Emulsions in The Petroleum Industry

1
Petroleum Emulsions
Basic Principles
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Laurier L . Schramm
Petroleum Recovery Institute, 3512 33rd Street N.W., Calgary, Alberta,

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Canada T 2 L 2A6
This chapter provides an introduction to the occurrence, properties,

and importance of petroleum emulsions. From light crude oils to
bitumens, spanning a wide array of bulk physical properties and
stabilities, a common starting point for understanding emulsions is
provided by the fundamental principles of colloid science. These prin-
ciples may be applied to emulsions in different ways to achieve quite
different results. A desirable emulsion that must be carefully stabi-
lized to assist one stage of an oil production process may be unde-
sirable in another stage and necessitate a demulsification strategy.
With an emphasis on the definition of important terms, the impor-
tance of interfacial properties to emulsion making and stability is
demonstrated. Demulsification is more complex than just the reverse
of emulsion making, but can still be approached from an understand-
ing of how emulsions can be stabilized.
Importance of Emulsions
I f t w o i m m i s c i b l e l i q u i d s are m i x e d together i n a c o n t a i n e r a n d t h e n shaken,
e x a m i n a t i o n w i l l reveal that o n e o f the two phases has b e c o m e a c o l l e c t i o n o f
d r o p l e t s that are d i s p e r s e d i n t h e o t h e r phase; a n e m u l s i o n has b e e n f o r m e d
( F i g u r e 1). E m u l s i o n s have l o n g b e e n o f great p r a c t i c a l interest because o f
t h e i r w i d e s p r e a d o c c u r r e n c e i n everyday l i f e . S o m e i m p o r t a n t a n d f a m i l i a r
e m u l s i o n s i n c l u d e those o c c u r r i n g i n foods ( m i l k , mayonnaise, etc.), c o s m e t
ics (creams a n d lotions), p h a r m a c e u t i c a l s (soluble v i t a m i n a n d h o r m o n e
p r o d u c t s ) , a n d a g r i c u l t u r a l p r o d u c t s (insecticide a n d h e r b i c i d e e m u l s i o n
f o r m u l a t i o n s ) . I n a d d i t i o n to t h e i r w i d e o c c u r r e n c e , e m u l s i o n s have i m p o r -
0065-2393/92/0231-0001 $13.25/0
© 1992 American Chemical Society
Schramm; Emulsions
Advances in Chemistry; American Chemical Society: Washington, DC, 1992.
2 E M U L S I O N S I N T H E P E T R O L E U M INDUSTRY
Figure 1. Photomicrograph of an emulsified droplet of a crude oil, dispersed in

the aqueous solution that was used to release it from the mineral matrix in
which it was originally held. An interfacial film is obvious at the surface of the
droplet.
tant p r o p e r t i e s that may b e desirable, f o r example, i n a n a t u r a l o r f o r m u l a t e d

p r o d u c t , o r u n d e s i r a b l e , s u c h as an u n w a n t e d e m u l s i o n i n an i n d u s t r i a l
process. P e t r o l e u m e m u l s i o n s m a y not b e as f a m i l i a r b u t have a s i m i l a r l y
widespread, long-standing, and important occurrence i n industry. E m u l
sions m a y be e n c o u n t e r e d at a l l stages i n the p e t r o l e u m r e c o v e r y a n d p r o
cessing i n d u s t r y ( d r i l l i n g fluid, p r o d u c t i o n , process p l a n t , a n d transportation
e m u l s i o n s ) . T h i s c h a p t e r p r o v i d e s an i n t r o d u c t i o n to the basic p r i n c i p l e s
i n v o l v e d i n the o c c u r r e n c e , m a k i n g , a n d b r e a k i n g o f p e t r o l e u m e m u l s i o n s .
C r u d e oils consist of, at least, a range o f h y d r o c a r b o n s (alkanes, n a p h -
thenes, a n d a r o m a t i c c o m p o u n d s ) as w e l l as p h e n o l s , carboxylic acids, a n d
metals. A significant f r a c t i o n o f s u l f u r a n d n i t r o g e n c o m p o u n d s m a y b e
present as w e l l . T h e c a r b o n n u m b e r s o f a l l these c o m p o n e n t s range f r o m 1
(methane) t h r o u g h 50 o r m o r e (asphaltenes). S o m e o f these c o m p o n e n t s c a n
f o r m films at o i l surfaces, a n d others are surface active. It is perhaps not
s u r p r i s i n g , t h e n , that the tendencies to f o r m stable o r unstable e m u l s i o n s o f
d i f f e r e n t k i n d s vary greatly a m o n g d i f f e r e n t oils. B e c a u s e o f the w i d e range
o f possible c o m p o s i t i o n s , c r u d e oils c a n exhibit a w i d e range o f viscosities
a n d densities, so m u c h so that these p r o p e r t i e s are u s e d to d i s t i n g u i s h l i g h t ,
heavy, a n d b i t u m i n o u s c r u d e oils. O n e set o f definitions c a n be c o m p i l e d as
follows ( 1 - 3 ) :
Schramm; Emulsions
1. SCHRAMM Basic Principles 3
Viscosity Range (mPa-s), Density Range (kg/m ), 3
Hydrocarbon at Reservoir Temperature at 15.6 °C

Light crude oil < 10,000 <934
Heavy crude oil < 10,000 934-1000
Extra heavy crude oil < 10,000 > 1000
Bitumen (tar) > 10,000 >1000
B e c a u s e the viscosities c o r r e s p o n d to a m b i e n t deposit t e m p e r a t u r e s ,

the v a r i a t i o n i n these p r o p e r t i e s over d i f f e r e n t t e m p e r a t u r e s is e v e n greater
t h a n the table suggests. F o r e x a m p l e , b i t u m e n i n the A t h a b a s c a deposit o f
n o r t h e r n A l b e r t a is c h e m i c a l l y s i m i l a r to c o n v e n t i o n a l o i l b u t has a viscosity,
at reservoir t e m p e r a t u r e , o f about 1 0 mPa-s (1 m i l l i o n times greater t h a n
6
that o f water). D u r i n g h e a t i n g , as part o f an o i l r e c o v e r y process s u c h as hot-

w a t e r flotation o r i n situ steam flooding, e m u l s i o n s h a v i n g a w i d e range o f
viscosities c a n be f o r m e d , p a r t i c u l a r l y i f they are o f the w a t e r d i s p e r s e d i n o i l
type. W h e n these d i f f e r e n t k i n d s o f oils are e m u l s i f i e d , the e m u l s i o n s m a y
have viscosities that are m u c h greater t h a n , s i m i l a r to, o r m u c h less t h a n the
viscosity o f the c o m p o n e n t o i l , a l l d e p e n d i n g o n the nature o f the e m u l s i o n
formed.
A s s h o w n i n T a b l e I, p e t r o l e u m e m u l s i o n s m a y b e desirable o r u n d e
sirable. F o r example, one k i n d o f o i l - w e l l d r i l l i n g fluid (or " m u d " ) is e m u l
sion based. H e r e a stable e m u l s i o n (usually o i l d i s p e r s e d i n water) is u s e d to
l u b r i c a t e the c u t t i n g b i t a n d to carry cuttings u p to the surface. T h i s e m u l
sion is o b v i o u s l y desirable, a n d great care goes i n t o its p r o p e r p r e p a r a t i o n .
A n e m u l s i o n may be desirable i n one part o f the o i l p r o d u c t i o n process
a n d u n d e s i r a b l e at the next stage. F o r e x a m p l e , i n the o i l fields, an i n s i t u
Table I. Examples of Emulsions in the

Petroleum Industry
Occurrence Usual Type a
Undesirable Emulsions
Well-head emulsions W/O
F u e l oil emulsions (marine) W/O
O i l sand flotation process, froth W/O or O/W
O i l sand flotation process, diluted froth O/W/O
O i l spill mousse emulsions W/O
Tanker bilge emulsions O/W
Desirable Emulsions
Heavy oil pipeline emulsion O/W
O i l sand flotation process slurry O/W
Emulsion drilling fluid, oil-emulsion mud O/W
Emulsion drilling fluid, oil-base mud W/O
Asphalt emulsion O/W
Enhanced oil recovery i n situ emulsions O/W
"W/O means water-in-oil; O/W means oil-in-water. See the section
"Definition and Classification of Emulsions".
Schramm; Emulsions
e m u l s i o n that is p u r p o s e l y c r e a t e d i n a reservoir as part o f a n o i l r e c o v e r y

process m a y change to a d i f f e r e n t , u n d e s i r a b l e type o f e m u l s i o n (water
d i s p e r s e d i n oil) w h e n p r o d u c e d at t h e w e l l h e a d . T h i s e m u l s i o n m a y have to
be b r o k e n a n d r e f o r m u l a t e d as a n e w e m u l s i o n suitable for t r a n s p o r t a t i o n b y
p i p e l i n e to a refinery. H e r e , t h e n e w e m u l s i o n w i l l have to b e b r o k e n a n d
w a t e r f r o m t h e e m u l s i o n r e m o v e d ; o t h e r w i s e t h e w a t e r w o u l d cause process
i n g p r o b l e m s i n t h e r e f i n i n g process.
E m u l s i o n s may c o n t a i n not just o i l a n d water, b u t also s o l i d particles a n d
e v e n gas. I n t h e large m i n i n g a n d p r o c e s s i n g operations a p p l i e d to C a n a d i a n
o i l sands, b i t u m e n is separated f r o m t h e sand matrix i n large t u m b l e r s as an
e m u l s i o n o f o i l d i s p e r s e d i n water, a n d t h e n f u r t h e r separated f r o m the
t u m b l e r s l u r r y b y a flotation process. T h e p r o d u c t o f the flotation process is
b i t u m i n o u s f r o t h , an e m u l s i o n that m a y b e e i t h e r w a t e r (and air) d i s p e r s e d
i n t h e o i l ( p r i m a r y flotation) o r t h e reverse, o i l (and air) d i s p e r s e d i n w a t e r
(secondary flotation). I n either case, t h e e m u l s i o n s must b e b r o k e n a n d t h e
w a t e r r e m o v e d b e f o r e t h e b i t u m e n c a n b e u p g r a d e d to synthetic c r u d e o i l ,
b u t t h e p r e s e n c e o f s o l i d particles a n d film-forming c o m p o n e n t s f r o m t h e
b i t u m e n c a n m a k e this r e m o v a l step v e r y d i f f i c u l t .
S o m e e m u l s i o n s are m a d e to r e d u c e viscosity so that a n o i l c a n b e m a d e
to flow. E m u l s i o n s o f asphalt, a s e m i s o l i d variety o f b i t u m e n d i s p e r s e d i n
water, are f o r m u l a t e d to b e b o t h less viscous t h a n t h e o r i g i n a l asphalt a n d
stable so that they c a n b e t r a n s p o r t e d a n d h a n d l e d . I n a p p l i c a t i o n , t h e
e m u l s i o n s h o u l d shear t h i n a n d b r e a k to f o r m a suitable w a t e r - r e p e l l i n g
roadway c o a t i n g m a t e r i a l . A n o t h e r example o f e m u l s i o n s that are f o r m u l a t e d
for l o w e r viscosity w i t h g o o d stability are those m a d e f r o m heavy oils a n d
i n t e n d e d f o r e c o n o m i c p i p e l i n e t r a n s p o r t a t i o n over large distances. H e r e
again t h e e m u l s i o n s s h o u l d b e stable f o r transport b u t w i l l n e e d to b e b r o k e n
at t h e e n d o f t h e p i p e l i n e .
F i n a l l y , m a n y k i n d s o f e m u l s i o n s pose d i f f i c u l t p r o b l e m s w h e r e v e r t h e y
may o c c u r . F o r example, c r u d e o i l w h e n s p i l l e d o n t h e o c e a n tends to
b e c o m e e m u l s i f i e d i n t h e f o r m o f " c h o c o l a t e m o u s s e " e m u l s i o n s , so n a m e d
f o r t h e i r c o l o r a n d s e m i s o l i d consistency. T h e s e w a t e r - i n - o i l e m u l s i o n s w i t h
h i g h w a t e r c o n t e n t t e n d to b e q u i t e stable d u e to t h e strong s t a b i l i z i n g films
that are present. M o u s s e e m u l s i o n s increase t h e q u a n t i t y o f p o l l u t a n t a n d
are u s u a l l y v e r y m u c h m o r e viscous than t h e o i l itself.
A l l o f t h e p e t r o l e u m e m u l s i o n applications o r p r o b l e m s just d i s c u s s e d
have i n c o m m o n t h e same basic p r i n c i p l e s o f c o l l o i d science that g o v e r n t h e
nature, stability, a n d p r o p e r t i e s o f e m u l s i o n s . T h e w i d e s p r e a d i m p o r t a n c e o f
e m u l s i o n s i n general a n d scientific interest i n t h e i r f o r m a t i o n , stability, a n d
p r o p e r t i e s have p r e c i p i t a t e d a w e a l t h o f p u b l i s h e d l i t e r a t u r e o n t h e subject.
T h i s c h a p t e r p r o v i d e s an i n t r o d u c t i o n a n d is i n t e n d e d to c o m p l e m e n t t h e
o t h e r chapters i n this b o o k o n p e t r o l e u m e m u l s i o n s . A g o o d starting p o i n t
f o r f u r t h e r basic i n f o r m a t i o n is o n e o f the classic texts: B e c h e r ' s Emulsions:
Theory and Practice (4) o r S u m n e r ' s Clayton's Theory of Emulsions and
Schramm; Emulsions
Their Technical Treatment (5) a n d n u m e r o u s o t h e r books o n e m u l s i o n s (6-

11). M o s t g o o d c o l l o i d c h e m i s t r y texts c o n t a i n i n t r o d u c t o r y chapters o n
e m u l s i o n s (12-14), a n d some chapters i n specialist m o n o g r a p h s (15,16) give
m u c h m o r e d e t a i l e d treatment o f advances i n specific e m u l s i o n areas.
Emulsions as Colloidal Systems

D e f i n i t i o n a n d Classification o f E m u l s i o n s . C o l l o i d a l d r o p
lets (or particles o r b u b b l e s ) , as they are u s u a l l y d e f i n e d , have at least o n e
d i m e n s i o n b e t w e e n about 1 a n d 1000 n m . E m u l s i o n s are a s p e c i a l k i n d o f
c o l l o i d a l d i s p e r s i o n : o n e i n w h i c h a l i q u i d is d i s p e r s e d i n a c o n t i n u o u s l i q u i d
phase o f d i f f e r e n t c o m p o s i t i o n . T h e d i s p e r s e d phase is sometimes r e f e r r e d
to as t h e i n t e r n a l (disperse) phase, a n d t h e c o n t i n u o u s phase as t h e external
phase. E m u l s i o n s also f o r m a rather special k i n d o f c o l l o i d a l system i n that
the droplets o f t e n e x c e e d t h e size l i m i t o f 1000 n m . I n p e t r o l e u m e m u l s i o n s
one o f the l i q u i d s is aqueous, a n d t h e o t h e r is h y d r o c a r b o n a n d r e f e r r e d to as
o i l . T w o types o f e m u l s i o n are n o w r e a d i l y d i s t i n g u i s h e d i n p r i n c i p l e , d e
p e n d i n g u p o n w h i c h k i n d o f l i q u i d forms t h e c o n t i n u o u s phase ( F i g u r e 2):
1. o i l - i n - w a t e r (O/W) f o r o i l d r o p l e t s d i s p e r s e d i n w a t e r
2. w a t e r - i n - o i l (W/O) f o r w a t e r droplets d i s p e r s e d i n o i l
T h i s k i n d o f classification is n o t always a p p r o p r i a t e . F o r e x a m p l e , O/W/O

denotes a m u l t i p l e e m u l s i o n c o n t a i n i n g o i l d r o p l e t s d i s p e r s e d i n aqueous
droplets that are i n t u r n d i s p e r s e d i n a c o n t i n u o u s o i l phase. T h e type o f
e m u l s i o n that is f o r m e d depends u p o n a n u m b e r o f factors. I f t h e ratio o f
phase v o l u m e s is v e r y large o r v e r y s m a l l , t h e n t h e phase h a v i n g t h e s m a l l e r
v o l u m e is f r e q u e n t l y t h e d i s p e r s e d phase. I f t h e ratio is closer to 1, t h e n
Figure 2. The two simplest kinds of emulsions. The droplet sizes have been
greatly exaggerated.
Schramm; Emulsions
o t h e r factors d e t e r m i n e the o u t c o m e . T a b l e I lists some s i m p l e examples o f

p e t r o l e u m e m u l s i o n types.
T w o v e r y d i f f e r e n t b r o a d types o f c o l l o i d a l dispersions have b e e n d i s t i n
g u i s h e d since G r a h a m i n v e n t e d the t e r m " c o l l o i d " i n 1861. O r i g i n a l l y , c o l
loids w e r e s u b d i v i d e d i n t o l y o p h o b i c a n d l y o p h i l i c c o l l o i d s (if the d i s p e r s i o n
m e d i u m is aqueous t h e n the terms h y d r o p h o b i c a n d h y d r o p h i l i e , respec
tively, are used). L y o p h i l i c c o l l o i d s are f o r m e d spontaneously w h e n the t w o
phases are b r o u g h t together, because the d i s p e r s i o n is t h e r m o d y n a m i c a l l y
m o r e stable t h a n the o r i g i n a l separated state. T h e t e r m l y o p h i l i c is less
f r e q u e n t l y u s e d i n m o d e r n p r a c t i c e because m a n y o f the dispersions that
w e r e o n c e t h o u g h t o f as l y o p h i l i c are n o w r e c o g n i z e d as single-phase sys
tems i n w h i c h large m o l e c u l e s are d i s s o l v e d . L y o p h o b i c c o l l o i d s , w h i c h
i n c l u d e a l l p e t r o l e u m e m u l s i o n s other t h a n the m i c r o e m u l s i o n s , are not
f o r m e d spontaneously o n c o n t a c t o f the phases because they are t h e r m o d y
n a m i c a l l y unstable c o m p a r e d w i t h the separated states. T h e s e dispersions
c a n b e f o r m e d b y o t h e r means, h o w e v e r . M o s t p e t r o l e u m emulsions that w i l l
be e n c o u n t e r e d i n p r a c t i c e c o n t a i n o i l , w a t e r , a n d an e m u l s i f y i n g agent. T h e
e m u l s i f i e r may c o m p r i s e one o r m o r e o f the f o l l o w i n g : s i m p l e i n o r g a n i c
electrolytes, surfactants, m a c r o m o l e c u l e s , o r finely d i v i d e d solids. T h e
e m u l s i f y i n g agent may be n e e d e d to r e d u c e i n t e r f a c i a l t e n s i o n a n d a i d i n the
f o r m a t i o n o f the i n c r e a s e d i n t e r f a c i a l area w i t h a m i n i m u m o f m e c h a n i c a l
energy i n p u t , o r it m a y b e n e e d e d to f o r m a p r o t e c t i v e film at the d r o p l e t
surfaces that acts to p r e v e n t coalescence w i t h other d r o p l e t s . T h e s e aspects
w i l l b e discussed later; the r e s u l t i n g e m u l s i o n may w e l l have c o n s i d e r a b l e
stability as a metastable d i s p e r s i o n .
M o s t k i n d s o f e m u l s i o n s that w i l l b e e n c o u n t e r e d i n p r a c t i c e are l y o p h o
bic, metastable e m u l s i o n s . H o w e v e r , t h e r e r e m a i n some grey areas i n w h i c h
the d i s t i n c t i o n b e t w e e n l y o p h i l i c a n d l y o p h o b i c dispersions is not c o m
p l e t e l y clear. A s p e c i a l class o f aggregated surfactant m o l e c u l e s t e r m e d
" m i c e l l e s " a n d the m i c r o e m u l s i o n s o f e x t r e m e l y s m a l l d r o p l e t size are u s u
ally b u t not always c o n s i d e r e d to be l y o p h i l i c , stable, c o l l o i d a l dispersions
and w i l l be d i s c u s s e d separately.
Stability. A c o n s e q u e n c e o f the s m a l l d r o p l e t size a n d p r e s e n c e o f an

