Colloids and Surfaces, 1 1 t 1984) 129--136 129

Elsevier Science Publishers B.V., Amsterdam -- Printed in The l~/etherlands

INTERACTION OF ENHANCED OIL RECOVERY SURFACTANTS WITH ;

MODEL CRUDE OIL SURFACTANTS

J.H. CLINT, E.L. NEUSTADTER and P.A. W H E E L E R

The British Petroleum Company pie, BP Research Centre, Chertsey Road,
8unbury-on-Thame~ Middlesex, T W I 6 7LN (United Kingdom)
(Received 24 J a n u a r y 1983; accepted in final form 15 December 1983)

ABSTRAC'Y

Transient minima r~re o f t e n observed in the Interracial tension o f enhanced oil recovery
surfactants against crude oil. One possible explanation for the time-dependence is t h e
interaction o f surfactants from the crude oil with those from t h e aqueous ph~.se at the
interface. The suggested mechanism involves the diffusion o f crude oil surfactants initially
into t h e interface forming a mixed layer responsible for the low tension followed by
solubilisation in t h e bulk aqueous solution. This mechanism has been investigated for a
carboxyhetaine surfactant with de ,~ane and decanoic acid as model oil and oil surfactant,
respectively. ]Rheological pzoperties and mlcellar sizes have been determined For two
regimes corresponding to different degrees o f enhancement o f surfac~ant concentration at
the interface. The lowest tensions are observed close t o the b o u n d a r y between viscous
surfactant solutions c o n t a i n i n g large micelles and a two-liquid-phase region. The low
tensions e x t e n d into the t w o - p h a l ~ e o m p o s i t i o n range. The occurrence o f low Interfaei~l
tensions is postulated to correspond t o the compositions f o r which hydrocarbon soiubll-
isation in the surfactant phase is a maximum.

INTRODUCTION

Primary and secondary crude oil recovery processes frequently leave

s u b s t a n t i a l q u a n t i t i e s r e m a i n i n g in p l a c e in t h e r e s e r v o i r . E s t i m a t e s r a n g e
f r o m 5 0 - - 7 0 % [1] o f t h e original reserves. C o n s i d e r a b l e e c o n o m i c b e , e f i t s
would accrue from the efficient recovery of a significant quantity of the
r e s i d u a l oil. T h i s o i l m a y b e m o b i l i s e d i f t h e i n t e r f a c i a l t e n s i o n b e t w e e n t h e
aqueous flooding phase and the crude can be reduced significantly to release
t r a p p e d off g a n g l i a . L o g i s t i c r e q u i r e m e n t s d i c t a t e t h a t t h e m o s t s u i t a b l e
e n h a n c e d o i l r e c o v e r y t e c h n i q u e f o r o f f - s h o r e r e s e r v o i r s is l i k e l y t o b e a l o w
concentration surfactant flood produced by continuous injection.
Theoretical consideratio, s and practical experience with model reservoirs
h a v e i n d i c a t e d t h a t i t is n e t . e s s a r y t o r e d u c e t h e i n t e r f a c i a l t e n s i o n b e t w e e n
crude oil and the surfactmit solution to approximately 10 -3 mN m -* [2].
One class of surfactants capable of achieving this target are carboxyhetaines.
However, these materials failed to displace significant quantities of oil from

0166-662218|1503.@0 © 1984 Elsevier Science Publishers B.V.

