro-
ceeds much more rapidly than coalescence
in the initial stages of aging. Within the
floccules, that part of each globule surface
which faces another globule flattens under
the influence of various hydrodynamic fac-
tors (13). The narrow column of continuous
phase between the flattened globule surfaces
is stabilized by the hydrated polyoxyethyl-
ene chains of the Tween 40 molecules. Each
S 8O
...~
OH
XXI
"" Polyoxyethylzne
chains
 EMULSION STABILITY
Tween 40 molecule has three such chains,
and they may interweave to provide a gel-
like structure. This structure provides good
stability to globule coalescence, but when
Span 80 is also present an additional sta-
bilizing mechanism is provided by the closely
packed hydrocarbon chains of alternating
Span 80 and Tween 40 molecules on the oil
side of the interface. In the vicinity of the
voids, the distance between the surfaces of
oil globules is such that the Tween 40 poly-
oxyethylene chains (~30 A when fully ex-
tended) are unable to link up across the
aqueous medium and the latter is conse-
quently less structured in this region.
The stabilization mechanism, which is
proposed, can now be extended to Span 80-
Tween 20 blends. In this case, the Tween
molecules have a shorter hydrocarbon chain
(Tween 40 is polyoxyethylene sorbitan
monopMmitate, Tween 20 is polyoxyethyl-
ene sorbitan monolaurate), and a corre-
spondingly shorter segment will project
into the oil side of the interface. The degree
of attraction between alternating hydrocar-
bon chains of Span 80 and Tween 20 mole-
cules adsorbed at the interface will thus be
sharply reduced. Similarly, the interfacial
orientation of adsorbed Tween 20 molecules
is such that it would be expected to be less
efficient in preventing globule coalescence
than Tween 40 when either emulsifier is
used alone. When Span 85 is used in con-
junction with Tween 40 or Tween 20, the
stability decreases relative to emulsions con-
taining Span 80 with the corresponding
Tween. Span 85 has three oleic acid chains;
whereas Span 80 only has one; and the Span
85 assumes a more open configuration at the
interface. This means that Span 85 mole-
cules cannot form such a condensed associ-
ated structure with either Tween as com-
pared with Span 80. Similarly reasoned
arguments can be advanced for Span 20-
Tween 20 blends.
Support for the stabilization mechanism
proposed here is offered by some preliminary
7r-A studies by our colleague Dr. P. Mussell-
white on Span 20-Tween 20 bleads adsorbed
at the air-water interface. At high ~ values,
the orientation of emulsifier molecules at
the air-water and oil-water interfaces
Journal of Colloid and Interface Science, Vol. 41, No. 2, N o v e m b e r 1972
365
should be similar. It was found that a 1:1
blend shows a larger area per molecule (A)
for surface pressures (Tr) between ~9-30
dyn cm-~ than either Span 20 or Tween 20
when used alone. If the Span and Tween
did not enter into some form of molecular
association, then the 1 : 1 blend would exhibit
~-A properties which are the mean of the
7r-A relationships of the two emulsifiers
when used independently. Similar observa-
tions have been made for 1 : 1 Span 60-Tween
60 blends. Penetration of Tween hydrocar-
bon chains between adsorbed Span mole-
cules would lead to a larger value of A at
any 7r value than would be shown by either
emulsifier on its own.
Blending Span 20 (sorbitan monolaurate),
which can stabilize O/W or W/O emulsions
depending on the concentration and condi-
tions employed (14), ~4th Span 80 or Span
85 does not produce a significant improve-
ment in the stability of W/O emulsions con-
taining only Span 80 or Span 85. This is
because the sorbitan rings of the Span 20
molecules function at the interface in the
same way as the sorbitan rings of Span 80
or Span 85, thus preventing the hydrocarbon
chains of alternating Span 80 and Span 20
molecules, or Span 85 and Span 20 molecules,
from packing more closely together than
when only Span 80 or Span 85 molecules are
present. Span 85-Span 20 blends provide
somewhat better stability than Span 80-
Span 20 blends because in the former ease
the trioleate radicles develop a more com-
plex structure in the oil phase. This struc-
ture will function to some extent like the
polyoxyethylene chains of Tween molecules
in O/W emulsions, although the trioleate
radicles do not react with the oil phase to
anything like the same extent that the poly-
oxyethylene chains react with the aqueous
phase. Nevertheless, as the thickness of the
oil film between water droplets in the W/O
emulsions should be less (;~ 36 A) than the
thickness (up to 70 80 A if one allows for
part of the Tween hydrocarbon chain lying
in the aqueous phase) of the water film be-
tween oil droplets in the O/W emulsions the
relative concentration of hydrocarbon chains
projecting into the oil phase in the W/O
emulsions could be of the same order as the
366 BOYD, PARKINSON, AND SHERMAN
concentration of polyoxyethylene chains pro-
jecting into the aqueous phase of the O/W
emulsions.