i n t e r f a c i a l film o n the droplets i n e m u l s i o n s is that q u i t e stable dispersions o f
these species c a n be m a d e . T h a t is, the s u s p e n d e d d r o p l e t s d o not settle out
o r float r a p i d l y , a n d the d r o p l e t s d o not coalesce q u i c k l y . S o m e use o f the
t e r m stability has already b e e n m a d e w i t h o u t d e f i n i t i o n .
C o l l o i d a l species c a n c o m e together i n v e r y d i f f e r e n t ways. I n the d e f i n i
t i o n o f e m u l s i o n stability, stability is c o n s i d e r e d against three d i f f e r e n t
processes: c r e a m i n g (sedimentation), aggregation, a n d coalescence. C r e a m
i n g is the opposite o f s e d i m e n t a t i o n a n d results f r o m a density d i f f e r e n c e
b e t w e e n the t w o l i q u i d phases. I n aggregation t w o o r m o r e droplets c l u m p
together, t o u c h i n g o n l y at c e r t a i n p o i n t s , a n d w i t h v i r t u a l l y no change i n
Schramm; Emulsions
total surface area. A g g r e g a t i o n is sometimes r e f e r r e d to as flocculation o r

c o a g u l a t i o n . I n coalescence t w o o r m o r e d r o p l e t s fuse t o g e t h e r to f o r m a
single larger u n i t w i t h a r e d u c e d total surface area.
I n aggregation t h e species r e t a i n t h e i r i d e n t i t y b u t lose t h e i r k i n e t i c
i n d e p e n d e n c e because the aggregate moves as a single u n i t . A g g r e g a t i o n o f
droplets m a y l e a d to coalescence a n d the f o r m a t i o n o f larger droplets u n t i l
the phases b e c o m e separated. I n coalescence, o n the o t h e r h a n d , t h e o r i g i
n a l species lose t h e i r i d e n t i t y a n d b e c o m e part o f a n e w species. K i n e t i c
stability c a n thus have d i f f e r e n t meanings. A n e m u l s i o n c a n b e k i n e t i c a l l y
stable w i t h respect to coalescence b u t unstable w i t h respect to aggregation.
O r , a system c o u l d b e k i n e t i c a l l y stable w i t h respect t o aggregation b u t
unstable w i t h respect to s e d i m e n t a t i o n o r flotation.
I n s u m m a r y , l y o p h o b i c e m u l s i o n s are t h e r m o d y n a m i c a l l y unstable b u t
may b e relatively stable i n a k i n e t i c sense. S t a b i l i t y must b e u n d e r s t o o d i n
terms o f a clearly d e f i n e d process.
M i c r o e m u l s i o n s . I n some systems t h e a d d i t i o n o f a f o u r t h c o m p o
nent, a cosurfactant, to a n o i l - w a t e r - s u r f a c t a n t system c a n cause the i n t e r f a -
c i a l t e n s i o n to d r o p t o near-zero values, easily o n t h e o r d e r o f 10~ to 1(Γ* 3
m N / m ; l o w i n t e r f a c i a l t e n s i o n allows spontaneous o r n e a r l y spontaneous

e m u l s i f i c a t i o n to v e r y s m a l l d r o p l e t sizes, c a . 10 n m o r s m a l l e r . T h e droplets
c a n b e so s m a l l that they scatter little l i g h t ; t h e e m u l s i o n s appear to b e
transparent a n d d o n o t break o n s t a n d i n g o r c e n t r i f u g i n g . U n l i k e coarse
e m u l s i o n s , these m i c r o e m u l s i o n s are usually t h o u g h t to b e t h e r m o d y n a m i
cally stable. T h e t h e r m o d y n a m i c stability is f r e q u e n t l y a t t r i b u t e d to t r a n
sient negative i n t e r f a c i a l tensions, b u t this hypothesis a n d t h e q u e s t i o n o f
w h e t h e r m i c r o e m u l s i o n s are r e a l l y l y o p h i l i c o r l y o p h o b i c dispersions are
areas o f some d i s c u s s i o n i n t h e literature (17). A s a p r a c t i c a l matter,
m i c r o e m u l s i o n s c a n b e f o r m e d , have some special qualities, a n d c a n have
i m p o r t a n t applications.
M i c r o e m u l s i o n s c a n f o r m t h e basis f o r a n e n h a n c e d o i l r e c o v e r y ( E O R )
process (18-20). I n an o i l - c o n t a i n i n g reservoir, t h e relative o i l a n d w a t e r
saturations d e p e n d u p o n t h e d i s t r i b u t i o n o f p o r e sizes i n t h e r o c k as f o l l o w s .
T h e c a p i l l a r y pressure ( F ) , o r pressure d i f f e r e n c e across a n o i l - w a t e r i n t e r
c
face s p a n n i n g a p o r e , is
P = 2y cos θ I r
c p (1)
w h e r e 7 is the o i l - w a t e r i n t e r f a c i a l t e n s i o n ; θ is t h e contact angle, w h i c h is

the angle m e a s u r e d t h r o u g h t h e w a t e r phase at t h e p o i n t o f o i l - w a t e r - r o c k
contact; a n d r is t h e p o r e r a d i u s . T h e basis f o r this e q u a t i o n is d i s c u s s e d
p
f u r t h e r i n a later section. I n a n i d e a l i z e d w a t e r - w e t reservoir, t h e i n t e r f a c i a l

t e n s i o n is fixed at some v a l u e , a n d t h e contact angle is z e r o . A n analogy c a n
be d r a w n w i t h t h e rise o f w a t e r i n c a p i l l a r y tubes o f d i f f e r i n g r a d i i . I n a
Schramm; Emulsions
E M U L S I O N S I N T H E P E T R O L E U M INDUSTRY
reservoir c o n s i s t i n g o f s u c h c a p i l l a r y tubes that c o n t a i n w a t e r a n d o i l , w a t e r

w i l l b e i m b i b e d most strongly i n t o the smallest radius pores, d i s p l a c i n g any
o i l present i n t h e m , u n t i l t h e hydrostatic a n d c a p i l l a r y pressures i n t h e
system balance. T h e largest pores w i l l r e t a i n h i g h o i l contents. N o w as w a t e r
is i n j e c t e d d u r i n g a secondary r e c o v e r y process, the a p p l i e d w a t e r pressure
increases a n d the larger pores w i l l i m b i b e m o r e water, d i s p l a c i n g o i l , w h i c h
may b e r e c o v e r e d at p r o d u c i n g w e l l s . T h e r e is a p r a c t i c a l l i m i t t o t h e extent
that t h e a p p l i e d pressure c a n b e c h a n g e d b y p u m p i n g w a t e r i n t o a reservoir,
h o w e v e r , so that after w a t e r - f l o o d i n g some r e s i d u a l o i l w i l l still b e left i n the
f o r m o f o i l ganglia t r a p p e d i n the larger pores w h e r e the viscous forces o f t h e
d r i v i n g w a t e r - f l o o d c o u l d n o t c o m p l e t e l y o v e r c o m e the c a p i l l a r y forces h o l d
ing the o i l i n place.
T h e ratio o f viscous forces t o c a p i l l a r y forces correlates w e l l w i t h r e s i d
ual o i l saturation a n d is t e r m e d t h e c a p i l l a r y n u m b e r (N ). O n e f o r m u l a t i o n
c
o f t h e c a p i l l a r y n u m b e r is
N = 7]v/y
c (2)
w h e r e η a n d υ are the viscosity a n d v e l o c i t y , respectively, o f the d i s p l a c i n g

fluid; a n d y is t h e i n t e r f a c i a l t e n s i o n . T h e f u n c t i o n a l f o r m o f t h e c o r r e l a t i o n
is i l l u s t r a t e d i n F i g u r e 3 . D u r i n g w a t e r - f l o o d i n g , N is about 10~ , a n d at t h e
c
6
10" 6
10" 5
10" 4
10" 3
10" 2
Capillary Number
Figure 3. A generalized capillary number correlation. (Courtesy of K. Taylor,

Petroleum Recovery Institute, Calgary.)
Schramm; Emulsions
e n d o f the w a t e r - f l o o d the r e s i d u a l o i l saturation is still a r o u n d 4 5 % . H o w

c o u l d a tertiary r e c o v e r y process b e d e s i g n e d so that the r e m a i n i n g o i l c o u l d
be r e c o v e r e d ? L o w e r i n g the r e s i d u a l o i l saturation r e q u i r e s i n c r e a s i n g the
c a p i l l a r y n u m b e r . T h i s increase c o u l d be d o n e b y r a i s i n g the viscous forces,
that is, viscosity a n d v e l o c i t y , b u t i n p r a c t i c e the d e s i r e d o r d e r s - o f - m a g n i -
t u d e increase w i l l not be a c h i e v e d . B u t , a d d i n g a suitable surfactant a n d
cosurfactant to the w a t e r w i l l decrease the i n t e r f a c i a l t e n s i o n f r o m about 30
m N / m b y 4 orders o f m a g n i t u d e a n d t h e r e b y increase the c a p i l l a r y n u m b e r
to about 10" . 2
T h e m i c e l l e s present also h e l p to s o l u b i l i z e the released o i l d r o p l e t s ;

h e n c e , this process is sometimes r e f e r r e d to as m i c e l l a r flooding. T h e e m u l
sions c a n b e f o r m u l a t e d to have m o d e r a t e l y h i g h viscosities that h e l p to
achieve a m o r e u n i f o r m d i s p l a c e m e n t front i n the reservoir; this u n i f o r m
f r o n t gives i m p r o v e d sweep efficiency. T h u s , a n u m b e r o f factors c a n b e
adjusted w h e n u s i n g a m i c r o e m u l s i o n system f o r e n h a n c e d o i l recovery.
T h e s e are discussed i n d e t a i l i n C h a p t e r 7.
M a k i n g E m u l s i o n s . M u c h o f this c h a p t e r is c o n c e r n e d w i t h e m u l
s i o n p r o p e r t i e s a n d stability, a n d as a p r a c t i c a l matter chemists f r e q u e n t l y
have to c o n t e n d w i t h a l r e a d y - f o r m e d e m u l s i o n s . N e v e r t h e l e s s , a f e w c o m
ments o n h o w e m u l s i o n s m a y b e m a d e are a p p r o p r i a t e . T h e b r e a k i n g o f
e m u l s i o n s w i l l be discussed later.
E m u l s i o n s o f any significant stability c o n t a i n o i l , water, a n d at least one
e m u l s i f y i n g agent. T h e e m u l s i f y i n g agent m a y l o w e r i n t e r f a c i a l t e n s i o n a n d
t h e r e b y m a k e it easier to create s m a l l d r o p l e t s . A n o t h e r e m u l s i f y i n g agent
may b e n e e d e d to stabilize the s m a l l droplets so that t h e y d o not coalesce to
f o r m larger d r o p l e t s , o r e v e n separate out as a b u l k phase. Just a straightfor
w a r d casual m i x i n g o f these c o m p o n e n t s s e l d o m , h o w e v e r , p r o d u c e s an
e m u l s i o n that persists for any l e n g t h o f t i m e . I n the classical m e t h o d o f
e m u l s i o n p r e p a r a t i o n , the e m u l s i f y i n g agent is d i s s o l v e d i n t o the phase i n
w h i c h it is most s o l u b l e , after w h i c h the s e c o n d phase is a d d e d , a n d the
w h o l e m i x t u r e is v i g o r o u s l y agitated. T h e agitation is c r u c i a l to p r o d u c i n g
sufficiently s m a l l d r o p l e t s , a n d f r e q u e n t l y , after an i n i t i a l m i x i n g , a s e c o n d
m i x i n g w i t h v e r y h i g h a p p l i e d m e c h a n i c a l shear forces is r e q u i r e d . T h i s
latter m i x i n g carrbe p r o v i d e d b y a p r o p e l l e r - s t y l e m i x e r , b u t m o r e c o m m o n l y
a c o l l o i d m i l l o r u l t r a s o u n d generator is e m p l o y e d .
A m e t h o d r e q u i r i n g m u c h less m e c h a n i c a l energy uses phase i n v e r s i o n
(see also the d i s c u s s i o n o f phase i n v e r s i o n t e m p e r a t u r e i n the section " E m u l
s i f y i n g A g e n t s " ) . F o r example, i f u l t i m a t e l y a W / O e m u l s i o n is d e s i r e d , t h e n
a coarse O / W e m u l s i o n is first p r e p a r e d b y the a d d i t i o n o f m e c h a n i c a l
energy, a n d the o i l content is progressively i n c r e a s e d . A t some v o l u m e
f r a c t i o n above 6 0 - 7 0 % , the e m u l s i o n w i l l s u d d e n l y i n v e r t a n d p r o d u c e a
W / O e m u l s i o n o f m u c h s m a l l e r w a t e r d r o p l e t sizes t h a n w e r e the o i l d r o p l e t s
i n the o r i g i n a l O / W e m u l s i o n .
Schramm; Emulsions
Physical Characteristics of Emulsions

A p p e a r a n c e . N o t a l l e m u l s i o n s e x h i b i t t h e classical " m i l k y " o p a q u e
ness w i t h w h i c h they are u s u a l l y associated. A t r e m e n d o u s range o f appear
ances is possible, d e p e n d i n g u p o n the d r o p l e t sizes a n d t h e d i f f e r e n c e i n
refractive i n d i c e s b e t w e e n t h e phases. A n e m u l s i o n c a n b e transparent i f
e i t h e r t h e refractive i n d e x o f each phase is t h e same, o r alternatively, i f t h e
d i s p e r s e d phase is m a d e u p o f droplets that are s u f f i c i e n t l y s m a l l c o m p a r e d
with the wavelength of the illuminating light. Thus an O/W microemulsion
o f e v e n a c r u d e o i l i n w a t e r may b e transparent. I f t h e droplets are o f t h e
o r d e r o f l - μ π ι d i a m e t e r , a d i l u t e O / W e m u l s i o n w i l l take o n a s o m e w h a t
m i l k y - b l u e cast; i f t h e droplets are v e r y m u c h larger, the o i l phase w i l l
b e c o m e q u i t e d i s t i n g u i s h a b l e a n d apparent.
P h y s i c a l l y t h e nature o f the s i m p l e e m u l s i o n types c a n b e d e t e r m i n e d b y
m e t h o d s s u c h as
• Texture. T h e texture o f an e m u l s i o n f r e q u e n t l y reflects that o f

the external phase. T h u s O / W e m u l s i o n s u s u a l l y f e e l w a t e r y o r
c r e a m y , a n d W / O e m u l s i o n s f e e l o i l y o r greasy. T h i s d i s t i n c
t i o n b e c o m e s less e v i d e n t as the e m u l s i o n viscosity increases,
so that a v e r y viscous O / W e m u l s i o n m a y f e e l o i l y .
• Mixing. A n e m u l s i o n r e a d i l y mixes w i t h a l i q u i d that is m i s c i
ble w i t h the c o n t i n u o u s phase. T h u s , m i l k (O/W) c a n b e d i
l u t e d w i t h water, a n d mayonnaise (W/O) c a n b e d i l u t e d w i t h
o i l . U s u a l l y , a n e m u l s i o n that retains a u n i f o r m a n d m i l k y
appearance w h e n greatly d i l u t e d is m o r e stable t h a n o n e that
aggregates u p o n d i l u t i o n (15).
• Dyeing. E m u l s i o n s are most r e a d i l y a n d consistently c o l o r e d

b y dyes s o l u b l e i n t h e c o n t i n u o u s phase.
• Conductance. O / W e m u l s i o n s u s u a l l y have a v e r y h i g h spe
cific c o n d u c t a n c e , l i k e that o f t h e aqueous phase itself, b u t
W / O e m u l s i o n s have a v e r y l o w specific c o n d u c t a n c e . A s i m p l e
test apparatus is d e s c r i b e d i n r e f e r e n c e 15.
• Inversion. I f a n e m u l s i o n is v e r y c o n c e n t r a t e d , i t w i l l p r o b a
bly i n v e r t w h e n d i l u t e d w i t h a d d i t i o n a l i n t e r n a l phase.
• Fluorescence. I f t h e o i l phase fluoresces, then fluorescence

m i c r o s c o p y c a n b e u s e d to d e t e r m i n e the e m u l s i o n type as
l o n g as t h e d r o p l e t sizes are larger t h a n the microscope's l i m i t
o f r e s o l u t i o n (>0.5 μ π ι ) .
E m u l s i o n s d o n o t always o c c u r i n t h e i d e a l i z e d f o r m o f droplets o f one

phase d i s p e r s e d i n another. T h e o c c u r r e n c e o f m u l t i p l e e m u l s i o n s , o f t h e
Schramm; Emulsions
types O/W/O a n d W / O A V , has already b e e n m e n t i o n e d . P e t r o l e u m e m u l

sions m a y also o c c u r w i t h i n another type o f c o l l o i d a l d i s p e r s i o n . F o r e x a m
p l e , i n a gas-flooding e n h a n c e d o i l r e c o v e r y process o n e o f t h e ways t o
i m p r o v e t h e areal sweep efficiency, that is, to m a x i m i z e t h e a m o u n t o f t h e
r e s e r v o i r c o n t a c t e d b y i n j e c t e d fluids, is t o inject t h e gas as p a r t o f a f o a m .
H o w e v e r , most s u c h foams are d e s t a b i l i z e d b y contact w i t h e v e n s m a l l
amounts o f c r u d e o i l . T h e m e c h a n i s m o f d e s t a b i l i z a t i o n appears (21 ) t o
i n v o l v e e m u l s i f i c a t i o n o f the o i l i n t o droplets that are s m a l l e n o u g h to p e r m i t
t h e i r passage i n s i d e t h e foam's l a m e l l a r s t r u c t u r e . S u c h e m u l s i f i e d o i l d r o p
lets are s h o w n i n F i g u r e 4. O n c e i n s i d e t h e f o a m l a m e l l a e , t h e o i l d r o p l e t s
have a d e s t a b i l i z i n g effect o n t h e f o a m b y p e n e t r a t i n g t h r o u g h a n d p o s s i b l y
s p r e a d i n g over t h e aqueous-gas interface. T h e l i m i t i n g step, h o w e v e r , is
a p p a r e n t l y the e m u l s i f i c a t i o n a n d i m b i b i t i o n o f o i l i n t o t h e f o a m .
D r o p l e t Sizes. A s stated p r e v i o u s l y , c o l l o i d a l d r o p l e t s are b e t w e e n

about 10" a n d 1 μ π ι i n d i a m e t e r , a n d i n p r a c t i c e , e m u l s i o n droplets are
3
o f t e n larger (e.g., t h e fat droplets i n m i l k ) . I n fact, e m u l s i o n droplets u s u a l l y
Figure 4. Photomicrograph of an enhanced oil recovery process foam contain

ing emulsified crude-oil droplets. The droplets have traveled within the narrow
lamellae to accumulate and sometimes coalesce in the plateau borders of the
foam, where they are held preferentially. The presence of such emulsified oil
droplets in the foam structure has a destabilizing effect on the foam.
Schramm; Emulsions
have diameters greater t h a n 0.2 μπι a n d m a y b e larger t h a n 50 μ ι η . E m u l