130 -

s a n d p a c k s u s e d as m o d e l r e s e r v o i r s . O n e r e a s o n f o r t h i s f a i l u r e w a s u n -
d o u b t e d l y t h e p r o p e n s i t y t o r e n d e r t h e s a n d oil w e t , t h u s e x t e n d i n g t h e
period required for recovery beyond the timescale of the experiment.
H o w e v e r , o f c o m p a r a b l e i m p o r t a n c e w a s t h e o b s e r v a t i o n t h a t ~d e s p i t e t h e
a c h i e v e m e n t o f v e r y l o w t r a n s i e n t i n t e r r a c i a l t e n s i o n s a g a i n s t c r u d e oil
( t y p i c a l l y ~ 4 × 1 0 -3 m N m -1 a f t e r 3 0 r a i n i n t h e s p i n n i n g d r o p t e n s i o m e t e r ) ,
e q u i l i b r i u m v a l u e s ( ; ~ 2 4 h ) w e r e in t h e r a n g e 0 . 2 - - 1 . 0 m N m - 1 .
U l t r a - l o w t r a n s i e n t t e n s i o n s a r e well k n o w n in l o w - c o n c e n t r a t i o n -
surfactant systems. A mixed anionie/zwitterionic surfactant system in which
t h e s e p h e n o m e n a a r e o b s e r v e d h a s b e e n d e s c r i b e d [ 3 ] . O n e p r o p o s e d ex-
p l a n a t i o n f o r t h e s e t r a n s i e n t t e n s i o n s is i n i t i a l d i f f u s i o n o f c r u d e oil
surfactants to the interface forming a mixed surfactant layer responsible for
t h e l o w t e n s i o n s . S u b s e q u e n t l y , s m a l l o,u a n t i t i e s o f t h e c r u d e oil s u r f a c t a n t s
are solubilised away from the interface into the bulk aqueous surfactant
s o l u t i o n a n d t h e t e n s i o n rises a g a i n . A s t u d y o f t h e i n f l u e n c e o f s u r f a c e -
a c t i v e c o m p o n e n t s o f t h e c r u d e o n r h e o l o g t c a l p r o p e r t i e s o f o i l / w a t e r inter-
faces h a s d e m ~ n . ~ t r a t e d t h e e x i s t e n c e o f v i s c o u s o r v i s c o e l a s t i c f i l m s [ 4 ] .
In o r d e r t o i n v e s t i g a t e t h e v a l i d i t y o f t h e p r o p o s e d e x p l a n a t i o ] t t h e rela-
tionship between phase behaviour, micellar properties and interracial tension
w a s i n v e s t i g a t e d f o r m i x t u r e s o f h c x a d c . ~ y l d i m e t h y l a m m o n i o m e t h a n e earb-
o x y l a t e ( S , ) a n d d e c a n o i c a c i d ($2) as m o d e l c r u d e oil s u r t ' a c t a n t . M i c e l l a r
sizes w e r e d e t e r m i n e d b y r h e o l o g i c a l m e a s u r e m e n t s in t w o c o t ~ c e n t r a t i o n
r e g i o n s ; 1 . 3 3 X 1 0 - 2 M Sj + 5 . 8 X 1 0 - 4 ~ 5 . 8 X 1 0 - 3 M S= r e p r e s e n t i n g
i n t e l ' f a c e c o n c e n t r a t i o n s s i m i l a r t o t h o s e in t h e b u l k a n d 1 . 5 3 X 1 0 - t M
S, + 5.8 × 1 0 - ~ - - 5 . 8 X 1 0 - = 3 / $ 2 r e f l e c t i n g t h e p o s s i b l e e n h a n c e m e n t o f
t h e cor, centrati(>n o f s u r f a c e - a c t l v e s p e c i e s a t t h e i n t e r f a c e .

MATERIALS AND MFoTHODS

Hexadecyldimethylammoniomethane c a r b o x y l a t e w a s p r e p a r e d b y re-
fluxing hexadecyldimethylamine with sodium chloroacetate and separating
t h e NaCI f r o m t h e p r o d u c t b y e x t r a c t i o n . H P L C analy-~is i n d i c a t e d t h e
s u r f a e t a n t w a s ~ 9 9 % p u r e . D e c a n o i c a c i d w a s F l u k a p u r i s s g r a d e . All ~olu-
t i o n s w e r e p r e p a r e d in f i l t e r e d s e a w a t e r a d j u s t e d t o p H 6 . 5 b y HCI a n d
NaOH solutions. Solutions were prepared by heating to 60--70°C for several
hours to ensure intimate mixing of components followed by equilibrating at
room temperature for at least seven days.
Interracial tensions were measured against decmle using the Texas spinning
drop tensiometer. Rheological measurements on the higher concentration
range samples were made using the Weissenberg Rheogonimeter fitted with
5 . 0 c m c o n e - a n d - p l a t e , u s i n g b o t h s t e a d y s h e a r a n d o s c i l l a t o o y mot~.~s. F o r
the lower concentration range a Contraves LS 30 concentric cylinder (low
s h e a r ) v i s c o m e t e r w a s u s e d . All m e a s u r e m e n t s w e r e m a d e a t 25°C.
i
 131