2. Structure w~thin Liquid Films Between
Globules. It is apparent from the preceding
discussion that the structure conferred by
emulsifier molecules on the thin films of
continuous phase separating flocculated
globules plays an important role in emulsion
stability. The relationship between stability
and the kinetics of thinning for these liquid
films has been studied in some detail (15),
although the situation is not yet fully clari-
fied for W/O emulsions. Now it would appear
equally worthwhile to study the structural
organization within these liquid films. Re-
cent studies [Friberg and Mandell (19),
Friberg et al. (17, 18), and Larsen (16)] are
particularly noteworthy in their attempts to
relate these phenomena to the properties of
emulsions. However, as in previous studies,
the emphasis was placed on the properties of
bulk solutions of emulsifiers; whereas it is
the properties of the thin liquid films be-
tween globules in the emulsions derived
from these solutions which is the important
factor. A possible line of approach would be
to combine film thinning studies with ex-
amination of these films by optical or other
techniques.
3. Mass Transfer of Tween Emulsifier to
the Oil Phase. Recent studies [Taubman and
Nikitina (20), Taubman et al. (21, 23),
Prigorodov et al. (22), and Nikitina et al.
(24)] support the concept of structural or-
ganization in the liquid films between glob-
ules in emulsions. They suggest, however,
that as a result of mass transfer of emulsifier
between the phases an ultramicroemulsion
with a multilayer structure is formed at the
oil-water interface during the emulsification
process. In surface theological studies on
Tween-Span blends at a model flat water-
oil interface, which are discussed in the
next section, it was observed that the oil
phase became cloudy but not the aqueous
phase. This suggests that Tween moves from
the aqueous phase to the oil phase but that
Span does not move to any extent in the
reverse direction. The other suggestion made
by the Russian workers, viz., formation of
an ultramicroemulsion at the oil-water inter-
face, must be rejected. It may occur at a
Journal of Colloid and Interface Science, Vol. 41, No. 2, November 1972
static model oil-water interface due to
diffusion of emulsifiers across the interface
and/or emulsification under the influence of
extraneous vibrations, but not in a practical
emulsion system.
The ultramicroemulsion probably consists
of hydrated hydrophilic segments of the
emulsifier molecules. This would correspond
to the highly hydrated polyoxyethylene
chains of adsorbed Tween molecules in the
present study, or to hydrated Tween mi-
celles.
4. Rheological Properties of Emulsifier
Films at the Oil-Water Interface, and Emul-
swn Stability. All the interfacial films pre-
pared from Span-Tween blends exhibited
viscoelastic behavior. The instantaneous
elasticity and the Newtonian viscosity at-
tain their maximum values at a Span-Tween
ratio which corresponds reasonably well
with the ratio at which stability is maxi-
mum, thus suggesting that there may be
some interrelationship between the inter-
facial rheological properties and emulsion
stability. It should be emphasized that an
emulsifier which is very effective in stabiliz-
ing an emulsion may be much less effective
in facilitating the production of an initial
small globule size and/or narrow globule
size distribution. A good example of this is
the protein bovine albumin. It forms visco-
elastic films at the oil-water interface and
it is very effective in stabilizing emulsions
(25), but it gives very coarse emulsions of
relatively large particle size. Bovine serum
albumin does not reduce the interfacial ten-
sion between oil and water to any large
extent when it is adsorbed; whereas Span-
Tween blends effectively stabilize emulsions,
although not so well as bovine serum albu-
min, and also reduce the interracial tension
to a low value.
The observed slight shift in the minimal
compliance to a somewhat lower HLB as the
interracial film ages at 25°C (Fig. 8) sug-
gests some form of time-dependent re-
arrangement in the association of Span and
Tween molecules. This rearrangement occurs
after too long a time for it to be caused by
differences between the respective rates of
adsorption of the two emulsifiers.
5JIany studies have been reported in
which emulsion stability has supposedly
 EMULSION STABILITY
correlated with the rheological properties of
emulsifier films adsorbed at the oil-water
interface. These data are of questionable
value since in some eases (20-22, 26) stabil-
ity was evaluated from the time required
for emulsions to break down completely,
while in other cases (27, 28) it has been
evaluated from the kinetics of coalescence
of single drops at model interfaces. Singu-
larly few investigators have studied stability
in a quantitative way. Of particular interest
in the present context is a study (29) on
O / W emulsions stabilized by bovine serum
albumin in the presence of 0.01 M KC1.