sion stability is not necessarily a f u n c t i o n o f d r o p l e t size, a l t h o u g h t h e r e m a y
b e a n o p t i m u m size f o r a n i n d i v i d u a l e m u l s i o n type. C h a r a c t e r i z i n g a n
e m u l s i o n i n terms o f a g i v e n d r o p l e t size is v e r y c o m m o n b u t g e n e r a l l y
i n a p p r o p r i a t e because t h e r e is i n e v i t a b l y a size d i s t r i b u t i o n . T h e size d i s t r i
b u t i o n is u s u a l l y r e p r e s e n t e d b y a h i s t o g r a m o f sizes, o r , i f there are suffi
cient data, a d i s t r i b u t i o n f u n c t i o n .
I n some e m u l s i o n s , a d r o p l e t size d i s t r i b u t i o n that is h e a v i l y w e i g h t e d
t o w a r d t h e s m a l l e r sizes w i l l represent t h e most stable e m u l s i o n . I n s u c h
cases changes i n the size d i s t r i b u t i o n c u r v e w i t h t i m e y i e l d a measure o f the
stability o f the e m u l s i o n s . T h e d r o p l e t size d i s t r i b u t i o n also has a n i m p o r t a n t
i n f l u e n c e o n the viscosity. F o r electrostatically o r sterically i n t e r a c t i n g d r o p
lets, e m u l s i o n viscosity w i l l b e h i g h e r w h e n droplets are smaller. T h e viscos
ity w i l l also b e h i g h e r w h e n the d r o p l e t sizes are relatively h o m o g e n e o u s ,
that is, w h e n t h e d r o p l e t size d i s t r i b u t i o n is n a r r o w rather t h a n w i d e (4).
I f t h e d r o p l e t size is large e n o u g h , t h e n o p t i c a l m i c r o s c o p y c a n b e u s e d
to d e t e r m i n e t h e size a n d size d i s t r i b u t i o n . E m u l s i o n s w i t h somewhat s m a l l
er d r o p l e t sizes c a n b e c h a r a c t e r i z e d b y u s i n g cryogenic-stage s c a n n i n g
e l e c t r o n m i c r o s c o p y . I f t h e e m u l s i o n c o n c e n t r a t i o n is not too h i g h , a n d the
droplets are v e r y s m a l l , l i g h t scattering c a n y i e l d d r o p l e t size i n f o r m a t i o n .
W h e n a b e a m o f l i g h t enters a n e m u l s i o n , some l i g h t is a b s o r b e d , some is
scattered, a n d some is t r a n s m i t t e d . M a n y d i l u t e , fine e m u l s i o n s s h o w a
noticeable t u r b i d i t y g i v e n b y
I //
t 0 =expM) (3)
w h e r e I is the i n t e n s i t y o f t h e t r a n s m i t t e d b e a m , I is the i n t e n s i t y o f the

t 0
i n c i d e n t b e a m , τ is t u r b i d i t y , a n d I is t h e l e n g t h o f the p a t h t h r o u g h the
s a m p l e . F r o m R a y l e i g h t h e o r y , t h e i n t e n s i t y o f l i g h t scattered f r o m e a c h
d r o p l e t d e p e n d s largely o n its size a n d shape a n d o n t h e d i f f e r e n c e i n
refractive i n d e x b e t w e e n the d r o p l e t a n d the m e d i u m . F o r a n e m u l s i o n , e a c h
s p h e r i c a l d r o p l e t scatters l i g h t h a v i n g a n i n t e n s i t y l at a distance χ f r o m t h e
d
d r o p l e t , a c c o r d i n g to t h e f o l l o w i n g r e l a t i o n s h i p :
I /I ocr /x K*
d 0
e 2
(4)
w h e r e λ is t h e w a v e l e n g t h o f t h e l i g h t a n d r is t h e d r o p l e t radius.
T h e scattering i n t e n s i t y is p r o p o r t i o n a l to l/λ , so b l u e l i g h t ( λ = 4 5 0
4
n m ) is scattered m u c h m o r e t h a n r e d l i g h t ( λ = 650 n m ) . W i t h i n c i d e n t w h i t e
light, a d i l u t e e m u l s i o n o f O . l - 1 - μ π ι size droplets w i l l , therefore, t e n d t o
appear b l u e w h e n v i e w e d at right angles t o t h e i n c i d e n t l i g h t b e a m . I f t h e
droplets are s m a l l e r t h a n 5 0 n m o r so, the e m u l s i o n w i l l appear to b e
transparent.
Schramm; Emulsions
T h e s e approaches to d e t e r m i n i n g d r o p l e t size d i s t r i b u t i o n s are d i s

c u s s e d i n d e t a i l i n C h a p t e r 3.
Conductivity. Conductivity can be used to distinguish O/W f r o m

W / O e m u l s i o n s b e c a u s e the c o n d u c t i v i t y is v e r y h i g h w h e n t h e aqueous
phase is c o n t i n u o u s a n d c o n d u c t i v i t y is v e r y l o w w h e n o i l is t h e c o n t i n u o u s
phase. O f the n u m e r o u s equations p r o p o s e d (4) to d e s c r i b e t h e c o n d u c t i v i t y
o f e m u l s i o n s (#c ), t w o are c i t e d h e r e f o r i l l u s t r a t i o n . I f t h e c o n d u c t i v i t y o f
E
the d i s p e r s e d phase ( K ) is m u c h s m a l l e r t h a n that o f t h e c o n t i n u o u s phase

d
(fCc), * C » *D>
_8KC(2-0)(1-0) ( 5 )
E
(4 + φ ) ( 4 - φ )
w h e r e φ is the dispersed-phase v o l u m e f r a c t i o n . If, o n t h e o t h e r h a n d , t h e

c o n d u c t i v i t y o f t h e d i s p e r s e d phase (#c ) is m u c h greater t h a n that o f t h e
D
c o n t i n u o u s phase ( K ) , K <K K ,
C C D
κ (1
0 + φ)(2 + φ)
(1-0(2-φ)
F u r t h e r discussion o f emulsion conductivity a n d some practical exam

ples f o r e m u l s i o n s flowing i n p i p e l i n e s are g i v e n i n C h a p t e r 5 .
Rheology. Bulk Viscosity Properties. T h e rheological properties

o f a n e m u l s i o n are v e r y i m p o r t a n t . H i g h viscosity m a y b e t h e reason that a n
e m u l s i o n is t r o u b l e s o m e , a resistance to flow that must b e dealt w i t h , o r a
d e s i r a b l e p r o p e r t y f o r w h i c h a n e m u l s i o n is f o r m u l a t e d . T h e s i m p l e s t d e
s c r i p t i o n applies to N e w t o n i a n b e h a v i o r i n l a m i n a r flow. T h e viscosity, rj, is
g i v e n i n t e r m s o f t h e shear stress, τ , a n d shear rate, 7, b y :
τ = 177 (7)
w h e r e 17 has units o f m i l l i p a s c a l seconds. M a n y c o l l o i d a l d i s p e r s i o n s , i n c l u d

i n g t h e m o r e c o n c e n t r a t e d e m u l s i o n s , d o n o t o b e y the N e w t o n i a n e q u a t i o n .
F o r n o n - N e w t o n i a n fluids, t h e coefficient o f viscosity is n o t a constant, b u t is
i t s e l f a f u n c t i o n o f t h e shear rate, thus:
7=17(7)7 ( ) 8
A c o n v e n i e n t w a y to s u m m a r i z e t h e flow p r o p e r t i e s o f fluids is b y
p l o t t i n g flow curves o f shear stress versus shear rate (τ versus 7 ) . T h e s e
Schramm; Emulsions
curves c a n be c a t e g o r i z e d i n t o several r h e o l o g i c a l classifications. E m u l s i o n s

are f r e q u e n t l y p s e u d o p l a s t i c : A s shear rate increases, viscosity decreases.
T h i s k i n d o f flow b e h a v i o r is also t e r m e d s h e a r - t h i n n i n g . A n e m u l s i o n may
also e x h i b i t a y i e l d stress, that is, the shear rate (flow) remains z e r o u n t i l a
t h r e s h o l d shear stress is reached—the y i e l d stress ( τ ) — t h e n p s e u d o p l a s t i c o r
γ
N e w t o n i a n flow begins. P s e u d o p l a s t i c flow that is t i m e d e p e n d e n t is t e r m e d

t h i x o t r o p i c . T h a t is, at constant a p p l i e d shear rate, viscosity decreases, a n d i n
a flow c u r v e hysteresis occurs. Several o t h e r r h e o l o g i c a l classifications are
c o v e r e d i n the G l o s s a r y : dilatancy, rheopexy, a n d rheomalaxi^. E v e n viscos
ity i t s e l f is r e p r e s e n t e d i n m a n y ways, as s h o w n i n T a b l e I I .
S o m e v e r y u s e f u l d e s c r i p t i o n s o f e x p e r i m e n t a l t e c h n i q u e s have b e e n
g i v e n b y W h o r l o w (22) a n d others (23, 24). V e r y o f t e n m e a s u r e m e n t s are
m a d e w i t h an e m u l s i o n sample p l a c e d i n the annulus b e t w e e n t w o c o n c e n
t r i c c y l i n d e r s . T h e shear stress is c a l c u l a t e d f r o m the m e a s u r e d t o r q u e
r e q u i r e d to m a i n t a i n a g i v e n r o t a t i o n a l v e l o c i t y o f o n e c y l i n d e r w i t h respect
to the other. K n o w i n g the geometry, the effective shear rate c a n b e c a l c u
l a t e d f r o m the r o t a t i o n a l v e l o c i t y . O n e reason for the relative lack o f r h e o
l o g i c a l data f o r e m u l s i o n s , c o m p a r e d w i t h that f o r o t h e r c o l l o i d a l systems, is
the d i f f i c u l t y associated w i t h p e r f o r m i n g the measurements i n these sys
tems. A s suggested b y F i g u r e 5, for a p r a c t i c a l O / W e m u l s i o n , the s a m p l e
m a y c o n t a i n s u s p e n d e d particles i n a d d i t i o n to the o i l d r o p l e t s . I n attempt
i n g to c o n d u c t a m e a s u r e m e n t , a n u m b e r o f changes m a y o c c u r i n the sample
Table II. Glossary of Bulk Viscosity Terms

Term Symbol Explanation
Absolute viscosity η η = τ/7 and can be traced to fundamental units
independent of the type of instrument
Apparent viscosity T|APP η ρρ = τ/7 but as determined for a non-

Α
Newtonian fluid, usually by a method suitable

only for Newtonian fluids
Differential viscosity ηϋ = dT/d"y
Specific increase
in viscosity η$ρ nsp = nRei - 1
Intrinsic viscosity [η] [η] = lim -»o lim ^ ^sv/C

C 0
[η] = lim ->o lim γ_> (1/C) In n j

C 0 Re
Reduced viscosity η Red nRed = Tjsp/C
Relative viscosity nRei = η/ηο

T|o = viscosity of the pure solvent or dispersion
medium
Schramm; Emulsions
c h a m b e r that make the measurements i r r e p r o d u c i b l e a n d not representative

o f t h e o r i g i n a l e m u l s i o n (25). T h e s e changes m a y i n c l u d e
• creaming o f the droplets, causing a n o n u n i f o r m distribution

w i t h i n t h e c h a m b e r , o r e v e n r e m o v a l o f a l l droplets i n t o a n
u p p e r phase away f r o m t h e r e g i o n i n w h i c h measurements are
made
• c e n t r i f u g a l separation o f o i l , water, a n d s o l i d phases, m a k i n g

the e m u l s i o n r a d i a l l y i n h o m o g e n e o u s , a n d p o s s i b l y b r e a k i n g
the e m u l s i o n
• s h e a r - i n d u c e d coalescence o r finer d i s p e r s i o n o f d r o p l e t s ,
c h a n g i n g t h e p r o p e r t i e s o f t h e sample
• s e d i m e n t a t i o n o f the solids, c a u s i n g a n o n u n i f o r m d i s t r i b u t i o n
w i t h i n t h e c h a m b e r , o r even r e m o v a l o f a l l solids f r o m t h e
r e g i o n i n w h i c h measurements are m a d e
It is f r e q u e n t l y desirable to b e able to d e s c r i b e e m u l s i o n viscosity i n

terms o f t h e viscosity o f t h e c o n t i n u o u s phase (%) a n d t h e a m o u n t o f
e m u l s i f i e d m a t e r i a l . A v e r y large n u m b e r o f equations have b e e n a d v a n c e d
f o r e s t i m a t i n g suspension (or e m u l s i o n , etc.) viscosities. M o s t o f these are
e m p i r i c a l extensions o f E i n s t e i n ' s e q u a t i o n f o r a d i l u t e suspension o f
spheres:
η=η (1
0 + 2.5φ) (9)
Figure 5. Some rheological measurement problems that may be encountered

with practical oil-field emulsions. Initially, the O/W sample contained in the
cylinders on the left may be homogeneous, containing oil droplets (·), fine
particles (—), and large particles (o). After some time, the sample may become
quite stratified, as shown at right.
Schramm; Emulsions
w h e r e η is the m e d i u m viscosity a n d φ is the dispersed-phase v o l u m e

0
f r a c t i o n a n d is <1. F o r e x a m p l e , the e m p i r i c a l equations t y p i c a l l y have the

f o r m (4):
η = %(1 + α φ 0 + αφ λ
2
+ αφ2
3
4- ···) (10)
w h e r e the a s are e m p i r i c a l constants, a n d the e m p i r i c a l equations may

i n c l u d e other t e r m s , as i n the T h o m a s e q u a t i o n ,
η = + 2 . 5 φ + 1 O . 5 0 + 0.00273 exp (16.60) ]

2
(11)
T h e s e equations assume N e w t o n i a n b e h a v i o r , o r at least a p p l y to the N e w t o

n i a n r e g i o n o f a flow c u r v e , a n d they usually a p p l y i f the droplets are not too
large a n d i f t h e r e are no strong electrostatic interactions. A m o r e d e t a i l e d
treatment o f these relationships is given i n C h a p t e r 4.
E m u l s i o n s c a n show v a r y i n g r h e o l o g i c a l , o r viscosity, behaviors. S o m e
times these p r o p e r t i e s are d u e to the e m u l s i f i e r o r o t h e r agents i n the
e m u l s i o n . H o w e v e r , i f the i n t e r n a l phase has a s u f f i c i e n t l y h i g h v o l u m e
f r a c t i o n (typically a n y w h e r e f r o m 10 to 50%) the e m u l s i o n viscosity i n
creases because o f d r o p l e t " c r o w d i n g " or s t r u c t u r a l viscosity a n d b e c o m e s
n o n - N e w t o n i a n . T h e m a x i m u m v o l u m e f r a c t i o n possible for an i n t e r n a l
phase made u p o f u n i f o r m , i n c o m p r e s s i b l e spheres is 74%, a l t h o u g h e m u l
sions w i t h an i n t e r n a l v o l u m e f r a c t i o n o f 9 9 % have b e e n m a d e (15). F i g u r e 6
shows h o w e m u l s i o n viscosity tends to v a r y w i t h v o l u m e f r a c t i o n ; the d r o p i n
viscosity at φ = 0.74 signifies i n v e r s i o n . A t this p o i n t the dispersed-phase
v o l u m e f r a c t i o n b e c o m e s 0.26, i n this e x a m p l e , a n d the l o w e r value o f φ is
r e f l e c t e d b y a m u c h l o w e r viscosity. I f i n v e r s i o n does not o c c u r , t h e n the
viscosity continues to increase. T h i s c o n d i t i o n is true f o r b o t h W / O a n d O / W
types.
A g r a p h i c a n d i m p o r t a n t example is f u r n i s h e d b y the o i l s p i l l " c h o c o l a t e
m o u s s e " e m u l s i o n s f o r m e d w h e n c r u d e o i l spills i n t o seawater. T h e s e w a t e r -
i n - o i l e m u l s i o n s have h i g h w a t e r contents that may e x c e e d 7 4 % a n d r e a c h φ
= 0.80 o r m o r e w i t h o u t i n v e r t i n g . A s t h e i r c o m m o n n a m e i m p l i e s , these
mousse e m u l s i o n s not o n l y h a e viscosities that are m u c h h i g h e r t h a n the
,r
o r i g i n a l c r u d e o i l b u t can b e c o m e s e m i s o l i d . W i t h i n c r e a s i n g t i m e after a
s p i l l , these e m u l s i o n s w e a t h e r (the o i l b e c o m e s d e p l e t e d i n its l o w e r b o i l i n g
fractions), a n d a p p a r e n t l y the e m u l s i o n s b e c o m e m o r e stable, m o r e s o l i d
l i k e , a n d c o n s i d e r a b l y m o r e d i f f i c u l t to h a n d l e a n d break.
Interfacial Viscosity. T h e f o r e g o i n g d i s c u s s i o n o f r h e o l o g y has dealt

w i t h the b u l k viscosity p r o p e r t i e s . A closely r e l a t e d a n d v e r y i m p o r t a n t
p r o p e r t y is the i n t e r f a c i a l viscosity, w h i c h c a n be t h o u g h t o f as the t w o -
d i m e n s i o n a l e q u i v a l e n t o f b u l k viscosity, operative i n the o i l - w a t e r i n t e r f a -
c i a l r e g i o n . A s d r o p l e t s i n an e m u l s i o n a p p r o a c h each other, the t h i n n i n g o f
Schramm; Emulsions
Inversion at
0 0.2 0.4 0.6 0.8 1.0
Volume Fraction of Oil

Figure 6. The influence of volume fraction on the emulsion type and viscosity of
a model emulsion. (Reproduced with permission from reference 4. Copyright
1965 Robert E. Krieger, Inc.)
the films b e t w e e n t h e droplets, a n d t h e i r resistance to r u p t u r e , are t h o u g h t

to b e o f great i m p o r t a n c e to t h e u l t i m a t e stability o f the e m u l s i o n . T h u s , a
h i g h i n t e r f a c i a l viscosity can p r o m o t e e m u l s i o n stability b y r e t a r d i n g the rate
o f d r o p l e t coalescence, as discussed i n later sections. F u r t h e r details o n the
p r i n c i p l e s , m e a s u r e m e n t , a n d applications to e m u l s i o n stability o f i n t e r f a c i a l
viscosity w e r e r e v i e w e d b y M a l h o t r a a n d W a s a n (26).
Properties of the Interfaces

I n s i m p l e two-phase c o l l o i d a l systems, a t h i n i n t e r m e d i a t e r e g i o n o r b o u n d
ary, k n o w n as t h e interface, lies b e t w e e n the d i s p e r s e d a n d d i s p e r s i n g
phases. Interfacial p r o p e r t i e s are v e r y i m p o r t a n t because e m u l s i f i e d d r o p
lets have a large i n t e r f a c i a l area, a n d even a modest i n t e r f a c i a l energy p e r
u n i t area c a n b e c o m e a c o n s i d e r a b l e total i n t e r f a c i a l energy to b e a c c o m m o
d a t e d . F o r example, suppose w e w i s h to e m u l s i f y o n e b a r r e l (159 L ) o f o i l
i n t o w a t e r . F o r this i l l u s t r a t i o n c o n s i d e r the o i l t o b e i n 1 large d r o p that w e
r e p e a t e d l y s u b d i v i d e i n t o d r o p s o f h a l f the p r e v i o u s radius. T h u s , t h e i n i t i a l
d r o p o f r = 33.6 c m b e c o m e s eight drops o f r = 16.8 c m , a n d so o n . F i g u r e 7
shows that the total surface o r i n t e r f a c i a l area p r o d u c e d increases b y a factor
o f 2 w i t h each cut. T h e i n i t i a l i n t e r f a c i a l area o f 1.42 m increases to 7.4 Χ 1 0
2 5
Schramm; Emulsions
cm tm nm
Sphere Radius
Figure 7. Total area and energy changes involved in emulsifying 1 barrel of oil
into water by dispersing into progressively finer droplets.
m b y the t i m e droplets o f 0.64-μιτι radius have b e e n p r o d u c e d . T h i s i n