THEORY

The theory of robber elasticity, used to obtain molecular weights between

i n t e r s e c t i o n s in e n t a n g l i n g p o l y m e r s o l u t i o n s , h a s b e e n s u c c e s s f u l l y e x t e n d e d
t o o b t a i n m o l e c u l a r w e i g h t s o f i n t e r a c t i n g c y l i n d r i c a l m i c e l l e s . B a r n e s e t al.
[5] evaluated a number of expressions for entanglement density derived
f r o m l i n e a r v i s c o e l a s t i c i t y t h e o r y a n d o b t a i n e d r e a s o n a b l e a g r e e m e n t be-
tween values of the mixed surfactant micellar weight. The most useful equa-
t i o n is g i v e n b y F e r r y [61
M- 3RTC0 •
GI (1)
5r1~ w2
where R -- gas constant, T = t e m p e r a t u r e ( K ) , Co = c o n c e n t r a t i o n ( k g m - 3 X
10-3), T/p = l o w shear rate viscosity plateau value, G l ~- storage m o d u l u s
(real p a r t o f the c o m p l e x elastic m o d u l u s ) , w - - o s c i l l a t o r y f r e q u e n c y ( s - l ) .
T h i s e q u a t i o n o n l y applies t o the region where rt ffi c o n s t a n t and G I / w 2 --
constant. T h i s e q u a t i o n w a s u s e d f o r s a m p l e s in t h e c o n c e n t r a t e d r a n g e
w h e r e G t v a l u e s w e r e large e n o u g h t o b e m e a s u r e d u c c u r a t e l y . F o r t h e s e
samples relaxation spectra were also calculated using the mathematical
approximations due to Ferry [6]

H(r)-- dGlldh, w + ½ d2GIId(in w) ~ 1 _- (2A)

to
1 Ir¸
it(7") = d G I / d i n w - ~ d 2 G I / d O n w ) 2 - (2B)
• to vf2

w h e r e H(r) = n u m b e r o f s p e c i e s w i t h r e l a x a t i o n t i m e T. E q u a t i o n ( 2 A ) is u s e d
w h e n t h e s l o p e o f H ( T ) : I n w is p o s i t i v e a n d E q n ( 2 b ) w h e n i t is n e g a t i v e .
A differe_,~t a p p r o a c h • w a s u s e d f o r d i l u t e s o l u t i o n s . S t e a d y s h e a r m e a s u r e -
ments only were made and for the most viscous (single phase) composition
t h e S i m h a [7,81 e q u a t i o n ( m o d i f i e d b y H o f f m a n n e t al. [ 9 ] ) w a s u s e d t o
o b t a i n a n e s t i m a t e o f m i c e l l e size.

--
0.933 +
p2 *
1
+
1
{rt) d 5d 31n(2p) - X In(2p) - X + 1
where
17 --T/0
{~ } : l i m
e-*0 ~0C
ffi v i s c o s i t y o f t h e s o l u t i o n , ~0 ffi v i s c o s i t y o f t h e s o l v e n t , C = s o l u t i o n c(:n-
centration, d - density of the s o l u t i o n , p = a / b w h e r e a ffi l o n g axis, b -- s h o r t
axis, ~ = 1 . 8 ( f o r r o d s ) .
Since this equation cannot e a s i l y b~ s o l v e d a n a l y t i c a l l y v a l u e s o f p w e r e
selected and the best fit found by iteration.
132