Emulsion stability was found to be curvi-
linearly related to both the shear elastic
modulus and the surface viscosity of the
adsorbed protein. Stability was evaluated in
the same way as in the present study but
over relatively short time periods. As the
rate of coalescence in the protein stabilized
emulsions was very much higher (of the
order of 10-5 see -1) than in the Span-Tween
stabilized emulsions the short-term evalua-
tion of stability may have been justified in
the former ease.
Collective plots of surface elasticity and
surface viscosity data against rate of globule
coalescence at 25 and 40°C indicate eurvi-
linear relationships between stability and
~2
o ®
5 Eo 10
FIG. 11. Correlation of emulsion stability data with surface elasticity and surface viscosity of
mixed Tween 20-Span 20 films. O VNat 40°C • vN at 25°0 ® Eo at 40°C × Eo at 25°C.
367
either theological parameter (Fig. 11), with
stability becoming independent of either
elasticity or viscosity when they exceed cer-
tain values. These observations are in gen-
eral agreement with the observations of
Srivastava and H a y d o n (29), and in fact
the rate of coalescence in their protein-
stabilized emulsions became independent of
surface elasticity at a value of elasticity
(~-~15 dyn cm -1) similar to that found in the
present study.
The double logarithmic plots of the data
suggest that the rate of coalescence is in-
fluenced to a larger extent by surface elas-
ticity (gradient ~ - 3 ) than by surface
viscosity (gradient ~ - 1).
Srivastava and H a y d o n (29) attribute
different functions to surface elasticity and
surface viscosity during coalescence, with
surface viscosity playing the major role in
that it controls the rate of flow of the film
away from the point at which globules make
contact. The surface elasticity is believed
only to prevent coalescence on impact.
When a force acts normal to a globule sur-
face, one can envisage a response by the
surface which is, in effect, a creep compli-
ance with time. The response will be pri-
marily dependent on the rheological prop-
erties of the adsorbed emulsifier film when
• x
Dynes~m 15 2O
Surface p0isz
4~o
Journal of Colloid and Interface Science, Vo]. 41, No. 2, N o v e m b e r 1972
368 BOYD, PARKINSON, AND SHERMAN
the film is elastic or viscoelastic. Although
the globules are subjected to a force normal
to their surfaces as they approach one
another, and surface rheological studies
measure shear properties in the same plane
as their surfaces, the properties in the two
planes are interrelated in a simple way.
Presumably the normal stress develops with
the close approach of globules, as the liquid
film between them thins out, until the re-
sultant strain is such that the instantaneous
elastic compliance of the adsorbed emulsifier
film is exceeded and its structure begins to
break down. Flow of the film away from this
region will begin when the degree of rupture
has reached a particular level. The main
difference between the explanation offered
here and Srivastava and Haydon's (29) view
is that in our view surface elasticity and sur-
face viscosity are both involved, and the
rate determining factor is the surface elas-
ticity because rupture of the emulsifier film
cannot begin until the strain exceeds the
instantaneous elastic compliance. The rate of
viscous flow of emulsifier film away from the
point of film rupture will depend on the
subsequent compliance (strain) pattern of
the film with time.
Film rupture will involve an activation
energy sufficient to overcome the van der
Waals' attraction forces between the hydro-
carbon chains of adjacent emulsifier mole-
cules adsorbed at the oil-water interface,
and also to bring about desorption of -CH2-
groups which have a free energy of desorp-
tion of ~1.5 kT/mole of -CH2- at the oil-
water interface (30). The free energy of co-
hesion is very much less than this.
Assuming that globule coalescence is in-
fluenced primarily by the surface elasticity
of the adsorbed emulsifier film, the activa-
tion energy for coalescence has been calcu-
lated from the elasticity data for films aged
for ~-~3 hr at 25 or 40°C. At HLB values of
8.7, 12.7, and 14.7, the respective values of
the activation energy (E) were 4.5, 6.0, and
5.2 kT. The significance of these values will
be discussed in the next section in the light
of activation energies derived from the
temperature dependence of the rate of
globule coalescence.
5. Temperature Dependence of Globule Co-
alescence. The first order kinetics equation
Journal of Colloid and Interface Science, Vol. 41, No. 2, November 1972
for globule coalescence can be treated fur-
ther to give
d{ln [(d/dt)(ln Nt)]} E
- [1]
d(1/T) k '
where k is the Boltzmann constant. Plots of
In [(d/dt)(ln N0] against 1/T for HLB values
9.5, 11.5, 13.5, and 15 gave respective values
for E of 13.3, 15.0, 16.4, and 11.5 kT (Fig.