2
crease is greater t h a n 5 orders o f m a g n i t u d e ! T h e larger i n t e r f a c i a l area w i l l

have a significant total free energy as s h o w n i n F i g u r e 7. I f the i n t e r f a c i a l
t e n s i o n is 35 m N / m , t h e n b y the t i m e the d r o p l e t size is r = 0.64 μ ι η , the total
e n e r g y w i l l have i n c r e a s e d f r o m 0.05 χ 1 0 to 2.6 χ 1 0 J . T h i s 2.6 χ 1 0 J o f
4 4 4
energy h a d to be a d d e d to the system to achieve the e m u l s i f i c a t i o n . I f this

a m o u n t o f energy cannot be p r o v i d e d , f o r e x a m p l e , b y m e c h a n i c a l shear,
t h e n a n o t h e r alternative is to use surfactant c h e m i s t r y to l o w e r the i n t e r f a -
c i a l free energy, o r i n t e r f a c i a l t e n s i o n .
T h e energy p l o t t e d i n F i g u r e 7 was o b t a i n e d b y m u l t i p l y i n g the total
area b y the i n t e r f a c i a l t e n s i o n . N o w i f a s m a l l quantity o f a surfactant was
a d d e d to the water, p o s s i b l y a f e w tenths o f a p e r c e n t , that l o w e r e d the
i n t e r f a c i a l t e n s i o n to 0.35 m N / m , it w o u l d l o w e r the a m o u n t o f m e c h a n i c a l
energy n e e d e d i n the example b y a factor o f 100. F r o m the area p e r m o l e c u l e
that the a d s o r b e d e m u l s i f y i n g agent o c c u p i e s , the m i n i m u m a m o u n t o f
e m u l s i f i e r n e e d e d f o r the e m u l s i o n c a n also be e s t i m a t e d . I n p r a c t i c e ,
l o w e r i n g i n t e r f a c i a l t e n s i o n alone m a y not be sufficient to stabilize an e m u l
sion, i n w h i c h case o t h e r i n t e r f a c i a l p r o p e r t i e s m u s t be adjusted as w e l l .
T h e s e s i m p l e calculations d o , h o w e v e r , s h o w h o w i m p o r t a n t the i n t e r f a c i a l
p r o p e r t i e s c a n b e c o m e w h e n c o l l o i d a l - s i z e d species are i n v o l v e d , as i n e m u l
sions.
Schramm; Emulsions
Surface a n d Interfacial Tensions, R e g a r d i n g the m o l e c u l e s i n a

l i q u i d , t h e attractive v a n d e r W a a l s forces b e t w e e n m o l e c u l e s are felt e q u a l l y
b y a l l m o l e c u l e s except those i n t h e i n t e r f a c i a l r e g i o n . T h i s i n e q u a l i t y i n t h e
van d e r W a a l s forces p u l l s t h e i n t e r f a c i a l m o l e c u l e s t o w a r d the i n t e r i o r o f
the l i q u i d . T h e interface thus has a t e n d e n c y to contract spontaneously. F o r
this reason, droplets o f l i q u i d a n d b u b b l e s o f gas t e n d to adopt a s p h e r i c a l
shape, because this shape reduces t h e surface free energy. F o r two i m m i s c i
b l e l i q u i d s , a s i m i l a r situation applies, except that i t m a y n o t b e so i m m e d i
ately obvious h o w t h e interface w i l l t e n d to c u r v e . T h e r e w i l l still b e a n
i m b a l a n c e o f i n t e r m o l e c u l a r forces a n d a c o n f i g u r a t i o n that m i n i m i z e s t h e
i n t e r f a c i a l free energy.
T h e surface free energy has units o f m i l l i j o u l e s p e r square m e t e r (1
m j / m = 1 erg/cm ), r e f l e c t i n g the fact that area expansion r e q u i r e s energy.
2 2
Surface free energies are usually d e s c r i b e d i n terms o f c o n t r a c t i n g forces

a c t i n g p a r a l l e l to t h e surface o r interface. Surface t e n s i o n ( 7 ) , o r i n t e r f a c i a l
0
t e n s i o n (7), is t h e force p e r u n i t l e n g t h a r o u n d a surface, o r t h e free energy

r e q u i r e d to create n e w surface area. T h u s , t h e units o f surface a n d i n t e r f a c i a l
t e n s i o n are m i l l i n e w t o n s p e r m e t e r (1 m N / m = 1 dyne/cm). T h e s e units f o r
surface a n d i n t e r f a c i a l t e n s i o n are n u m e r i c a l l y e q u a l t o t h e surface free
energy. I n t e r f a c i a l tensions are f r e q u e n t l y i n t e r m e d i a t e b e t w e e n t h e values
o f t h e surface tensions o f t h e l i q u i d s i n v o l v e d a n d are smallest w h e n t h e
l i q u i d s are the most c h e m i c a l l y s i m i l a r (for p u r e l i q u i d s ) .
M a n y m e t h o d s f o r t h e m e a s u r e m e n t o f surface a n d i n t e r f a c i a l tensions,
details o f the e x p e r i m e n t a l t e c h n i q u e s , a n d t h e i r l i m i t a t i o n s are d e s c r i b e d i n
several g o o d reviews (27-29). S o m e methods that are u s e d most i n e m u l s i o n
w o r k are t h e d u N o u y r i n g , d r o p w e i g h t o r v o l u m e , p e n d a n t d r o p , a n d the
s p i n n i n g d r o p . T h e s p i n n i n g d r o p t e c h n i q u e is a p p l i c a b l e t o t h e v e r y l o w
i n t e r f a c i a l tensions e n c o u n t e r e d i n t h e e n h a n c e d o i l r e c o v e r y a n d
m i c r o e m u l s i o n fields (30). I n a l l cases, w h e n solutions r a t h e r t h a n p u r e
l i q u i d s are i n v o l v e d , a p p r e c i a b l e changes c a n take p l a c e w i t h t i m e at t h e
surfaces a n d interfaces.
Young-Laplace Equation. I n t e r f a c i a l t e n s i o n causes a pressure d i f

f e r e n c e to exist across a c u r v e d surface, the pressure b e i n g greater o n t h e
concave side (i.e., o n t h e i n s i d e o f a d r o p l e t ) . I n an interface b e t w e e n phase
A i n a d r o p l e t a n d phase Β s u r r o u n d i n g t h e d r o p l e t , t h e phases w i l l have
pressures p a n d p . I f t h e p r i n c i p a l r a d i i o f c u r v a t u r e are R a n d R , t h e n
A B x 2
Ap=p -p A B = 7 ( l / B + l/R )
1 a (12)
E q u a t i o n 12 is t h e Y o u n g - L a p l a c e e q u a t i o n (31). It shows that p > p ; t h e A B
pressure i n s i d e a d r o p l e t exceeds that outside. F o r s p h e r i c a l droplets i n a n

emulsion,
Ap=p -p A B = 2y/R (13)
Schramm; Emulsions
so that Δ ρ varies w i t h t h e r a d i u s , R. ( M o r e details are g i v e n i n refs. 13 a n d

31.) T h e Y o u n g - L a p l a c e e q u a t i o n forms t h e basis f o r some i m p o r t a n t m e t h
ods f o r m e a s u r i n g surface a n d i n t e r f a c i a l tensions, s u c h as t h e p e n d a n t ,
sessile, a n d s p i n n i n g d r o p m e t h o d s a n d t h e m a x i m u m b u b b l e pressure
m e t h o d (27-30). I n p r i m a r y o i l r e c o v e r y f r o m u n d e r g r o u n d reservoirs, the
c a p i l l a r y forces d e s c r i b e d b y this e q u a t i o n are r e s p o n s i b l e f o r h o l d i n g back
m u c h o f t h e o i l (residual o i l ) i n parts o f t h e p o r e s t r u c t u r e i n t h e r o c k o r
sand. A n y secondary o r e n h a n c e d (tertiary) o i l r e c o v e r y process strategies
are i n t e n d e d to o v e r c o m e these same forces (32). I n t h e example i n v o l v i n g
m i c r o e m u l s i o n s i n e n h a n c e d o i l r e c o v e r y (discussed u n d e r t h e h e a d i n g
" M i c r o e m u l s i o n s " ) , the Y o u n g - L a p l a c e e q u a t i o n was u s e d , w i t h o u t i n t r o
d u c t i o n , to d e m o n s t r a t e h o w l o w e r i n g i n t e r f a c i a l t e n s i o n c a n facilitate e m u l
sification a n d i n c r e m e n t a l o i l recovery. I n that e x a m p l e r , t h e p o r e radius,
was u s e d i n p l a c e o f R i n t h e Y o u n g - L a p l a c e e q u a t i o n , a n d t h e contact angle
was i n c l u d e d .
Contact Angles and Wetting. W h e n a d r o p l e t o f o i l i n w a t e r comes

i n t o contact w i t h a s o l i d surface, t h e o i l m a y f o r m a b e a d o n t h e surface, o r i t
m a y s p r e a d a n d f o r m a film. A l i q u i d h a v i n g a s t r o n g affinity for t h e s o l i d w i l l
seek to m a x i m i z e its contact (interfacial area) a n d f o r m a film. A l i q u i d w i t h
m u c h w e a k e r affinity m a y f o r m i n t o a b e a d . T h e affinity is t e r m e d t h e
w e t t a b i l i t y . B e c a u s e there c a n b e degrees o f s p r e a d i n g , another q u a n t i t y is
n e e d e d . T h e contact angle, Θ, i n a n o i l - w a t e r - s o l i d system is d e f i n e d as t h e
angle, m e a s u r e d t h r o u g h t h e aqueous phase, that is f o r m e d at the j u n c t i o n o f
the three phases. W h e r e a s i n t e r f a c i a l t e n s i o n is d e f i n e d f o r t h e b o u n d a r y
b e t w e e n t w o phases, t h e contact angle is d e f i n e d f o r a three-phase j u n c t i o n .
I f t h e i n t e r f a c i a l forces a c t i n g a l o n g t h e p e r i m e t e r o f t h e d r o p l e t are
r e p r e s e n t e d b y t h e i n t e r f a c i a l tensions, t h e n a n e q u i l i b r i u m force balance
c a n b e w r i t t e n as
7w/o cos θ = 7s/ - 7SAV 0 ( 14)
w h e r e t h e subscripts refer to w a t e r ( W ) , o i l ( O ) , a n d s o l i d (S). E q u a t i o n 14 is

Y o u n g ' s e q u a t i o n . T h e s o l i d is c o m p l e t e l y w a t e r - w e t t e d i f θ = 0 a n d o n l y
p a r t i a l l y w e t t e d o t h e r w i s e . E q u a t i o n 14 is f r e q u e n t l y u s e d to d e s c r i b e w e t
t i n g p h e n o m e n a , so two p r a c t i c a l points are i m p o r t a n t . I n t h e o r y c o m p l e t e
n o n w e t t i n g b y w a t e r w o u l d m e a n that θ = 180°, b u t this contact angle is n o t
seen i n p r a c t i c e . A l s o , values o f θ < 90° are o f t e n c o n s i d e r e d to r e p r e s e n t
" w a t e r - w e t t i n g " , a n d values o f θ > 90° are c o n s i d e r e d to represent " n o n -
w a t e r - w e t t i n g " . T h i s assignment is r a t h e r a r b i t r a r y because i t is b a s e d o n
c o r r e l a t i o n w i t h v i s u a l appearance o f d r o p l e t s o n surfaces.
T h e s e considerations c o m e i n t o p l a y i n o i l r e c o v e r y schemes a p p l i e d to
reservoirs o f m i x e d w e t t a b i l i t y o r w h e r e t h e r o c k is p r e d o m i n a n t l y o i l -
w e t t i n g . A n o t h e r example is t h e case o f t h e s o - c a l l e d P i c k e r i n g e m u l s i o n s ,
Schramm; Emulsions
e m u l s i o n s s t a b i l i z e d b y fine p a r t i c l e s . A film o f c l o s e - p a c k e d particles has

c o n s i d e r a b l e m e c h a n i c a l strength, w h i c h c o n t r i b u t e s to t h e stability o f a n
e m u l s i o n . T h e most stable e m u l s i o n s o c c u r w h e n t h e contact angle is close
to 90°, so that t h e particles w i l l c o l l e c t at t h e interface. C o m b i n i n g Y o u n g ' s
e q u a t i o n w i t h t h e o r i e n t e d w e d g e t h e o r y (see later, " E m u l s i f y i n g A g e n t s " )
allows some p r e d i c t i o n s to b e m a d e . I f the contact angle f o r a fine p a r t i c l e at
the O / W interface is θ < 90°, t h e n most o f t h e p a r t i c l e w i l l reside i n t h e
aqueous phase. I n this case a n O / W e m u l s i o n is i n d i c a t e d . C o n v e r s e l y , i f θ >
90°, t h e n t h e p a r t i c l e w i l l b e m o s t l y i n t h e o i l phase, a n d W / O is p r e d i c t e d .
Adsorption at Interfaces: Surface Activity. Surfactants.

S o m e c o m p o u n d s , l i k e s h o r t - c h a i n fatty acids, c a n b e p a r t l y s o l u b l e i n b o t h
w a t e r a n d o i l . T h i s d u a l s o l u b i l i t y is because s u c h m o l e c u l e s are a m p h i p h i l i c
or a m p h i p a t h i c ; that is, they have one part that has a n affinity f o r t h e o i l (the
n o n p o l a r h y d r o c a r b o n c h a i n ) , a n d o n e part that has a n affinity f o r t h e w a t e r
(the p o l a r g r o u p ) . T h e e n e r g e t i c a l l y most favorable o r i e n t a t i o n f o r these
m o l e c u l e s is at t h e o i l - w a t e r interface, so that each p a r t o f the m o l e c u l e c a n
reside i n t h e solvent f o r w h i c h i t has the greatest affinity (see F i g u r e 8).
Figure 8. Surfactant associations in an O/W emulsion. The size of the surfac

tant molecules compared to the oil droplets has been exaggerated for the
purposes of illustration.
Schramm; Emulsions
T h e s e m o l e c u l e s that f o r m o r i e n t e d monolayers at interfaces s h o w surface

activity a n d are t e r m e d surfactants. A s t h e r e w i l l b e a balance b e t w e e n
a d s o r p t i o n a n d d e s o r p t i o n (due to t h e r m a l m o t i o n s ) , the i n t e r f a c i a l c o n d i
t i o n r e q u i r e s some t i m e to establish. B e c a u s e o f this t i m e r e q u i r e d , surface
activity s h o u l d b e c o n s i d e r e d a d y n a m i c p h e n o m e n o n . T h i s fact can b e seen
b y m e a s u r i n g surface t e n s i o n versus t i m e f o r a freshly f o r m e d surface.
A c o n s e q u e n c e o f surfactant a d s o r p t i o n at an interface is that it p r o v i d e s
an e x p a n d i n g force acting against the n o r m a l i n t e r f a c i a l t e n s i o n . I f ττ is this
e x p a n d i n g pressure (surface pressure), t h e n 7 = 7 i - ττ. T h u s , surfactants
i n i t i a
t e n d to l o w e r i n t e r f a c i a l t e n s i o n ; i f a l o w e n o u g h value o f 7 is r e a c h e d ,
e m u l s i f i c a t i o n c a n take p l a c e because o n l y a s m a l l increase i n surface free
energy is r e q u i r e d , f o r e x a m p l e , w h e n ττ ~ 7 i t i a i - I f s o l u t e - s o l v e n t forces are
i n
greater t h a n s o l v e n t - s o l v e n t forces o n the o t h e r h a n d , t h e n m o l e c u l a r m i

g r a t i o n away f r o m the interface can o c c u r a n d cause i n c r e a s e d surface
t e n s i o n (e.g., N a C l [aq]).
G i b b s has t h e r m o d y n a m i c a l l y d e s c r i b e d the l o w e r i n g o f surface free
e n e r g y that results f r o m surfactant a d s o r p t i o n . T h e g e n e r a l G i b b s adsorp
t i o n e q u a t i o n f o r a b i n a r y , i s o t h e r m a l system c o n t a i n i n g excess electrolyte is
T = - (1 /RT)
s (dy/d In C )s (15)
w h e r e F is the surface excess o f surfactant (mol/cm ), C is the s o l u t i o n

s
2
s
c o n c e n t r a t i o n o f the surfactant ( M ) , a n d 7 m a y be e i t h e r surface o r i n t e r f a -

c i a l t e n s i o n ( m N / m ) . T h i s e q u a t i o n c a n b e a p p l i e d to d i l u t e surfactant s o l u
tions i n w h i c h the surface c u r v a t u r e is not great a n d w h e r e the a d s o r b e d film
c a n b e c o n s i d e r e d a m o n o l a y e r . T h e p a c k i n g density o f surfactant i n a
m o n o l a y e r at the interface c a n b e c a l c u l a t e d as f o l l o w s . T h e surface excess i n
a t i g h t l y p a c k e d m o n o l a y e r c a n be c a l c u l a t e d f r o m the slope o f the l i n e a r
p o r t i o n o f a p l o t o f surface t e n s i o n versus the l o g a r i t h m o f s o l u t i o n c o n
c e n t r a t i o n (see F i g u r e 9). F r o m this slope, the area p e r a d s o r b e d m o l e c u l e
(a ) c a n be c a l c u l a t e d f r o m
s
β = 1/(2Ϋ Γ.)
β Α (16)
where N A is A v o g a d r o ' s n u m b e r . Numerous examples are given by

R o s e n (33).
Surface Films. I n s o l u b l e p o l a r m o l e c u l e s (e.g., l o n g - c h a i n fatty ac

ids) e x h i b i t an extreme k i n d o f a d s o r p t i o n at l i q u i d surfaces. T h a t is, t h e y can
b e m a d e to c o n c e n t r a t e i n one m o l e c u l a r layer at the surface. T h e s e i n t e r f a -
c i a l films o f t e n p r o v i d e the s t a b i l i z i n g i n f l u e n c e i n e m u l s i o n s because they
c a n b o t h l o w e r i n t e r f a c i a l t e n s i o n a n d increase the i n t e r f a c i a l viscosity.
I n c r e a s i n g i n t e r f a c i a l viscosity p r o v i d e s a m e c h a n i c a l resistance to coales
c e n c e . S u c h systems also l e n d themselves to the study o f size, shape, a n d
Schramm; Emulsions
CMC
Surfactant Surfactant
Monomers Micelles
Log Concentration
Figure 9. The association behavior of surfactants in solution, showing the

critical micelle concentration (CMC).
o r i e n t a t i o n o f m o l e c u l e s at an interface. H a v i n g an a d s o r b e d layer lowers the

surface t e n s i o n (to y) b y the surface pressure ττ = 7 i - 7, as already n o t e d .
i n i t i a
I n a surface balance ( p i o n e e r e d b y L a n g m u i r a n d others) ττ versus t h e

available area o f surface (A) c a n b e d e t e r m i n e d d i r e c t l y . A n o t h e r a p p r o a c h is
to measure t h e l o w e r e d surface tension ( W i l h e l m y plate) a n d calculate ττ.
F o r v e r y l o w film pressures, an i d e a l gas l a w analogy,
TTA = nRT = nN kT A (17)
allows c a l c u l a t i o n o f the effective area p e r m o l e c u l e (A/nN ) i n the m o n o

A
layer; here η is t h e n u m b e r o f moles, R is t h e gas constant, Γ is absolute

t e m p e r a t u r e , a n d k is the B o l t z m a n n constant.
Classification of Surfactants, Surfactants are classified a c c o r d i n g to

the nature o f the p o l a r ( h y d r o p h i l i c ) part o f the m o l e c u l e , as i l l u s t r a t e d i n
T a b l e I I I . I n - d e p t h discussions o f surfactant structure a n d c h e m i s t r y c a n b e
f o u n d i n references 3 3 - 3 5 .
I n aqueous s o l u t i o n , d i l u t e concentrations o f surfactant act m u c h as
n o r m a l electrolytes, b u t at h i g h e r concentrations v e r y d i f f e r e n t b e h a v i o r
results. T h i s b e h a v i o r (illustrated i n F i g u r e s 8 a n d 9) was e x p l a i n e d b y
M c B a i n i n terms o f o r g a n i z e d aggregates c a l l e d m i c e l l e s i n w h i c h the l i p o
p h i l i c parts o f the surfactants associate i n the i n t e r i o r o f the aggregate a n d
leave h y d r o p h i l i c parts to face t h e aqueous m e d i u m . ( D e t a i l s are g i v e n i n
refs. 16 a n d 31.) T h e c o n c e n t r a t i o n at w h i c h m i c e l l e f o r m a t i o n b e c o m e s
Schramm; Emulsions
Table III. Surfactant Classifications
Class Examples ^ Structures
+
Anionic N a stéarate 3
CH (CH ) CO<XNa 2 1 6
+
N a dodecyl sulfate CH3(CH )iiS0 ~Na 2 4
+
N a dodecyl benzene sulfonate 3
CH (CH ) C6H S03~Na2 11 4
+
Cationic Laurylamine hydrochloride 3
CH (CH )iiNH3 Cr 2
+
Cetyl trimethylammonium bromide 3 2
CH (CH ) N (CH )3Br- 15 3
Nonionic Polyoxyethylene alcohol 2n+