RESULTS

High c o n c e n t r a t i o n range

Viscosities, r e l a x a t i o n times, m i c e l l a r weights (calctilated using E q n (1))

a n d t h e c o r r e s p o n d i n g m i c e l l e l e ngt hs ace s h o w n in Table 1. Micelle sizes
w e r e c a l c u l a t e d ~ u m i n g t h e radius t o be 2.5 n m a n d t h e s u rface area p e r
s u r f a c t a n t m o l e c u l e h e a d g r o u p to be a p p r o x , m a t e l y 0.5 n m ~ [ I 0 ] . T h e
large values o f G * observed ( 1 0 0 - - 2 0 0 0 N m - 2 ) suggest e x t e n s i v e n e t w o r k
f o r m a t i o n w h i c h c o u l d o n l y arise f r o m a s y m m e t r i c aggregates. S imilar be-
h a v i o u r in o t h e r mL~ed s u r f a c t a n t s y s t e m s has b e e n a t t r i b u t e d t o t h e pre-
s e n c e o f c yl i ndr i c a l micelles [ 5 , 1 1 ] . T h e o c c u r r e n c e o f similar aggregation
b e h a v i o u r in t h e s e s y s t e m s is v e r y likely (see Discussion), T h e m[cellar
w e i g h t declines sharply a b o v e a d e c a n o i c a c i d c o n c e n t r a t i o n o f 2.9 ×
10 - 2 M. T h e r e is n o a p p a r e n t r e a s o n fo r t h e l o w v alu e o b s e r v e d a t 2 . 3 2 X
10 -2 M.

TABLE1

1.5 X 10-a 2tf C a r b o x y t ~ e t a i n e so|utlorut -- rhe~logleat parameters

Deeanotc acid Platea~ blteelle Mleelle Relaxation

(hi) viscosity (MW) length (nm) time (s)
(PaS)
0.73 -- -- --
5.81X 10 -3 4.38 3.3X I0 s 30 0.3
1.16 X 10 -I 6.11 1,5 X I0' 140 0.3, 0.6
1.74 X 10 -I 4.86 6.6 X I0' 600 0,3, I.G
2.3"! X I0 -z 8.9-7 3.9 X I0* 3dO 0.4, 1.5
2.90 X 10 -1 6.23 8.1 X 10' 740 0.4, 0,8, 1.5
3.31 X 10 -I 4.62 5.0 X 10 ~ 46 0.3
3.71 Y 10 -I 3.65 4.1 X 10 s 38

T h e inter-facial textsion b e h a v i o u r b e t w e e n d e e a n e a n d s u r f a c t a n t s o l u t i o n s
is s h o w n in T a b l e 2. F o r these samples ( a n d for t h e d i l u t e c o n c e n t r a t i o n
range descrilced b e l o w ) e q u i l i b r i u m interfacial tensions against d e c a n e w e r e
a c h i e v e d in a few m i n u t e s suggesting t h a t it was o n l y n ecessary f o r t h e d r o p
to a t t a i n physical stability w i t h i n t he capillary. T h e shallow m i n i m a with
t i m e o b s e r v e d m a y be d u e to small a m o u n t s o f i m p u r i t i e s in t h e d e c a n e . [n
general, t h e results suggest a t r e n d o f d e c r e a s i n g interfacial ten s io n w i t h
increasing m i c e l l a r weight. C o m p o s i t i o n s in t h e h i g h e r c o n c e n t r a t i o n range
e x i s t e d as single phase, c l e a r s o l u t i o n s u p t o 2.91 X 1 0 -2- M d ec an o ic acid.
A t h i g h e r c o n c e n t r a t i o n s t h e s o l u t i o n s w e r e slightly c l o u d y a l t h o u g h t h e r e
was n o e v i d e n c e o f gross phase s e p a r a t i o n . T h e r e l a x a t i o n ~times (T) fall
generally i n t o t w o ranges; i- ~ 0.3--=0.-t $ a n d T ;~ 1,0 s. T h e i r significance is
discussed b e l o w .
TABLE 2 ."-,!~ " . -
- - , . . ,

1.63 X l O - ' M C a , b o x y b e t a i n e z O i u t i o n s , interracial tensions (7) vs decane ( 2 5 ° C )

Decanole acid Lowest T (ran m-' ) "lime to minimum Equilibrium ? (raN m-, )

5.8 x 10 - 4 0.25 constant 0.25

1.74 x I O - ' 0.13 20 rain 0,14
2 . 3 2 x 10 - z 0.09 70 min 0.12
2;90 X 10 - z 0,060 40 rain 0,065
3.3 X 10 -s 0.040 2 mln 0,049

Low concentration range

Figure 1 s h o w s t h e relationship b e t w e e n viscosity and phase behaviour.