12). These values are higher than the values
derived from surface elasticity data, and
they are more reliable since the latter data
were obtained from measurements at only
two temperatures. The discrepancy between
the two sets of activation energies may be
due to partial dehydration of polyoxyethyl-
ene chains in the Tween molecules with in-
creasing temperature, and removal of water
molecules which can link together some of
the ethylene oxide groups on adjacent poly-
oxyethylene chains.
6. Appraisal of the HLB Concept. The
HLB approach for formulating emulsions
has several limitations as it cannot explain
the following observations:
1. A single emulsifier, e.g., polyoxyethyl-
ene alkyl aryl ether can produce an O/W or
W/O emulsion depending on the tempera-
ture at which the emulsion is prepared (31).
.01
%
#2 3!~ 3!G 3'.8
1/T (o[[I) (x10-3)
FIG. 12. D e r i v a t i o n of a c t i v a t i o n e n e r g y of
coalescence f r o m t e m p e r a t u r e d e p e n d e n c e of coa-
lescence.
 EMULSION STABILITY
2. When using high concentrations of
oil, a single emulsifier such as Span 20,
or some Tweens, can produce an O/W
emulsion if the emulsifier concentration is
low or a W/O emulsion if a relatively high
emulsifier concentration is used (32). If
the emulsifier is distributed between the
oil and water phases a similar effect is ob-
served (33).
3. The stability of emulsions prepared
with blends of emulsifiers of the opposite
type, e.g., Spans and Tweens, varies ac-
cording to how the two emulsifiers are
partitioned between the oil and water
phases (34, 35).
4. O/W emulsions can be prepared with
certain emulsifiers over the whole HLB
range of 2-17 (36).
5. There is no correlation between non-
ionic emulsifier HLB and emulsion sta-
bility when oleic acid and glycerol are
emulsified (37).
In view of these shortcomings, and of
Shinoda's criticisms (5), none of the meth-
ods which have been proposed (4) for de-
termining HLB values of the fluid phases
and of the emulsifiers gives a truly reliable
guide to emulsion stability. Theoretical
calculations of HLB may be particularly
misleading when using blends of emulsi-
fiers which undergo molecular association
at the oil-water interface, since the associa-
tion complex has properties which are far
removed from the mean of the properties
of the individual emulsifiers involved.
The range of emulsifiers for which HLB
values have been published is rather lim-
ited, and values have not been determined
for many emulsifiers of commercial interest
other than Spans and Tweens. In order to
obtain reliable estimates of HLB values, or
of some equivalent parameter, the stabil-
ities of emulsions prepared from these
emulsifiers must be studied quantitatively.
Only in this way can one account for the
influence of the two liquid phases on emul-
sifier performance.
Quantitative evaluation of emulsion sta-
bility is a rather tedious and time-consum-
ing procedure involving particle size distri-
bution analyses over many days aging.
Shinoda (5) has suggested that the phase
inversion temperature of emulsions pro-
Journal of Colloid and Interface Science, Vol. 41, No. 2, November 1972
369
vides a very reliable index of the true HLB.
He defines the true HLB as "...the HLB pro-
viding a phase inversion temperature that
is 20-60°C higher than the storage tem-
perature," but this definition does not
really indicate which emulsifier, or emulsi-
fier blend, will provide maximum stability.
Investigations in the authors' laboratory
indicate a relationship between phase in-
version temperature and the rate of globule
coalescence in O/W emulsions. These find-
ings will be reported elsewhere.
SUMMARY
The optimum stability of O/W emulsions
stabilized by 1:1 molar ratios of Spans and
Tweens is due to association between the
emulsifier molecules adsorbed at the oil-
water interface. Emulsion stability is re-
lated to both surface elasticity and surface
viscosity, as derived from interfacial rheo-
logical measurements, with a greater de-
pendence on the first named parameter.
Discrepancies between activation energies
calculated from the temperature dependence
of emulsion stability and of surface elas-
ticity suggest that some additional factor
is also involved in globule coalescence, e.g.,
dehydration of the Tween polyoxyethylene
chains. Coalescence may be due to the
force pressing adjacent globules together
giving rise to a compressive stress which
increases with time. When it exceeds a
critical value, which will be related to the
maximum deformation which the globules
can withstand, the interfacial film around
the globules begins to break down and coa-
lescence begins.
The various analytical procedures for de-
termining HLB values of emulsifiers do
not account for interaction between the
emulsifiers and the aqueous and oil phases.
It may be possible to derive more meaning-
ful values from phase inversion tempera-
ture determinations on the emulsions.
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