C„H i(OCH2CH ) OH 2 m
Alkylphenol ethoxylate 9
C Hi9-C H -(OCH CH ) OH6 4 2 2 n
Schramm; Emulsions
+
Zwitterionic Lauramidopropyl betaine n 2 3
C H CONH(CH ) N (CH )2CH COO" 2 3 3 2
Cocoamido-2-hydroxypropyl
+
sulfobetaine n
C H 2 n + iCONH(CH ) N (CH ) CH CH(OH)CH S0 - 2 3 3 2 2 2 3

significant is c a l l e d the c r i t i c a l m i c e l l e c o n c e n t r a t i o n ( C M C ) . T h e C M C is a
p r o p e r t y o f the surfactant a n d several o t h e r factors, because m i c e l l i z a t i o n is
o p p o s e d b y t h e r m a l a n d electrostatic forces. A l o w C M C is f a v o r e d b y
i n c r e a s i n g the m o l e c u l a r mass o f the l i p o p h i l i c p a r t o f the m o l e c u l e , l o w e r
i n g the t e m p e r a t u r e (usually), a n d a d d i n g e l e c t r o l y t e . Surfactant m o l e c u l a r
weights range f r o m a f e w h u n d r e d u p to several t h o u s a n d .
S o m e t y p i c a l C M C values f o r l o w electrolyte concentrations at r o o m
t e m p e r a t u r e are
Surfactant Class CMC (M)

Nonionic KH-IO" 4
Anionic KH-IO" 2
Amphoteric KH-IQ - 1
T h e s o l u b i l i t i e s o f m i c e l l e - f o r m i n g surfactants show a s t r o n g increase

above a c e r t a i n t e m p e r a t u r e , t e r m e d the K r a f f t p o i n t ( T ) . T h i s increase i n
K
s o l u b i l i t y is e x p l a i n e d b y the fact that the single surfactant m o l e c u l e s have

l i m i t e d s o l u b i l i t y , whereas the m i c e l l e s are v e r y s o l u b l e . R e f e r r i n g to F i g u r e
10, b e l o w the K r a f f t p o i n t the s o l u b i l i t y o f the surfactant is too l o w for
m i c e l l i z a t i o n , a n d s o l u b i l i t y alone d e t e r m i n e s the surfactant m o n o m e r c o n
c e n t r a t i o n . A s t e m p e r a t u r e increases, the s o l u b i l i t y increases u n t i l at T the K
C M C is r e a c h e d . A t this t e m p e r a t u r e a relatively large a m o u n t o f surfactant

c a n be d i s p e r s e d i n m i c e l l e s , a n d s o l u b i l i t y increases greatly. A b o v e the
Figure 10. The solubility-micellization behavior of surfactants in solution,

showing the Krafft point.
Schramm; Emulsions
K r a f f t p o i n t , m a x i m u m r e d u c t i o n i n surface o r i n t e r f a c i a l t e n s i o n occurs at
the C M C because n o w the C M C d e t e r m i n e s the surfactant m o n o m e r c o n
centration.
C o h e s i o n , A d h e s i o n , a n d Spreading. T w o phases A a n d Β may

have a n interface b e t w e e n t h e m , A B . C o h e s i o n , a d h e s i o n , a n d s p r e a d i n g can
be d e n n e d f o r the changes s h o w n i n F i g u r e 11 ( i n v o l v i n g always u n i t surface
area). T h e w o r k o f c o h e s i o n represents the energy r e q u i r e d to increase
i n t e r f a c i a l area b y two square u n i t s . T h u s the energy r e q u i r e d to disperse o i l
i n t o finer a n d finer droplets, to make a n e m u l s i o n , increases as the i n t e r f a -
Figure 11. Cohesion, adhesion, and spreading. All indicated changes are per
unit area, AG is the Gibbs free energy change, and the subscripts denote oil
(O), water (W) and air (A).
Schramm; Emulsions
c i a l t e n s i o n b e t w e e n t h e droplets increases. T h e w o r k o f a d h e s i o n is t h e
energy i n v o l v e d w h e n t w o surfaces, i n i t i a l l y i n contact w i t h each other, are
separated to each contact a t h i r d phase. T h e w o r k o f a d h e s i o n relates t o , f o r
e x a m p l e , surface e n e r g y changes i n v o l v e d w h e n a n o i l d r o p l e t i n i t i a l l y i n
contact w i t h a s o l i d p a r t i c l e b e c o m e s released i n t o water. S p r e a d i n g occurs
w h e n , f o r e x a m p l e , e m u l s i f i e d o i l droplets r e a c h t h e a i r - w a t e r interface a n d
spread over the surface. T h i s s p r e a d i n g is a m e c h a n i s m f o r d e m u l s i f i c a t i o n ; a
negative s p r e a d i n g coefficient s h o u l d thus t e n d to c o n t r i b u t e to e m u l s i o n
stability. S p r e a d i n g is also a m e c h a n i s m f o r d e f o a m i n g b y e m u l s i o n s (36).
P e t r o l e u m e m u l s i o n s have b e e n u s e d to p r e v e n t t h e f o r m a t i o n o f foams, o r
destroy foams already generated, i n various i n d u s t r i a l processes (37).
Stability of Emulsions
M e a n i n g o f Stability. M o s t e m u l s i o n s are not t h e r m o d y n a m i c a l l y
stable. R a t h e r t h e y possess some degree o f k i n e t i c stability, a n d i t is i m p o r
tant t o d i s t i n g u i s h t h e degree o f change a n d t h e t i m e scale. A s m e n t i o n e d
p r e v i o u s l y , coalescence a n d aggregation are processes i n w h i c h p a r t i c l e s ,
d r o p l e t s , o r b u b b l e s are b r o u g h t together w i t h (coalescence) o r w i t h o u t
(aggregation) large changes i n surface area. T h u s , t h e r e c a n b e d i f f e r e n t
k i n d s o f k i n e t i c stability. T h i s d i s c u s s i o n o f c o l l o i d stability w i l l explore t h e
reasons w h y c o l l o i d a l dispersions c a n have d i f f e r e n t degrees o f k i n e t i c s t a b i l
ity a n d h o w these are i n f l u e n c e d , a n d c a n t h e r e f o r e b e m o d i f i e d , b y s o l u t i o n
a n d surface p r o p e r t i e s . T h e d i s c u s s i o n is c a r r i e d f u r t h e r , a n d i n m o r e d e t a i l ,
i n C h a p t e r 2.
E n c o u n t e r s b e t w e e n particles i n a d i s p e r s i o n c a n o c c u r f r e q u e n t l y b e
cause o f B r o w n i a n m o t i o n , s e d i m e n t a t i o n , o r s t i r r i n g . T h e stability o f t h e
d i s p e r s i o n d e p e n d s u p o n h o w t h e particles interact w h e n these e n c o u n t e r s
h a p p e n . T h e m a i n cause o f r e p u l s i v e forces is t h e electrostatic r e p u l s i o n
b e t w e e n l i k e - c h a r g e d objects. T h e m a i n attractive forces are t h e v a n d e r
W a a l s forces b e t w e e n objects.
Electrostatic F o r c e s . Charged Interfaces. M o s t substances ac

q u i r e a surface e l e c t r i c charge w h e n b r o u g h t i n t o contact w i t h a p o l a r
m e d i u m s u c h as water. F o r e m u l s i o n s , t h e o r i g i n o f t h e charge c a n b e
i o n i z a t i o n , as w h e n surface a c i d f u n c t i o n a l i t i e s i o n i z e w h e n o i l droplets are
d i s p e r s e d i n t o a n aqueous s o l u t i o n , o r the o r i g i n c a n b e a d s o r p t i o n , as w h e n
surfactant ions o r c h a r g e d particles adsorb o n t o a n o i l d r o p l e t surface. S o l i d
particles c a n have a d d i t i o n a l m e c h a n i s m s o f c h a r g i n g . O n e is t h e u n e q u a l
d i s s o l u t i o n o f cations a n d anions that m a k e u p t h e crystal s t r u c t u r e ( i n t h e
salt type m i n e r a l s , f o r example). A n o t h e r is t h e d i f f u s i o n o f c o u n t e r i o n s away
f r o m t h e surface o f a s o l i d w h o s e i n t e r n a l crystal structure carries a n o p p o
site charge because o f i s o m o r p h i c s u b s t i t u t i o n ( i n clays, f o r example). T h e
Schramm; Emulsions
surface charge influences t h e d i s t r i b u t i o n o f n e a r b y ions i n t h e p o l a r m e

d i u m . Ions o f opposite charge (counterions) are attracted to t h e surface, b u t
those o f l i k e charge (co-ions) are r e p e l l e d . A n e l e c t r i c d o u b l e layer, w h i c h is
diffuse because o f m i x i n g c a u s e d b y t h e r m a l m o t i o n , is thus f o r m e d .
I n a p r a c t i c a l p e t r o l e u m e m u l s i o n s i t u a t i o n , t h e d e g r e e o f surface c h a r g
i n g is m o r e c o m p l i c a t e d . A n example is t h e b i t u m e n - w a t e r interface, w h i c h
b e c o m e s negatively c h a r g e d i n alkaline aqueous solutions as a result o f t h e
i o n i z a t i o n o f surface c a r b o x y l i c a c i d groups b e l o n g i n g t o n a t u r a l surfactants
present i n t h e b i t u m e n . T h e degree o f negative c h a r g i n g is v e r y i m p o r t a n t to
the success o f b i t u m e n r e c o v e r y processes f r o m i n situ o i l sands a n d also
separation processes f r o m surface o i l sands, s u c h as t h e h o t - w a t e r flotation
process (38-42). T h e degree o f negative charge at t h e interface d e p e n d s o n
the ρ H a n d i o n i c strength o f the s o l u t i o n (38, 39) a n d also o n the c o n c e n t r a
t i o n o f n a t u r a l surfactant m o n o m e r s present i n t h e aqueous phase (40, 41).
W i t h b i t u m e n , as w i t h o t h e r heavy c r u d e oils, m o r e t h a n o n e k i n d o f surfac
tant m a y b e p r o d u c e d (42), a n d t h e s o l u t i o n concentrations o f the
surfactants d e p e n d also o n r e a c t i o n c o n d i t i o n s (temperature, etc.) a n d o n
the extent o f c o m p e t i n g reactions s u c h as t h e a d s o r p t i o n o f t h e surfactants
o n t o s o l i d (clay) particles that are present (43, 44).
Electric Double Layer. T h e e l e c t r i c d o u b l e layer ( E D L ) consists o f

the c h a r g e d surface a n d a n e u t r a l i z i n g excess o f c o u n t e r i o n s over co-ions,
d i s t r i b u t e d near t h e surface (see F i g u r e 12). T h e E D L c a n b e v i e w e d as
b e i n g c o m p o s e d o f t w o layers:
• a n i n n e r layer that m a y i n c l u d e a d s o r b e d ions

• a d i f f u s e layer i n w h i c h ions are d i s t r i b u t e d a c c o r d i n g to t h e
i n f l u e n c e o f e l e c t r i c a l forces a n d t h e r m a l m o t i o n
G o u y a n d C h a p m a n p r o p o s e d a s i m p l e quantitative m o d e l f o r t h e diffuse
d o u b l e layer, a s s u m i n g , a m o n g other things, a n i n f i n i t e , flat, u n i f o r m l y
c h a r g e d surface a n d p o i n t - c h a r g e ions. ( F u r t h e r details are g i v e n i n refs. 14,
3 1 , a n d 45.) T a k i n g t h e surface p o t e n t i a l to b e ψ°, t h e p o t e n t i a l ψ at a
distance χ f r o m t h e surface is a p p r o x i m a t e l y
ψ = ψ° exp (-κχ) ( 18)
T h e surface charge density is g i v e n as σ° = βκψ , w h e r e e is the p e r m i t t i v i t y

0
a n d κ is n o t c o n d u c t i v i t y b u t a special v a r i a b l e d e f i n e d i n e q u a t i o n 19; thus,

ψ° d e p e n d s o n surface charge density a n d t h e s o l u t i o n i o n i c c o m p o s i t i o n
( t h r o u g h κ). T h e variable l/κ is c a l l e d t h e d o u b l e - l a y e r thickness, a n d f o r
w a t e r at 25 °C i t is g i v e n b y
κ = 3.288V/ (nm" ) 1
(19)
Schramm; Emulsions
Figure 12. Simplified illustrations of the electrical double layer around a

negatively charged colloidal emulsion droplet. The left view shows the change
in charge density around the droplet. The right view shows the distribution of
ions around the charged droplet. (Courtesy of L. A. Ravina, Zeta-Meter, Inc.,
Long Island City, NY.)
w h e r e I is the i o n i c strength, g i v e n b y I = (1/2) Σ<<% , i n w h i c h c are t h e

2
{
i n d i v i d u a l i o n c o n c e n t r a t i o n s a n d z are t h e respective i o n - c h a r g e n u m b e r s .
{
F o r a 1 - 1 electrolyte,
1/K=lnmfor/ = 1 0 M 1
1/K = 10 n m f o r / = ΙΟ" M 3
(20)
I n fact a n i n n e r layer exists because ions are not r e a l l y p o i n t charges a n d

an i o n c a n a p p r o a c h a surface o n l y to t h e extent a l l o w e d b y its h y d r a t i o n
s p h e r e . T h e S t e r n m o d e l specifically i n c o r p o r a t e s a layer o f s p e c i f i c a l l y
a d s o r b e d ions b o u n d e d b y a p l a n e , t h e S t e r n p l a n e (see F i g u r e 13 a n d refs.
14, 3 1 , a n d 45). I n this case t h e p o t e n t i a l changes f r o m ψ° at t h e surface, t o
ψ(§) at t h e S t e r n p l a n e , t o ψ = 0 i n b u l k s o l u t i o n .
Electrokinetic Phenomena. E l e c t r o k i n e t i c m o t i o n occurs w h e n t h e

m o b i l e part o f the e l e c t r i c d o u b l e layer is s h e a r e d away f r o m t h e i n n e r l a y e r
Schramm; Emulsions
Figure 13. Simplified illustration of the surface and zeta potentials for a
charged emulsion droplet dispersed in high and low electrolyte concentration
aqueous solutions. (Courtesy of L. A. Ravina, Zeta-Meter, Inc., Long Island
City, NY.)
(charged surface). T h e f o u r types o f e l e c t r o k i n e t i c m e a s u r e m e n t s are elec

trophoresis, electro-osmosis, s t r e a m i n g p o t e n t i a l , a n d s e d i m e n t a t i o n p o t e n
tial, o f w h i c h electrophoresis finds the most use i n i n d u s t r i a l p r a c t i c e . G o o d
d e s c r i p t i o n s o f p r a c t i c a l e x p e r i m e n t a l t e c h n i q u e s i n electrophoresis a n d
t h e i r l i m i t a t i o n s c a n be f o u n d i n references 4 6 - 4 8 .
I n electrophoresis an e l e c t r i c field is a p p l i e d to a sample a n d causes
c h a r g e d droplets o r particles a n d any attached m a t e r i a l o r l i q u i d to m o v e
t o w a r d the o p p o s i t e l y c h a r g e d e l e c t r o d e . T h u s the results c a n be i n t e r p r e t e d
o n l y i n terms o f charge density ( σ ) or p o t e n t i a l (ψ) at the p l a n e o f shear. T h e
latter is also k n o w n as the zeta p o t e n t i a l . B e c a u s e the exact l o c a t i o n o f the
shear p l a n e is g e n e r a l l y not k n o w n , the zeta p o t e n t i a l is u s u a l l y taken to be
a p p r o x i m a t e l y e q u a l to the p o t e n t i a l at the S t e r n p l a n e ( F i g u r e 13):
ζ = Ψ(δ) (21)
w h e r e δ is the distance f r o m the d r o p l e t surface to the S t e r n p l a n e . I n

m i c r o e l e c t r o p h o r e s i s the d i s p e r s e d droplets are v i e w e d u n d e r a m i c r o s c o p e ,
a n d t h e i r e l e c t r o p h o r e t i c v e l o c i t y is m e a s u r e d at a l o c a t i o n i n the sample c e l l
w h e r e the e l e c t r i c field gradient is k n o w n . T h i s m e a s u r e m e n t m u s t b e d o n e
at c a r e f u l l y selected planes w i t h i n the c e l l because the c e l l walls b e c o m e
c h a r g e d as w e l l a n d cause e l e c t r o - o s m o t i c flow o f the b u l k l i q u i d i n s i d e the
cell.
T h e e l e c t r o p h o r e t i c m o b i l i t y , μ , is d e f i n e d as the e l e c t r o p h o r e t i c v e
Ε
l o c i t y d i v i d e d b y the e l e c t r i c field gradient at the l o c a t i o n w h e r e t h e v e l o c i t y
Schramm; Emulsions
was m e a s u r e d . It r e m a i n s t h e n to relate t h e e l e c t r o p h o r e t i c m o b i l i t y to t h e
z e t a p o t e n t i a l ( ζ ) . T w o s i m p l e relations c a n b e u s e d to calculate zeta p o t e n
tials i n l i m i t i n g cases:
• H i i c k e l t h e o r y . F o r d r o p l e t s o f s m a l l radius (r) w i t h " t h i c k "

e l e c t r i c d o u b l e layers, m e a n i n g that Kr < 1, i t is a s s u m e d that
Stokes' l a w applies a n d t h e e l e c t r i c a l f o r c e is e q u a t e d to t h e
f r i c t i o n a l resistance o f t h e d r o p l e t , μ Ε = £e/(1.5r/).
• S m o l u c h o w s k i t h e o r y . F o r large d r o p l e t s w i t h " t h i n " e l e c t r i c

d o u b l e layers, m e a n i n g droplets f o r w h i c h Κ Γ > 100, μ Ε = ζβ/τ/.
T h e s e theories are d i s c u s s e d i n m o r e d e t a i l i n r e f e r e n c e s 14 a n d 50.

W i t h these relations zeta potentials c a n b e c a l c u l a t e d f o r m a n y p r a c t i c a l
systems. W i t h i n e a c h set o f l i m i t i n g c o n d i t i o n s t h e e l e c t r o p h o r e t i c m o b i l i t y
is i n d e p e n d e n t o f p a r t i c l e size a n d shape as l o n g as t h e ζ p o t e n t i a l is c o n
stant. F o r i n t e r m e d i a t e values o f fcr, the H e n r y e q u a t i o n a n d m a n y o t h e r
equations a p p l y (46, 47, 49).
Repulsive Forces. I n t h e s i m p l e s t e x a m p l e o f c o l l o i d stability, e m u l

s i o n d r o p l e t s w o u l d b e s t a b i l i z e d e n t i r e l y b y t h e r e p u l s i v e forces created
w h e n t w o c h a r g e d surfaces a p p r o a c h each o t h e r a n d t h e i r e l e c t r i c d o u b l e
layers o v e r l a p . T h e r e p u l s i v e energy, V , f o r s p h e r i c a l d r o p l e t s is g i v e n
R
a p p r o x i m a t e l y as
V = R
B e k
^ \ x p ( - K H )
n
(22)
Ζ
w h e r e t h e spheres have radius r a n d are separated b y distance Η , Β is a

constant (3.93 χ 1 0 3 9
A~ s~ ), ζ is the c o u n t e r i o n charge n u m b e r , a n d
2 2
exp [zeijj(S) / 2kT] - 1 ^

exp[%é?i/<S)/2fcT] + l
Dispersion Forces, v a n d e r W a a l s p o s t u l a t e d that n e u t r a l m o l e

cules exert forces o f attraction o n each o t h e r that are c a u s e d b y e l e c t r i c a l
i n t e r a c t i o n s b e t w e e n t h r e e types o f d i p o l a r configurations. T h e attraction
results f r o m t h e o r i e n t a t i o n o f d i p o l e s that m a y b e (1) t w o p e r m a n e n t
d i p o l e s , (2) d i p o l e - i n d u c e d d i p o l e , o r (3) i n d u c e d d i p o l e - i n d u c e d d i p o l e .
I n d u c e d d i p o l e - i n d u c e d d i p o l e forces b e t w e e n n o n p o l a r m o l e c u l e s are also
c a l l e d L o n d o n d i s p e r s i o n forces. E x c e p t f o r q u i t e p o l a r materials, t h e L o n
d o n d i s p e r s i o n forces are t h e m o r e significant o f t h e t h r e e . F o r m o l e c u l e s
the force varies i n v e r s e l y w i t h t h e sixth p o w e r o f the i n t e r m o l e c u l a r d i s
tance.
F o r d i s p e r s e d d r o p l e t s (or p a r t i c l e s , etc.) t h e d i s p e r s i o n forces c a n b e
a p p r o x i m a t e d b y a d d i n g t h e attractions b e t w e e n a l l i n t e r d r o p l e t pairs o f
Schramm; Emulsions
m o l e c u l e s . W h e n a d d e d this w a y , the d i s p e r s i o n force b e t w e e n t w o d r o p l e t s

decays less r a p i d l y as a f u n c t i o n o f separation distance t h a n is the case f o r
i n d i v i d u a l m o l e c u l e s . F o r t w o spheres o f radius r i n a v a c u u m , separated b y
distance H , the attractive e n e r g y V c a n b e a p p r o x i m a t e d b y
A
V
A
A = - —
12H
(24)
f o r H < 1 0 - 2 0 n m a n d H « r . T h e constant A is k n o w n as the H a m a k e r

constant a n d d e p e n d s o n the density a n d p o l a r i z a b i l i t y o f atoms i n the
p a r t i c l e s . T y p i c a l l y 1 0 " J < A < 1 0 " J . W h e n the p a r t i c l e s are i n a m e d i u m
20 19
o t h e r t h a n v a c u u m , the attraction is r e d u c e d . T h i s r e d u c e d attraction c a n be

a c c o u n t e d f o r b y u s i n g an effective H a m a k e r constant
A= ( V Â , - ^ ) 2
(25)
w h e r e the subscripts denote the m e d i u m (1) a n d particles (2).