T h e m a x i m u m viscosity lies very c l o s e to the phase b o u n d a r y suggesting that
mtcellar size is a m a x i m u m at that c o m p o s i t i o n . A t this p o i n t the solutions

O-t. 11,0
O SHEAR RATE :0.S Is-I |
& SHEAR RATE ; 5 " 1 ~ I t~ I
X

0.3 30

o_
..~u.
P! TWO LIQUID
z 0-2 PHASI~S 2o u)
E o
(J
>o (/ii

\
0.! x 1 I°

!oo 2o0 300 soo 900

OECANOlC ACID concn (ppm}
Fig. 1. lnterfaojal tension and viscosity vs d~Lcano|o ae|d c o n c e n t r a t i o n in 0.5% S,. (o)
:~zear rate = 0.51 s - s ; (A) s h e a r rate ,, 6.1 g " ' ; ( X ) i n t e r r a c i a l tension.
134

are also a p p r e c i a b l y viscoelastic. In t h e t w o - p h a s e region an u p p e r viscous

clear l a y e r is in e q u i l i b r i u m w i t h a l o w e r , c l o u d y , less viscous layer. T h e
u p p e r : l o w e r phase v o l u m e r a t i o varies f r o m 2 :1 c l o s e to t h e p h a s e b o u n d a r y
t o 1 : 5 at 1.53 × 10 - 2 M Sl ÷ 5 . 8 2 × 10 - 3 M d e c a n o i c acid. O n c e h o m o -
genised by v i g o r o u s s h a k i n g t h e mLxtures in t h e t w o - p h a s e r e g i o n r e q u i r e
several h o u r s fo r full s e p a r a t i o n . T h e a p p r o x i m a t e viscosities m e a s u r e d fo r
th ese h o m o g e n i s e d c o m p o s i t i o n s are m u c h l o w e r t h a n t h o s e in t h e single-
ph ase region close t o t h e p h a s e b o u n d a r y .
It was n o t possible t o use t h e m e t h o d o f F e r r y t o o b t a i n m o l e c u l a r
weights o f i n t e r a c t i n g u n i t s be c a us e t h e s a m p l e viscosities a n d elasticities
were t o o low. H o w e v e r , t h e m e t h o d d u e t o S i m h a was a p p l i e d t o a s a m p l e
with c o m p o s i t i o n 1.53 X 10 - 2 M SI + 3 . 4 9 X 1 0 - 3 M d e c a n o i e acid w h i c h
lies v e r y c l o s e t o t h e b o u n d a r y with t h e t w o - p h a s e region. T h e results in-
d i c a t e d a c y l i n d r i c a l micellar size o f a p p r o x i m a t e l y 2 4 0 n m .
Int e rra c i a l t e n s i o n d a t a against d e c a n e a t 25°C are also p l o t t e d as a func-
tion o f c o m p o s i t i o n in Fig. 1. T e n s i o n s d e c r e a s e s t e a d i l y with increasing
d e c a n o i c acid c o n c e n t r a t i o n a n d r e a c h a n a p p r o x i m a t e l y c o n s t a n t value in
t h e t w o - p h a s e region.