T h e effective H a m a k e r constant e q u a t i o n shows that the attraction b e
t w e e n particles is weakest w h e n the particles a n d m e d i u m are most c h e m i
cally s i m i l a r (A ~ A ) . T h e H a m a k e r constants are u s u a l l y not w e l l k n o w n
1 2
a n d m u s t be a p p r o x i m a t e d .
D L V O Theory. Derjaguin and Landau, and independently Verwey

a n d O v e r b e e k (45), d e v e l o p e d a quantitative t h e o r y f o r the stability o f l y o
p h o b i c c o l l o i d s , n o w k n o w n as the D L V O theory. It was d e v e l o p e d i n an
attempt to a c c o u n t f o r the o b s e r v a t i o n that c o l l o i d s coagulate q u i c k l y at h i g h
electrolyte c o n c e n t r a t i o n s , slowly at l o w c o n c e n t r a t i o n s , a n d w i t h a v e r y
n a r r o w electrolyte c o n c e n t r a t i o n range over w h i c h the t r a n s i t i o n f r o m one to
the o t h e r o c c u r s . T h i s n a r r o w electrolyte c o n c e n t r a t i o n range defines the
c r i t i c a l c o a g u l a t i o n c o n c e n t r a t i o n ( C C C ) . T h e D L V O t h e o r y accounts f o r
the energy changes that take p l a c e w h e n t w o droplets (or particles) a p p r o a c h
each other, a n d involves e s t i m a t i n g the energy o f attraction ( L o n d o n - v a n
d e r W a a l s ) versus i n t e r p a r t i c l e distance a n d the energy o f r e p u l s i o n (electro
static) versus distance. T h e s e , V a n d V , respectively, are t h e n a d d e d to
A R
gether to y i e l d the total i n t e r a c t i o n e n e r g y V . A t h i r d i m p o r t a n t force occurs

at v e r y s m a l l separation distances w h e r e the a t o m i c e l e c t r o n c l o u d s o v e r l a p
a n d causes a s t r o n g r e p u l s i o n , c a l l e d B o r n r e p u l s i o n . T h e t h e o r y has b e e n
d e v e l o p e d f o r several s p e c i a l cases, i n c l u d i n g the i n t e r a c t i o n b e t w e e n t w o
spheres, a n d refinements are constantly b e i n g m a d e .
T h e value o f V decreases e x p o n e n t i a l l y w i t h i n c r e a s i n g separation dis
R
tance a n d has a range about e q u a l to κ" , a n d V decreases i n v e r s e l y w i t h

1
A
i n c r e a s i n g separation distance. F i g u r e 14 shows a single attractive e n e r g y

c u r v e a n d t w o d i f f e r e n t r e p u l s i v e energy curves, r e p r e s e n t i n g t w o v e r y
d i f f e r e n t levels o f electrolyte c o n c e n t r a t i o n . T h e figure shows the total
i n t e r a c t i o n e n e r g y curves that result i n each case. E i t h e r the attractive v a n
Schramm; Emulsions
d e r W a a l s forces or the r e p u l s i v e electric d o u b l e - l a y e r forces can p r e d o m i

nate at d i f f e r e n t i n t e r d r o p l e t distances.
W i t h a positive p o t e n t i a l e n e r g y m a x i m u m , a d i s p e r s i o n s h o u l d b e stable
if V kT, that is, i f the energy is large c o m p a r e d to the t h e r m a l energy o f the
particles (15&Tis c o n s i d e r e d i n s u r m o u n t a b l e ) . I n this case c o l l i d i n g d r o p l e t s
s h o u l d r e b o u n d w i t h o u t contact, a n d the e m u l s i o n s h o u l d b e stable to ag
gregation. If, o n the o t h e r h a n d , the p o t e n t i a l energy m a x i m u m is not v e r y
great, V ~ kT, t h e n slow aggregation s h o u l d o c c u r . T h e h e i g h t o f the energy
b a r r i e r d e p e n d s o n the surface p o t e n t i a l , ψ(δ) a n d o n the range o f the
r e p u l s i v e forces, κ . F i g u r e 14 shows that an energy m i n i m u m c a n o c c u r at
- 1
larger i n t e r p a r t i c l e distances. I f this energy m i n i m u m is reasonably d e e p

c o m p a r e d to kT, t h e n a loose, easily r e v e r s i b l e aggregation s h o u l d o c c u r .
Practical G u i d e l i n e s . T h e D L V O calculations c a n b e c o m e q u i t e
i n v o l v e d , r e q u i r i n g c o n s i d e r a b l e k n o w l e d g e about the systems o f interest.
A l s o , t h e y present some p r o b l e m s . F o r e x a m p l e , some d i s t o r t i o n o f the
s p h e r i c a l e m u l s i o n droplets w i l l o c c u r as they a p p r o a c h each o t h e r a n d b e g i n
to seriously interact; these interactions cause a flattening. A l s o , o u r v i e w o f
Figure 14. The effect of different repulsive potential energy curves (1 and 2) on
the total interaction energy for a given attractive energy curve. (Reproduced
with permission from reference 16. Copyright 1981 Butterworth Heinemann
Ltd.)
Schramm; Emulsions
the v a l i d i t y o f the t h e o r y is c h a n g i n g as m o r e b e c o m e s k n o w n about t h e

i n f l u e n c e o f a d d i t i o n a l forces s u c h as those d u e to surface h y d r a t i o n . T h e
D L V O t h e o r y nevertheless f o r m s a v e r y u s e f u l starting p o i n t i n a t t e m p t i n g
to u n d e r s t a n d c o m p l e x c o l l o i d a l systems s u c h as p e t r o l e u m e m u l s i o n s . E m
p i r i c a l " r u l e s o f t h u m b " c a n b e u s e d to give a first estimate o f the d e g r e e o f
c o l l o i d a l stability that a system is l i k e l y to have i f the zeta potentials o f t h e
d r o p l e t s are k n o w n .
Zeta Potential Criteria. M a n y types o f c o l l o i d s t e n d to adopt a nega

tive surface charge w h e n d i s p e r s e d i n aqueous solutions h a v i n g i o n i c c o n
centrations a n d p H t y p i c a l o f n a t u r a l waters. F o r s u c h systems o n e r u l e o f
t h u m b stems f r o m observations that the c o l l o i d a l particles are q u i t e stable
w h e n t h e zeta p o t e n t i a l is about -30 m V o r m o r e negative, a n d q u i t e unsta
b l e because o f a g g l o m e r a t i o n w h e n the zeta p o t e n t i a l is b e t w e e n +5 a n d -5
m V . A n e x p a n d e d set o f g u i d e l i n e s , d e v e l o p e d f o r p a r t i c l e suspensions, is
g i v e n i n r e f e r e n c e 48. S u c h c r i t e r i a are f r e q u e n t l y u s e d to d e t e r m i n e o p t i
m a l dosages o f p o l y v a l e n t m e t a l electrolytes, s u c h as a l u m , u s e d to effect
c o a g u l a t i o n i n treatment plants.
F o r example, as stated earlier, i n o r d e r to separate b i t u m e n f r o m o i l
sands, a significant negative charge must b e present at t h e o i l - w a t e r i n t e r
face. T h i s negative charge is n e e d e d to a i d i n t h e release o f the b i t u m e n f r o m
the sand matrix, a n d is also n e e d e d to p r e v e n t attachment o f the released
a n d e m u l s i f i e d d r o p l e t s to c o d i s p e r s e d s o l i d particles s u c h as clays. I n fact,
i n the flotation r e c o v e r y process f o r b i t u m e n the o p t i m a l p r o c e s s i n g c o n d i
t i o n correlates w i t h m a x i m i z i n g the negative charge, o r zeta p o t e n t i a l , o n t h e
droplets (41). O n - l i n e m e a s u r e m e n t s o f the e m u l s i f i e d b i t u m e n d r o p l e t zeta
potentials c a n b e u s e d to m o n i t o r a n d c o n t r o l the c o n t i n u o u s o i l r e c o v e r y
process, as i n d i c a t e d i n F i g u r e 15 (50). I n the F i g u r e 15 example, the m a x i
m u m (negative) e m u l s i o n d r o p l e t zeta p o t e n t i a l a c h i e v e d was about -35 m V ,
w h i c h is consistent w i t h the " g o o d s t a b i l i t y " g u i d e l i n e just d e s c r i b e d .
Schulze-Hardy Rule. T h e t r a n s i t i o n f r o m stable d i s p e r s i o n to ag

gregation u s u a l l y occurs over a f a i r l y s m a l l range o f electrolyte c o n c e n t r a
t i o n . T h i s c o n d i t i o n makes it possible to d e t e r m i n e aggregation c o n c e n t r a
tions, o f t e n r e f e r r e d to as c r i t i c a l c o a g u l a t i o n concentrations ( C C C ) . T h e
S c h u l z e - H a r d y r u l e s u m m a r i z e s t h e general t e n d e n c y o f the C C C to v a r y
i n v e r s e l y w i t h the sixth p o w e r o f the c o u n t e r i o n charge n u m b e r (for i n d i f f e r
ent electrolyte). F u r t h e r details a n d o r i g i n a l references are g i v e n i n refer
ences 13 a n d 51.
A p r e d i c t i o n f r o m D L V O t h e o r y c a n b e m a d e b y d e r i v i n g the c o n d i t i o n s
u n d e r w h i c h V = 0 a n d dV/dH = 0. T h e result is
_9.75JBVfc rV 5
(26)
eN Az
2
A
2 6
Schramm; Emulsions
Figure 15. Flot of oil recoveries versus process aid addition level from the hot
water flotation processing of an oil sand in a continuous pilot plant. Also shown
is the correspondence with the zeta potentials, measured on-line, of emulsified
bitumen droplets in the extraction solution. (Plotted from data in reference 50.)
s h o w i n g that f o r h i g h potentials (7 —» 1), the C C C varies i n v e r s e l y w i t h z . A s 6
an i l l u s t r a t i o n , f o r a h y p o t h e t i c a l e m u l s i o n , e q u a t i o n 26 p r e d i c t s a C C C o f
1.18 M i n solutions o f s o d i u m c h l o r i d e . T h e c r i t i c a l c o a g u l a t i o n c o n c e n t r a
tions i n p o l y v a l e n t m e t a l c h l o r i d e s w o u l d t h e n decrease as f o l l o w s :
Dissolved CCC
Salt ζ (mol/L)
NaCl 1 1.18
CaCl 2 2 0.018
AICI3 3 0.0016
Broad Influence on Stability. I n g e n e r a l , w h e n e l e c t r i c a l surface

charge is a n i m p o r t a n t d e t e r m i n a n t o f stability, i t is easier to f o r m u l a t e a v e r y
stable O / W e m u l s i o n t h a n a W / O e m u l s i o n because the e l e c t r i c d o u b l e - l a y e r
thickness is m u c h greater i n w a t e r t h a n i n o i l . (This c o n d i t i o n is sometimes
i n c o r r e c t l y stated i n terms o f greater charge b e i n g present o n droplets i n an
O / W e m u l s i o n ) . T h i s is not to say that W / O e m u l s i o n s cannot b e s t a b i l i z e d ,
h o w e v e r . M a n y reasonably stable o i l - f i e l d W / O e m u l s i o n s are s t a b i l i z e d b y
a n o t h e r m e c h a n i s m : t h e p r o t e c t i v e action o f viscoelastic, p o s s i b l y r i g i d , films
f o r m e d o n the droplets b y m a c r o m o l e c u l e s o r s o l i d particles.
Schramm; Emulsions
36 EMULSIONS IN THE PETROLEUM INDUSTRY
K i n e t i c s . T h u s far this c h a p t e r has m o s t l y b e e n c o n c e r n e d w i t h an

u n d e r s t a n d i n g o f the d i r e c t i o n i n w h i c h reactions w i l l p r o c e e d . H o w e v e r ,
f r o m an e n g i n e e r i n g p o i n t o f v i e w , it is j u s t as i m p o r t a n t to k n o w the rates at
w h i c h s u c h reactions w i l l p r o c e e d . T w o p r i n c i p a l factors d e t e r m i n e the rate
o f aggregation o f droplets i n an e m u l s i o n : the f r e q u e n c y o f d r o p l e t e n c o u n
ters a n d the p r o b a b i l i t y that the t h e r m a l e n e r g y o f the d r o p l e t s is sufficient
to o v e r c o m e the p o t e n t i a l energy b a r r i e r to aggregation. T h e rate o f ag
gregation c a n b e g i v e n as -(dn/dt) = k n w h e r e k is the rate constant a n d η
2
2
2
is the n u m b e r o f droplets p e r u n i t v o l u m e at t i m e t. F o r η - n at t = 0, 0
1/n = k t + l / n
2 0 (27)
D u r i n g the process o f aggregation, k m a y not r e m a i n constant.

2
I f the energy b a r r i e r to aggregation is r e m o v e d (e.g., b y a d d i n g excess

electrolyte) t h e n aggregation is d i f f u s i o n c o n t r o l l e d ; o n l y B r o w n i a n m o t i o n
o f i n d e p e n d e n t droplets o r particles is present. F o r a m o n o d i s p e r s e suspen
s i o n o f spheres, S m o l u c h o w s k i d e v e l o p e d an e q u a t i o n for this " r a p i d c o a g u
lation"
(28)
1 + 8<nDrn t 0
w h e r e r is the radius, a n d the d i f f u s i o n coefficient D = kT/(6ir^). Nowk = 2
4kT/(3ri), w h e r e k is the rate constant f o r d i f f u s i o n - c o n t r o l l e d aggregation.

2
W h e n t h e r e is an energy b a r r i e r to aggregation, o n l y a f r a c t i o n IfW o f

encounters l e a d to attachment. T h e variable W is the stability ratio, W =
k lk . U s i n g W gives " s l o w c o a g u l a t i o n " ( h i n d e r e d ) t i m e s . I n this case, the
2 2
i n t e r a c t i o n energy a n d h y d r o d y n a m i c viscous d r a g forces must b e c o n s i d

e r e d (16).
F i n a l l y , particles c a n also b e b r o u g h t i n t o i n t e r a c t i o n distances b y stir
r i n g or s e d i m e n t a t i o n so that the relative m o t i o n s o f t w o adjacent regions o f
fluid, each c a r r y i n g particles, c a n cause p a r t i c l e e n c o u n t e r s . C o a g u l a t i o n
d u e to s u c h i n f l u e n c e is c a l l e d " o r t h o k i n e t i c c o a g u l a t i o n " as d i s t i n g u i s h e d
f r o m the B r o w n i a n i n d u c e d " p e r i k i n e t i c c o a g u l a t i o n " . T h e t h e o r y for o r t h o -
k i n e t i c c o a g u l a t i o n is m u c h m o r e c o m p l i c a t e d t h a n that f o r p e r i k i n e t i c a n d is
not discussed h e r e . H o w e v e r , shear can also cause d i s p e r s i o n i f the e n e r g y
i n t r o d u c e d allows the i n t e r a c t i o n energy b a r r i e r to b e o v e r c o m e .
Stability to C o a l e s c e n c e . U p to this p o i n t , stability to aggregation

has b e e n c o n s i d e r e d . H o w e v e r , o n c e aggregation has t a k e n p l a c e i n an
e m u l s i o n , there r e m a i n s the q u e s t i o n o f stability to coalescence. U s u a l l y
e m u l s i o n s m a d e b y m i x i n g t o g e t h e r two p u r e l i q u i d s are not v e r y stable. T o
increase the stability, an a d d i t i o n a l c o m p o n e n t is u s u a l l y n e e d e d , a n d it
f o r m s a film a r o u n d the d i s p e r s e d droplets to p r o v i d e a b a r r i e r to b o t h
Schramm; Emulsions
aggregation a n d coalescence. A l t h o u g h n u m e r o u s agents a n d m e c h a n i s m s

are effective, the a d d i t i o n a l c o m p o n e n t is f r e q u e n t l y a surfactant. S t a b i l i t y
to coalescence involves the m e c h a n i c a l p r o p e r t i e s o f the i n t e r f a c i a l films.
M e c h a n i c a l p r o p e r t i e s w i l l b e c o n s i d e r e d f u r t h e r i n the next section.
C o n s i d e r i n g stability to b o t h aggregation a n d c o a l e s c e n c e , the factors
f a v o r i n g e m u l s i o n stability c a n be s u m m a r i z e d as f o l l o w s :
• L o w i n t e r f a c i a l tension—low i n t e r f a c i a l free energy makes it

easier to m a i n t a i n large i n t e r f a c i a l area.
• M e c h a n i c a l l y strong film—this acts as a b a r r i e r to coalescence
and m a y b e e n h a n c e d b y a d s o r p t i o n o f fine solids o r o f close-
p a c k e d surfactant m o l e c u l e s .
• E l e c t r i c d o u b l e - l a y e r repulsion—this r e p u l s i o n acts to p r e v e n t
collisions a n d aggregation.
• S m a l l v o l u m e o f d i s p e r s e d phase—this reduces the f r e q u e n c y
o f collisions a n d aggregation. H i g h e r v o l u m e s are possible (for
c l o s e - p a c k e d spheres the dispersed-phase v o l u m e f r a c t i o n
w o u l d b e 0.74), b u t i n p r a c t i c e the f r a c t i o n can even b e h i g h e r .
• S m a l l d r o p l e t size, i f the droplets are electrostatically o r steri-

cally i n t e r a c t i n g .
• H i g h viscosity—this slows the rates o f c r e a m i n g a n d coales

cence.
A n assessment o f e m u l s i o n stability involves the d e t e r m i n a t i o n o f the

t i m e v a r i a t i o n o f some e m u l s i o n p r o p e r t y s u c h as those d e s c r i b e d i n the
e a r l i e r section " P h y s i c a l C h a r a c t e r i s t i c s o f E m u l s i o n s " . T h e classical m e t h
ods are w e l l d e s c r i b e d i n r e f e r e n c e 9. S o m e n e w e r approaches i n c l u d e the
use o f p u l s e n u c l e a r m a g n e t i c resonance spectroscopy o r d i f f e r e n t i a l scan
n i n g c a l o r i m e t r y (52).
Emulsifying Agents. O n e g e n e r a l t h e o r y o f e m u l s i o n type states

that i f an e m u l s i f y i n g agent is p r e f e r e n t i a l l y w e t t e d b y one o f the phases,
t h e n m o r e o f the agent c a n be a c c o m m o d a t e d at the interface i f that i n t e r
face is convex t o w a r d that phase; that is, i f that phase is the c o n t i n u o u s
phase. T h i s t h e o r y w o r k s for b o t h solids a n d soaps as e m u l s i f y i n g agents. F o r
surfactant m o l e c u l e s it is r e f e r r e d to as B a n c r o f t ' s r u l e ; the l i q u i d i n w h i c h
the surfactant is most s o l u b l e b e c o m e s the c o n t i n u o u s phase. V e r y o f t e n ,
mixtures o f e m u l s i f y i n g agents are m o r e effective t h a n single c o m p o n e n t s .
S o m e m i x e d emulsifiers m a y f o r m a c o m p l e x at the interface a n d thus y i e l d
l o w i n t e r f a c i a l t e n s i o n a n d a strong i n t e r f a c i a l film.
A s e c o n d g e n e r a l r u l e specifies that soaps o f m o n o v a l e n t m e t a l cations
t e n d to p r o d u c e O / W e m u l s i o n s , b u t those o f p o l y v a l e n t m e t a l cations w i l l
Schramm; Emulsions
t e n d to p r o d u c e W / O e m u l s i o n s . F i g u r e 16 illustrates the c o n c e p t . I n t h e
example s h o w n , the c a l c i u m ions each c o o r d i n a t e to t w o surfactant m o l e
cules that are a l i g n e d w i t h t h e i r p o l a r groups near the m e t a l i o n . T h i s
c o o r d i n a t i o n forces t h e h y d r o c a r b o n tails i n t o a w e d g e l i k e o r i e n t a t i o n . T h e
h y d r o c a r b o n tails i n a c l o s e - p a c k e d i n t e r f a c i a l layer are most easily a c c o m
m o d a t e d i f the o i l phase is t h e c o n t i n u o u s phase. T h u s , the o r i e n t e d - w e d g e
t h e o r y p r e d i c t s that t h e c a l c i u m soap w i l l p r o d u c e a W / O e m u l s i o n . F o r t h e
s o d i u m soap, t h e c h a r g e d p o l a r groups o f the surfactant t e n d to r e p e l e a c h
o t h e r m o r e strongly. T h i s fact, together w i t h the single c a t i o n - s u r f a c t a n t
c o o r d i n a t i o n , makes i t most favorable f o r t h e p o l a r groups to b e i n t h e
c o n t i n u o u s phase, a n d an O / W e m u l s i o n results.
A n analogous r u l e to the o r i e n t e d - w e d g e a n d B a n c r o f t theories states
that t h e l i q u i d that p r e f e r e n t i a l l y wets t h e s o l i d particles w i l l t e n d to f o r m
the c o n t i n u o u s phase. T h u s i f t h e r e is a l o w contact angle ( m e a s u r e d t h r o u g h
the w a t e r phase), t h e n a n O / W e m u l s i o n s h o u l d f o r m . E x c e p t i o n s o c c u r f o r
each o f these rules, a n d s o m e t i m e s o n e w i l l w o r k w h e r e t h e others d o n o t .
They do remain useful for making initial predictions.
A n e m p i r i c a l scale d e v e l o p e d f o r c a t e g o r i z i n g s i n g l e - c o m p o n e n t o r
m i x e d (usually n o n i o n i c ) e m u l s i f y i n g agents, u s i n g this p r i n c i p l e , is t h e
h y d r o p h i l e - l i p o p h i l e balance o r H L B scale. T h i s d i m e n s i o n l e s s scale ranges
f r o m 0 to 2 0 ; a l o w H L B (<9) refers to a l i p o p h i l i c surfactant (oil-soluble)
and a h i g h H L B (>11) to a h y d r o p h i l i c (water-soluble) surfactant. I n g e n -
Figure 16. The oriented-wedge theory of emulsion type.
Schramm; Emulsions
e r a l , W / O emulsifiers exhibit H L B values i n t h e range o f 3 - 8 , a n d O / W

emulsifiers have H L B values o f about 8 - 1 8 . E m p i r i c a l tables o f H L B values
r e q u i r e d to make e m u l s i o n s o u t o f various materials have b e e n p u b
l i s h e d (53). I f the value is n o t k n o w n , t h e n laboratory e m u l s i f i c a t i o n tests are
r e q u i r e d , u s i n g a series o f e m u l s i f y i n g agents o f k n o w n H L B values.
F o r example, to make a 1 5 % O / W e m u l s i o n o f a p a r a f f m i c m i n e r a l o i l , a
set o f e m u l s i o n tests is p e r f o r m e d w i t h a series o f b l e n d s o f emulsifiers A
( H L B 4.7) a n d Β ( H L B 14.9):
Emulsifier Blend HLB Emulsion Test

100% A 4.7 no emulsion
87% A + 13% Β 6 no emulsion
68% A + 32% Β 8 moderate emulsion
48% A + 52% Β 10 stable emulsion
28% A + 72% Β 12 moderate emulsion
6% A + 94% Β 14 no emulsion
100% Β 14.9 no emulsion
In this case a n H L B o f 10 is r e q u i r e d to make the O / W m i n e r a l o i l e m u l s i o n .

V a r i o u s c o m p i l a t i o n s a n d equations f o r d e t e r m i n i n g e m u l s i f i e r H L B
values have b e e n p u b l i s h e d (J5, 53, 54). F o r e x a m p l e , i n p o l y o x y e t h y l e n e
alcohols, C H n 2 n + 1( O C H C H ) O H , a class o f n o n i o n i c surfactants, the H L B
2 2 m
c a n b e c a l c u l a t e d f r o m H L B = E/5, w h e r e Ε is the p e r c e n t a g e b y mass o f

ethylene oxide i n the m o l e c u l e . E x p e r i m e n t a l l y , t h e u n k n o w n H L B o f an
e m u l s i f i e r c a n b e d e t e r m i n e d b y m i x i n g it w i t h an e m u l s i f i e r o f k n o w n H L B
and a n o i l f o r w h i c h t h e H L B r e q u i r e d f o r e m u l s i f i c a t i o n is k n o w n . A series
o f tests s u c h as just i l l u s t r a t e d i n t h e example c a n b e u s e d t o d e t e r m i n e the
u n k n o w n H L B . F r o m the p r e v i o u s d e f i n i t i o n o f s p r e a d i n g i t m i g h t s e e m that
i f an o i l does n o t s p r e a d o n w a t e r , t h e n i t s h o u l d b e e m u l s i f i e d i n i t , a n d v i c e
versa. Ross et a l . (55) d i d , i n fact, find a c o r r e l a t i o n b e t w e e n H L B a n d the
s p r e a d i n g coefficients o f o i l a n d water. T h e y f o u n d that f o r a g i v e n type o f
e m u l s i o n , b o t h l o w i n t e r f a c i a l t e n s i o n a n d a negative v a l u e o f t h e a p p r o p r i
ate s p r e a d i n g coefficient are necessary.
A l i m i t a t i o n o f the H L B system is that o t h e r factors are i m p o r t a n t as
w e l l . A l s o , t h e H L B is an i n d i c a t o r o f the e m u l s i f y i n g characteristics o f a n
e m u l s i f i e r b u t n o t the efficiency o f an e m u l s i f i e r . T h u s , a l t h o u g h a l l e m u l s i
fiers h a v i n g a h i g h H L B w i l l t e n d to p r o m o t e O / W e m u l s i o n s , the e f f i c i e n c y
w i t h w h i c h those emulsifiers act w i l l vary c o n s i d e r a b l y f o r any g i v e n system.
F o r example, usually mixtures o f surfactants w o r k b e t t e r t h a n p u r e c o m
p o u n d s o f the same H L B .
Just as solubilities o f e m u l s i f y i n g agents vary w i t h t e m p e r a t u r e , so does
the H L B , especially f o r the n o n i o n i c surfactants. A surfactant m a y thus
stabilize O / W e m u l s i o n s at l o w t e m p e r a t u r e b u t W / O e m u l s i o n s at some
h i g h e r t e m p e r a t u r e . T h e t r a n s i t i o n t e m p e r a t u r e , that at w h i c h the surfactant
Schramm; Emulsions
changes f r o m s t a b i l i z i n g O / W to W / O e m u l s i o n s , is k n o w n as the phase

i n v e r s i o n t e m p e r a t u r e ( P I T ) . A t the P I T , the h y d r o p h i l i c a n d o l e o p h i l i c
natures o f the surfactant are essentially the same (another t e r m f o r this is the
H L B t e m p e r a t u r e ) . A s a p r a c t i c a l matter, e m u l s i f y i n g agents are c h o s e n so
that t h e i r P I T is far f r o m the expected storage a n d use temperatures o f the
d e s i r e d e m u l s i o n s . I n one m e t h o d (56) an e m u l s i f i e r w i t h a P I T o f about
50 °C h i g h e r t h a n the s t o r a g e - u s e t e m p e r a t u r e is selected. T h e e m u l s i o n
is t h e n p r e p a r e d at the P I T w h e r e v e r y s m a l l d r o p l e t sizes are most easily
c r e a t e d . N e x t , the e m u l s i o n is r a p i d l y c o o l e d to the d e s i r e d use t e m p e r a t u r e ,
at w h i c h n o w the coalescence rate w i l l be slow, a n d a stable e m u l s i o n results.
Protective Agents a n d Sensitization. T h e stability o f a d i s p e r

s i o n c a n be e n h a n c e d (protection) o r r e d u c e d (sensitization) b y the a d d i t i o n
o f m a t e r i a l that adsorbs o n t o p a r t i c l e surfaces. P r o t e c t i v e agents c a n act i n
several ways. T h e y c a n increase d o u b l e - l a y e r r e p u l s i o n i f t h e y have i o n i z a b l e
g r o u p s . T h e a d s o r b e d layers c a n l o w e r the effective H a m a k e r constant. A n
a d s o r b e d film m a y necessitate d e s o r p t i o n b e f o r e particles can a p p r o a c h
closely e n o u g h f o r v a n d e r W a a l s forces to cause attraction. I f the a d s o r b e d
m a t e r i a l extends out significantly f r o m the p a r t i c l e surface, t h e n an e n t r o p y
decrease c a n a c c o m p a n y p a r t i c l e a p p r o a c h (steric stabilization). F i n a l l y , the
a d s o r b e d m a t e r i a l may f o r m s u c h a r i g i d film that it poses a m e c h a n i c a l
b a r r i e r to d r o p l e t coalescence.
O i l - f i e l d W / O e m u l s i o n s m a y be s t a b i l i z e d b y the p r e s e n c e o f a p r o t e c
tive film a r o u n d the w a t e r d r o p l e t s . S u c h a film c a n be f o r m e d f r o m the
asphaltene a n d r e s i n fractions o f the c r u d e o i l . W h e n d r o p l e t s a p p r o a c h each
o t h e r d u r i n g the process o f aggregation, the rate o f o i l film drainage w i l l be
d e t e r m i n e d i n i t i a l l y b y the b u l k o i l viscosity, b u t w i t h i n a c e r t a i n distance o f
a p p r o a c h the i n t e r f a c i a l viscosity b e c o m e s i m p o r t a n t . A h i g h i n t e r f a c i a l
viscosity w i l l significantly r e t a r d the final stage o f film drainage a n d p r o m o t e
k i n e t i c e m u l s i o n stability. I f the films are viscoelastic, t h e n a m e c h a n i c a l
b a r r i e r to coalescence w i l l be p r o v i d e d , y i e l d i n g a h i g h degree o f e m u l s i o n
stability. M o r e d e t a i l e d d e s c r i p t i o n s are g i v e n i n references 26, 57, a n d 58.
S e n s i t i z i n g agents can be p r o t e c t i v e agents that are a d d e d i n s m a l l e r
amounts t h a n w o u l d be u s e d n o r m a l l y . S e n s i t i z i n g agents have several p o s s i
b l e m e c h a n i s m s o f action. I f the additive is o p p o s i t e l y c h a r g e d to the dis
p e r s e d particles, t h e n d e c r e a s e d d o u b l e - l a y e r r e p u l s i o n w i l l result. I n some
k i n d s o f p r o t e c t i n g a d s o r p t i o n , a b i l a y e r is f o r m e d w i t h the o u t e r layer
h a v i n g l y o p h i l i c groups exposed o u t w a r d s . A d d i t i o n o f e n o u g h a d d i t i v e to
f o r m o n l y the single layer w i l l have l y o p h o b i c groups o r i e n t e d o u t w a r d w i t h
a s e n s i t i z i n g effect. I f the additive is o f l o n g c h a i n l e n g t h , sometimes a
b r i d g i n g b e t w e e n particles occurs a n d i n d u c e s aggregation (at h i g h e r c o n
centrations p r o t e c t i v e a c t i o n takes over because the p o t e n t i a l b r i d g i n g sites
become covered).
Schramm; Emulsions
Creaming, Inversion, and Demulsification

C r e a m i n g . D r o p l e t s i n a n e m u l s i o n w i l l have s o m e t e n d e n c y to rise
o r settle a c c o r d i n g to Stokes' l a w . A n u n c h a r g e d s p h e r i c a l d r o p l e t i n a fluid
w i l l s e d i m e n t i f its density is greater t h a n that o f the fluid. T h e d r i v i n g f o r c e
is that o f gravity; t h e resisting f o r c e is viscous a n d is a p p r o x i m a t e l y p r o p o r
t i o n a l to the d r o p l e t velocity. A f t e r a short p e r i o d o f t i m e the p a r t i c l e reaches
t e r m i n a l (constant) v e l o c i t y , dx/dt, w h e n t h e t w o forces are m a t c h e d . T h u s
dx_2r (p -p )g8
2 1 ( 2 g )
dt 9η
w h e r e r is t h e p a r t i c l e radius, p is t h e d r o p l e t density, p is t h e external fluid

2 x
density, g is t h e gravitational constant, a n d η is t h e b u l k viscosity. I f t h e

d r o p l e t has a l o w e r density t h a n t h e external phase, t h e n i t rises i n s t e a d
(negative s e d i m e n t a t i o n ) . E m u l s i o n droplets are n o t r i g i d spheres, so they
may d e f o r m i n shear flow. A l s o , w i t h the p r e s e n c e o f e m u l s i f y i n g agents at
the interface, t h e droplets w i l l n o t b e n o n i n t e r a c t i n g , as is a s s u m e d i n t h e
theory. T h u s , Stokes' l a w w i l l n o t strictly a p p l y a n d may u n d e r e s t i m a t e o r
e v e n overestimate t h e real t e r m i n a l velocity.
T h e process i n w h i c h e m u l s i o n droplets rise o r settle w i t h o u t significant
coalescence is c a l l e d c r e a m i n g ( F i g u r e 17). T h i s process is n o t e m u l s i o n
b r e a k i n g , b u t p r o d u c e s two separate layers o f e m u l s i o n that have d i f f e r e n t
d r o p l e t concentrations a n d are usually d i s t i n g u i s h a b l e f r o m each o t h e r b y
c o l o r o r opacity. T h e t e r m c o m e s f r o m t h e f a m i l i a r separation o f c r e a m f r o m
raw m i l k . A c c o r d i n g to Stokes' law, c r e a m i n g w i l l o c c u r faster w h e n t h e r e is
a larger density d i f f e r e n c e a n d w h e n t h e droplets are larger. T h e rate o f
separation can b e e n h a n c e d b y r e p l a c i n g t h e gravitational d r i v i n g force b y a
c e n t r i f u g a l field. C e n t r i f u g a l force, l i k e gravity, is p r o p o r t i o n a l to t h e mass,
b u t t h e p r o p o r t i o n a l i t y constant is n o t g b u t ω χ , w h e r e ω is t h e angular
2
v e l o c i t y (equal to 2ΊΓ x revolutions p e r second) a n d χ is t h e distance o f t h e

p a r t i c l e f r o m the axis o f r o t a t i o n . T h e d r i v i n g force f o r s e d i m e n t a t i o n b e
comes (p - ρ ) ω χ . B e c a u s e ω χ is s u b s t i t u t e d f o r g, o n e speaks o f m u l t i p l e s
2 χ
2 2
o f g, o r " g s " , i n a c e n t r i f u g e . T h e c e n t r i f u g a l acceleration i n a c e n t r i f u g e is

not r e a l l y a constant t h r o u g h o u t t h e system b u t varies w i t h x. T h e actual
distance f r o m t o p to b o t t o m o f a s e d i m e n t i n g c o l u m n is usually s m a l l c o m
p a r e d to t h e distance f r o m t h e c e n t e r o f r e v o l u t i o n , so t h e average accelera
t i o n is u s e d . T h e t e r m i n a l v e l o c i t y t h e n b e c o m e s
dx _ 2 r ( p - Pi) ω χ
2
2
2
^
dt 9η
T h e p r o b l e m o f deaerated b i t u m i n o u s f r o t h p r o d u c e d f r o m t h e h o t -
w a t e r flotation o f b i t u m e n f r o m o i l sands c a n serve as a n i l l u s t r a t i o n . T h i s
Schramm; Emulsions
Figure 17. Creaming, aggregation, and coalescence in an O/W emulsion.
f r o t h is a W / O e m u l s i o n f r o m w h i c h t h e w a t e r must b e r e m o v e d p r i o r to
u p g r a d i n g a n d r e f i n i n g . A t process t e m p e r a t u r e (80 °C) t h e e m u l s i o n viscos
ity is s i m i l a r to that o f t h e b i t u m e n , b u t t h e density, because o f e n t r a i n e d
solids, is h i g h e r . T a k i n g η = 5 0 0 mPa-s (59) a n d p = 1.04 g/mL, t h e rate o f
x
rise o f 2 0 - μ π ι d i a m e t e r w a t e r droplets u n d e r gravitational force w i l l b e v e r y

slow. A c c o r d i n g to e q u a t i o n 2 9 :
rlr
— = -3.05xl0" 6
cm/s
di
ek
— = 96 cm/year u p w a r d
dt
I n a c o m m e r c i a l o i l sands p l a n t , a c e n t r i f u g e process is u s e d to s p e e d u p
the separation. T h e c o n t i n u o u s centrifuges c a n operate at 2500 x g , t h e
Schramm; Emulsions
droplets h a v i n g to travel 9 c m to reach the p r o d u c t stream. W i t h the centrif

u g a l force a d d e d , a c c o r d i n g to e q u a t i o n 30, the d r o p l e t v e l o c i t y w o u l d
become
dx àx
= 2500
.di. dt
dx
= 7.63 X 1 0 " 3
cm/s o u t w a r d
l dï I
T h i s result is 2500 x faster t h a n w i t h gravity alone, b u t the r e s i d e n c e t i m e i n

the c e n t r i f u g e w o u l d have to be about 20 m i n , a n d this l e n g t h o f t i m e is not
p r a c t i c a l . T o s p e e d u p the separation, n a p h t h a is a d d e d to the l e v e l o f 2 5 % .
T h e n a p h t h a lowers the viscosity to about 4.5 mPa-s (59) a n d lowers the
density o f the c o n t i n u o u s phase to 0.88 g/mL. N o w the w a t e r d r o p l e t s w o u l d
s e d i m e n t rather than rise u n d e r gravitational force, a n d a l t h o u g h the e m u l
s i o n density is m u c h r e d u c e d , the absolute value o f the density d i f f e r e n c e
changes v e r y l i t t l e : Δ ρ = - 0 . 0 7 g/mL o r i g i n a l l y , a n d b e c o m e s Δ ρ = +0.09
g/mL! T h e o v e r a l l effect is to l o w e r the viscosity b y about 2 orders o f
m a g n i t u d e . T h e d r o p l e t v e l o c i t y n o w b e c o m e s ( c k / d i ) = 1.1 cm/s, w h i c h
n
yields a satisfactory residence t i m e o f about 8 s.

I n general, f o r g i v e n l i q u i d densities, c r e a m i n g w i l l o c c u r m o r e s l o w l y
the greater the e l e c t r i c a l charge o n the droplets a n d the h i g h e r the e m u l s i o n
viscosity. A l t h o u g h a d i s t i n c t process, c r e a m i n g does p r o m o t e coalescence
b y i n c r e a s i n g the d r o p l e t c r o w d i n g a n d h e n c e the p r o b a b i l i t y o f d r o p l e t -
droplet collisions.
Inversion. I n v e r s i o n refers to the process i n w h i c h an e m u l s i o n

s u d d e n l y changes f o r m , f r o m O / W to W / O , or v i c e versa. T h i s process was
e n c o u n t e r e d i n the example o f c h a n g i n g e m u l s i o n viscosity g i v e n i n the
e a r l i e r section, " P h y s i c a l C h a r a c t e r i s t i c s o f E m u l s i o n s " , subsection " B u l k
V i s c o s i t y P r o p e r t i e s " ( F i g u r e 6). T h e m a x i m u m v o l u m e f r a c t i o n possible f o r
an i n t e r n a l phase m a d e u p o f u n i f o r m , i n c o m p r e s s i b l e spheres is 74%.
Although emulsions with a higher internal volume fraction do occur, usually
i n v e r s i o n occurs w h e n the i n t e r n a l v o l u m e f r a c t i o n exceeds some value
reasonably close to φ = 0.74. O t h e r factors have a b e a r i n g as w e l l , o f course,
i n c l u d i n g the nature a n d c o n c e n t r a t i o n o f emulsifiers a n d p h y s i c a l i n f l u
ences s u c h as t e m p e r a t u r e or the a p p l i c a t i o n o f m e c h a n i c a l shear.
T h e exact m e c h a n i s m o f i n v e r s i o n r e m a i n s u n c l e a r , a l t h o u g h o b v i o u s l y
some processes o f c o a l e s c e n c e a n d d i s p e r s i o n are i n v o l v e d . I n the r e g i o n o f
the i n v e r s i o n p o i n t m u l t i p l e e m u l s i o n s m a y be e n c o u n t e r e d . T h e process is
also not always exactly r e v e r s i b l e . T h a t is, hysteresis m a y o c c u r i f the i n v e r
s i o n p o i n t is a p p r o a c h e d f r o m d i f f e r e n t sides o f the c o m p o s i t i o n scale.
F i g u r e 18 shows the i r r e v e r s i b l e i n v e r s i o n o f a d i l u t e d b i t u m e n - i n - w a t e r
e m u l s i o n b r o u g h t about b y the a p p l i c a t i o n o f shear (60).
Schramm; Emulsions
Low Shear Moderate Shear High Shear
\ O/W
• \
•
S /
Remains W/O \
^ Inverts to W/O
-y Finer Droplets
1 1 i I 1 1 1 1 1
Shear Rate
Figure 18. Example of the shear-induced inversion of an emulsion of diluted
bitumen in water. (Reproduced with permission from Syncrude Canada Lim-
ited.
Demulsification (Emulsion Breaking). T h e stability o f a n

e m u l s i o n is o f t e n a p r o b l e m . D e m u l s i f i c a t i o n involves t w o steps. F i r s t ,
a g g l o m e r a t i o n o r coagulation o f droplets m u s t o c c u r . T h e n , t h e agglomer
ated droplets must coalesce. O n l y after these t w o steps c a n c o m p l e t e phase
separation o c c u r . E i t h e r step c a n b e rate d e t e r m i n i n g for the d e m u l s i f i c a
t i o n process. A t y p i c a l W / O p e t r o l e u m e m u l s i o n f r o m a p r o d u c t i o n w e l l
m i g h t c o n t a i n 6 0 - 7 0 % water. S o m e o f this (free water) w i l l r e a d i l y settle out.
T h e rest (bottom settlings*) r e q u i r e s s o m e k i n d o f specific e m u l s i o n treat
ment.
T h e first step i n systematic e m u l s i o n b r e a k i n g is t o c h a r a c t e r i z e t h e
e m u l s i o n to be b r o k e n i n terms o f its nature (O/W o r W / O ) , the nature o f the
two phases, a n d t h e sensitivity o f the emulsifiers. O n t h e basis o f s u c h a n
evaluation, a c h e m i c a l a d d i t i o n c o u l d b e m a d e t o n e u t r a l i z e the effect o f the
e m u l s i f i e r , f o l l o w e d b y m e c h a n i c a l means t o c o m p l e t e the phase separation.
F o r example, b u t t e r results f r o m t h e c r e a m i n g , b r e a k i n g , a n d i n v e r s i o n o f
e m u l s i f i e d droplets i n m i l k .
It follows d i r e c t l y f r o m the p r e v i o u s considerations o f e m u l s i o n stability
that i f an e m u l s i o n is s t a b i l i z e d b y e l e c t r i c a l r e p u l s i v e forces, t h e n d e m u l s i f i -
* Hence the field term "bottom settlings and water", or BS&W, used to characterize petroleum
samples. {See also the Glossary.)
Schramm; Emulsions
c a t i o n c o u l d be b r o u g h t about b y o v e r c o m i n g o r r e d u c i n g these forces. I n

this context the a d d i t i o n o f electrolyte to an O / W e m u l s i o n c o u l d b e u s e d to
achieve the c r i t i c a l c o a g u l a t i o n c o n c e n t r a t i o n , i n a c c o r d w i t h the S c h u l z e -
H a r d y r u l e . S i m i l a r l y , d e m u l s i f y i n g agents, d e s i g n e d to r e d u c e e m u l s i o n
stability b y d i s p l a c i n g o r d e s t r o y i n g the effectiveness o f p r o t e c t i v e agents,
c a n b e a p p l i e d . A n example is antagonistic a c t i o n , that is, a d d i t i o n o f an O / W
p r o m o t e r to b r e a k a W / O e m u l s i o n (see the e a r l i e r section " P r o t e c t i v e
A g e n t s a n d Sensitization")- T h e s e considerations are d i s c u s s e d i n f u r t h e r
d e t a i l i n C h a p t e r 9.
A p a r t f r o m the a f o r e m e n t i o n e d c h e m i c a l treatments, a variety o f p h y s i
cal m e t h o d s are u s e d i n e m u l s i o n b r e a k i n g . T h e s e p h y s i c a l m e t h o d s are a l l
d e s i g n e d to accelerate c o a g u l a t i o n a n d coalescence. F o r example, o i l - f i e l d
W / O e m u l s i o n s m a y b e t r e a t e d b y some o r a l l o f settling, h e a t i n g , e l e c t r i c a l
d e h y d r a t i o n , c h e m i c a l treatment, c e n t r i f u g a t i o n , a n d filtration. T h e m e
c h a n i c a l m e t h o d s , s u c h as c e n t r i f u g i n g or filtering, r e l y o n i n c r e a s i n g the
c o l l i s i o n rate o f d r o p l e t s a n d a p p l y i n g an a d d i t i o n a l force that drives coales
c e n c e . A n increase i n t e m p e r a t u r e w i l l increase t h e r m a l m o t i o n s to e n h a n c e
the c o l l i s i o n rate, a n d also r e d u c e viscosities ( i n c l u d i n g i n t e r f a c i a l viscosity),
and thus increase the l i k e l i h o o d o f coalescence. I n the extremes, v e r y h i g h
temperatures w i l l cause d e h y d r a t i o n d u e to e v a p o r a t i o n , a n d f r e e z e - t h a w
cycles w i l l break some e m u l s i o n s . E l e c t r i c a l m e t h o d s m a y i n v o l v e e l e c t r o
phoresis o f o i l d r o p l e t s , c a u s i n g t h e m to c o l l i d e , to b r e a k O / W e m u l s i o n s .
W i t h W / O e m u l s i o n s , the m e c h a n i s m involves d e f o r m a t i o n o f w a t e r d r o p
lets, because W / O e m u l s i o n s are essentially n o n c o n d u c t i n g e m u l s i o n s . H e r e
the e l e c t r i c field causes an increase i n the d r o p l e t area a n d disrupts the
i n t e r f a c i a l film. I n c r e a s e d d r o p l e t contacts increase the coalescence rate a n d
t h e r e b y break the e m u l s i o n . M o r e details o n the a p p l i c a t i o n o f these m e t h
ods i n large-scale c o n t i n u o u s processes are g i v e n i n C h a p t e r 10.
List of Symbols
as area p e r a d s o r b e d m o l e c u l e
A available area o f surface .sp 0.2 H a m a k e r constant
Β a constant (3.93 χ 1 0 39
A~Y ) 2
C s s o l u t i o n c o n c e n t r a t i o n o f the surfactant ( M )
c{ i n d i v i d u a l i o n concentrations
D d i f f u s i o n coefficient
àx/dt t e r m i n a l (constant) v e l o c i t y (in c r e a m i n g )
e e l e m e n t a r y e l e c t r o n i c charge
g gravitational constant
H distance separating s p h e r i c a l e m u l s i o n droplets
I i o n i c strength
Schramm; Emulsions
I 0 i n t e n s i t y o f i n c i d e n t l i g h t b e a m (in l i g h t - s c a t t e r i n g experiments)
I
d i n t e n s i t y o f l i g h t scattered (in l i g h t - s c a t t e r i n g experiments)
I
t intensity o f t r a n s m i t t e d b e a m o f l i g h t (in l i g h t - s c a t t e r i n g e x p e r i
ments)
k B o l t z m a n n constant
k 2 rate constant
k 2 rate constant for d i f f u s i o n - c o n t r o l l e d aggregation
I l e n g t h o f p a t h t h r o u g h sample (in l i g h t - s c a t t e r i n g experiments)
η n u m b e r o f moles; n u m b e r o f d r o p l e t s p e r u n i t v o l u m e at t i m e t
n 0 n u m b e r o f droplets p e r u n i t v o l u m e at t i m e t = 0
N A Avogadro's number
N c capillary number
Ρ> ΡPB p r e s s u r e , pressure i n phase A , pressure i n phase Β
F c c a p i l l a r y pressure
r radius o f s m a l l d r o p l e t s
r p p o r e radius
R radius o f s p h e r i c a l droplets
also u s e d as the gas constant
R R l 2 principal radii of curvature
t time
Γ absolute t e m p e r a t u r e
T K t e m p e r a t u r e , t e r m e d the K r a f f t p o i n t , at w h i c h solubilities o f
surfactants show a s t r o n g increase d u e to m i c e l l e f o r m a t i o n
υ v e l o c i t y o f d i s p l a c i n g fluid
V total i n t e r a c t i o n energy
V A attractive energy f o r s p h e r i c a l d r o p l e t s
V R r e p u l s i v e energy f o r s p h e r i c a l d r o p l e t s
W stability ratio
χ distance f r o m d r o p l e t at w h i c h i n t e n s i t y o f scattered l i g h t is taken
(in l i g h t - s c a t t e r i n g e x p e r i m e n t )
ζ c o u n t e r i o n charge n u m b e r
z { individual ion-charge numbers
Greek
a , a , a 0 x 2 e m p i r i c a l constants i n equations d e s c r i b i n g e m u l s i o n viscosity

7 o i l - w a t e r i n t e r f a c i a l t e n s i o n also u s e d as a t e r m i n the r e p u l s i v e
energy expression for s p h e r i c a l d r o p l e t s
7 shear rate
7° surface t e n s i o n
T s surface excess o f surfactant
δ distance f r o m d r o p l e t surface to S t e r n p l a n e
e permittivity
ζ zeta p o t e n t i a l
Ύ] viscosity
Schramm; Emulsions
i n t r i n s i c viscosity
viscosity o f c o n t i n u o u s phase
apparent viscosity
VD d i f f e r e n t i a l viscosity
%ed r e d u c e d viscosity
%el relative viscosity
specific increase i n viscosity
θ contact angle o f a n o i l - w a t e r interface i n contact w i t h a s o l i d
surface
Ι/κ d o u b l e - l a y e r thickness
Kc c o n d u c t i v i t y o f c o n t i n u o u s phase
«Ό c o n d u c t i v i t y o f d i s p e r s e d phase
conductivity o f emulsions
λ w a v e l e n g t h o f l i g h t (in l i g h t - s c a t t e r i n g e x p e r i m e n t )
μ Ε
electrophoretic mobility
ΤΓ e x p a n d i n g pressure (surface pressure)
Pi external fluid density
Ρ 2
d r o p l e t density
σ charge density
σ° surface charge density
τ turbidity
shear stress
Τγ y i e l d stress
Φ dispersed-phase v o l u m e f r a c t i o n
Ψ potential
surface p o t e n t i a l
ω angular v e l o c i t y
Acknowledgments
I t h a n k E d d y Isaacs ( A l b e r t a R e s e a r c h C o u n c i l ) a n d K a r i n M a n n h a r d t (Pe
t r o l e u m R e c o v e r y Institute) f o r v e r y h e l p f u l discussions a n d suggestions
r e g a r d i n g the m a n u s c r i p t . V a l u a b l e suggestions o f f e r e d b y the external ref
erees are also gratefully a c k n o w l e d g e d .
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2. Danyluk, M.; Galbraith, B.; Omana, R. In The Future of Heavy Crude and Tar
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Schramm; Emulsions
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Measurement; Wiley: New York, 1963.
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glewood Cliffs, N J , 1964.
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K. L . , E d . ; A C S Symposium Series 8; American Chemical Society: Washington,
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297-329.
38. Takamura, K . Can. J. Chem. Eng. 1982, 60, 538-545.
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New York, 1977.
52. Cavallo, J. L.; Chang, D . L. Chem. Eng. Prog. 1990; 86, 54-59.
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R E C E I V E D for review December 18, 1990. A C C E P T E D revised manuscript A p r i l 26,

1991.
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1

Petroleum Recovery Institute, 3512 33rd Street N.W., Calgary, Alberta,

This chapter provides an introduction to the occurrence, properties,

Figure 1. Photomicrograph of an emulsified droplet of a crude oil, dispersed in

tant p r o p e r t i e s that may b e desirable, f o r example, i n a n a t u r a l o r f o r m u l a t e d

Viscosity Range (mPa-s), Density Range (kg/m ), 3

Hydrocarbon at Reservoir Temperature at 15.6 °C

B e c a u s e the viscosities c o r r e s p o n d to a m b i e n t deposit t e m p e r a t u r e s ,

that o f water). D u r i n g h e a t i n g , as part o f an o i l r e c o v e r y process s u c h as hot-

Table I. Examples of Emulsions in the

e m u l s i o n that is p u r p o s e l y c r e a t e d i n a reservoir as part o f a n o i l r e c o v e r y

Their Technical Treatment (5) a n d n u m e r o u s o t h e r books o n e m u l s i o n s (6-

Emulsions as Colloidal Systems

T h i s k i n d o f classification is n o t always a p p r o p r i a t e . F o r e x a m p l e , O/W/O

o t h e r factors d e t e r m i n e the o u t c o m e . T a b l e I lists some s i m p l e examples o f

Stability. A c o n s e q u e n c e o f the s m a l l d r o p l e t size a n d p r e s e n c e o f an

total surface area. A g g r e g a t i o n is sometimes r e f e r r e d to as flocculation o r

m N / m ; l o w i n t e r f a c i a l t e n s i o n allows spontaneous o r n e a r l y spontaneous

w h e r e 7 is the o i l - w a t e r i n t e r f a c i a l t e n s i o n ; θ is t h e contact angle, w h i c h is

f u r t h e r i n a later section. I n a n i d e a l i z e d w a t e r - w e t reservoir, t h e i n t e r f a c i a l

reservoir c o n s i s t i n g o f s u c h c a p i l l a r y tubes that c o n t a i n w a t e r a n d o i l , w a t e r

w h e r e η a n d υ are the viscosity a n d v e l o c i t y , respectively, o f the d i s p l a c i n g

Figure 3. A generalized capillary number correlation. (Courtesy of K. Taylor,

e n d o f the w a t e r - f l o o d the r e s i d u a l o i l saturation is still a r o u n d 4 5 % . H o w

T h e m i c e l l e s present also h e l p to s o l u b i l i z e the released o i l d r o p l e t s ;

Physical Characteristics of Emulsions

• Texture. T h e texture o f an e m u l s i o n f r e q u e n t l y reflects that o f

• Dyeing. E m u l s i o n s are most r e a d i l y a n d consistently c o l o r e d

• Fluorescence. I f t h e o i l phase fluoresces, then fluorescence

E m u l s i o n s d o n o t always o c c u r i n t h e i d e a l i z e d f o r m o f droplets o f one

types O/W/O a n d W / O A V , has already b e e n m e n t i o n e d . P e t r o l e u m e m u l ­

D r o p l e t Sizes. A s stated p r e v i o u s l y , c o l l o i d a l d r o p l e t s are b e t w e e n

o f t e n larger (e.g., t h e fat droplets i n m i l k ) . I n fact, e m u l s i o n droplets u s u a l l y

Figure 4. Photomicrograph of an enhanced oil recovery process foam contain­

have diameters greater t h a n 0.2 μπι a n d m a y b e larger t h a n 50 μ ι η . E m u l ­

w h e r e I is the i n t e n s i t y o f t h e t r a n s m i t t e d b e a m , I is the i n t e n s i t y o f the

T h e s e approaches to d e t e r m i n i n g d r o p l e t size d i s t r i b u t i o n s are d i s ­

Conductivity. Conductivity can be used to distinguish O/W f r o m

the d i s p e r s e d phase ( K ) is m u c h s m a l l e r t h a n that o f t h e c o n t i n u o u s phase

w h e r e φ is the dispersed-phase v o l u m e f r a c t i o n . If, o n t h e o t h e r h a n d , t h e

F u r t h e r discussion o f emulsion conductivity a n d some practical exam­

Rheology. Bulk Viscosity Properties. T h e rheological properties

w h e r e 17 has units o f m i l l i p a s c a l seconds. M a n y c o l l o i d a l d i s p e r s i o n s , i n c l u d ­

curves c a n be c a t e g o r i z e d i n t o several r h e o l o g i c a l classifications. E m u l s i o n s

N e w t o n i a n flow begins. P s e u d o p l a s t i c flow that is t i m e d e p e n d e n t is t e r m e d

Table II. Glossary of Bulk Viscosity Terms

Apparent viscosity T|APP η ρρ = τ/7 but as determined for a non-

Newtonian fluid, usually by a method suitable

Differential viscosity ηϋ = dT/d"y

Intrinsic viscosity [η] [η] = lim -»o lim ^ ^sv/C

[η] = lim ->o lim γ_> (1/C) In n j

Reduced viscosity η Red nRed = Tjsp/C

Relative viscosity nRei = η/ηο

c h a m b e r that make the measurements i r r e p r o d u c i b l e a n d not representative

• creaming o f the droplets, causing a n o n u n i f o r m distribution

• c e n t r i f u g a l separation o f o i l , water, a n d s o l i d phases, m a k i n g

It is f r e q u e n t l y desirable to b e able to d e s c r i b e e m u l s i o n viscosity i n

Figure 5. Some rheological measurement problems that may be encountered

w h e r e η is the m e d i u m viscosity a n d φ is the dispersed-phase v o l u m e

f r a c t i o n a n d is <1. F o r e x a m p l e , the e m p i r i c a l equations t y p i c a l l y have the

w h e r e the a s are e m p i r i c a l constants, a n d the e m p i r i c a l equations may

η = + 2 . 5 φ + 1 O . 5 0 + 0.00273 exp (16.60) ]

T h e s e equations assume N e w t o n i a n b e h a v i o r , o r at least a p p l y to the N e w t o ­

types O/W/O a n d W / O A V , has already b e e n m e n t i o n e d . P e t r o l e u m e m u l

Figure 4. Photomicrograph of an enhanced oil recovery process foam contain

have diameters greater t h a n 0.2 μπι a n d m a y b e larger t h a n 50 μ ι η . E m u l

T h e s e approaches to d e t e r m i n i n g d r o p l e t size d i s t r i b u t i o n s are d i s

F u r t h e r discussion o f emulsion conductivity a n d some practical exam

w h e r e 17 has units o f m i l l i p a s c a l seconds. M a n y c o l l o i d a l d i s p e r s i o n s , i n c l u d

T h e s e equations assume N e w t o n i a n b e h a v i o r , o r at least a p p l y to the N e w t o

m b y the t i m e droplets o f 0.64-μιτι radius have b e e n p r o d u c e d . T h i s i n

Young-Laplace Equation. I n t e r f a c i a l t e n s i o n causes a pressure d i f

Figure 8. Surfactant associations in an O/W emulsion. The size of the surfac

greater t h a n s o l v e n t - s o l v e n t forces o n the o t h e r h a n d , t h e n m o l e c u l a r m i

Surface Films. I n s o l u b l e p o l a r m o l e c u l e s (e.g., l o n g - c h a i n fatty ac

allows c a l c u l a t i o n o f the effective area p e r m o l e c u l e (A/nN ) i n the m o n o

Electrostatic F o r c e s . Charged Interfaces. M o s t substances ac

surface charge influences t h e d i s t r i b u t i o n o f n e a r b y ions i n t h e p o l a r m e

(charged surface). T h e f o u r types o f e l e c t r o k i n e t i c m e a s u r e m e n t s are elec

Repulsive Forces. I n t h e s i m p l e s t e x a m p l e o f c o l l o i d stability, e m u l

Dispersion Forces, v a n d e r W a a l s p o s t u l a t e d that n e u t r a l m o l e