DISCUSSION

Relationship b e t w e e n micellar size a n d interfactal tension

Increasing t h e c o n c e n t r a t i o n o f d e c a n o i c acid s i m u l a t e s t h e d i f f u s i o n o f
c r u d e oil surfactmlts t o t h e i n t e r f a c e w h i c h o c c u r s w h e n c r u d e oil is in con-
t a c t w i t h s u r f a v t a n t s o l u t i o n . This is a c c o m p a n i e d by g r a d u a l l y d e c r e a s i n g
interracial t e n s i o n . T h e d e c a ~ o i c a c i d c o m i c e | l i s e s with th e c a r b o x y b e t a i n e ;
t h e negative citarge o n t h e d e c a n o a t e in teracts s t r o n g l y w i t h t h e positively-
c h a r g e d n i t r o g e n resulting in a d e c r e a s e d negative c h a r g e d e n s i t y a t t h e
surface t h u s l o w e r i n g i n t e z m o l e c u l a r repulsions. T h e s e repulsions are a l r e a d y
r e d u c e d by t he high e l e c t r o l y t e c o n t e n t o f t h e s e a w a t e r s o l v e n t a n d t h u s
c o n d i t i o n s are f a v o u r a b l e f o r t h e f o r m a t i o n o f a s y m m e t r i c micelles [ 9 , 1 1 ] .
T h e m a r k e d viscoelastic e f f e c t s o b s e r v e d in these s y s t e m s suggest t h a t these
micelles are cylindrical. In t h e high c o n c e n t r a t i o n region micelle sizes in-
crease w i t h d e c a n o i c acid c o n c e n t r a t i o n in t h e m o l e c u l a r w e i g h t rmlge 3 X
1 0 s - - 8 X 10 +. S t r o n g i n t e r a c t i o n s w o u l d be e x p e c t e d w i t h i n s u c h asym-
m e t r i c aggregates a n d t he s e m o l e c u l a r weights are ty p ical o f t h o s e observed
in viscoelastic surf:tctant m i x t u r e s . T h e largest aggregates have m o l e c u l a r
weights ~ 8 X 10 + c o r r e s p o n d i n g t o a length o f ~ 7 4 0 n m . [t has b e e n sug-
gest :d t h a t liquid c r ys t a l phases a r e c h a r a c t e r i s e d by l o n g range o r d e r o f at
least 1 0 0 0 n m [ 1 2 | . H e n c e , it is n o t surprising t h a t this c o m p o s i t i o n is close
to t h e l i mi t o f e x i s t e n c e o f t h e isoh-opic liquid phase.
R e l a x a t i o n times ( p o s i t i o n s o f m a x i m a in t h e r e l a x a t i o n spectra} general-
ly fall i n t o t w o groups viz. 0.3, 0.45 a n d ~ 1.5 s. T h e f o r m e r p r o b a b l y re-
flect o r i e n t a t i o n a l r e l a x a t i o n o f individual mfcelles f o l l o w i n g shearing. T h e
 135

l a t t e r c o r r e s p o n d s t o a r e l a x a t i o n t i m e o f t h e m i c e l l a r n e t w o r k since these
c o r r e s p o n d t o t h e t i m e s c a l e o f visually-observed viscoelastic r e l a x a t i o n .
F u r t h e r m o r e , t h e l o n g e r r e l a x a t i o n t i m e is o n l y o b s e r v e d a t h i g h e r d e c a n o i c
acid c o n c e n t r a t i o n s w h e r e t h e large micelles r e q u i r e d f o r fo~li~ing a visco-
elastic n e t w o r k are present.
In t h e l o w c o n c e n t r a t i o n region, t h e micelles increase in size u n t i l t h e y
c a n a c c o m m o d a t e n o f u r t h e r d e c a n o i c acid a n d a s e p a r a t e p h a s e rich in t h e
l a t t e r c o m p o n e n t is f o r m e d . In t h e two-phas~ region it is likely t h a t t h e
u p p e r viscous pha~e c o n t a i n s large c y l i n d r i c a l micelles. As t h e d e c a n o i c a c i d
is f u r t h e r i n c r e a s e d m o r e o f t h e c l o u d y l o w e r ~p h as e rich in act.J is e v i d e n t .
T h e c o m p o s i t i o n r a t i o a t w h i c h t h e viscosity m a x i m u m o c c u r s c o r r e s p o n d s
t o t h a t a t t h e h i g h e r c o n c e n t r a t i o n s . This in d icates t h a t t h e c o n c e p t o f a
critical d e c a n o i c acid level e x t e n d s over a w i d e c o n c e n t r a t i o n range.
T h e interracial t e n s i o n in b o t h high a n d l o w c o n c e n t r a t i o n ranges de-
creases w i t h i n c r e ~ i n g m i c e l l a r size a n d r e m a i n s l o w b e y o n d t h e l i m i t o f
e x i s t e n c e o f a single phase in t h e d i l u t e region. T h e interracial t e n s i o n be-
t w e e n d e c a n e a n d t h e u p p e r clea~" pha se is o f t h e s a m e o r d e r as t h a t for t h e
w h o l e c o m p o s i t i o n . ( T h e o p a c i t y p r e v e n t e d t h e t e n s i o n o f t h e lower, c l o u d y ,
ph as e against d e c a n e f r o m being m e a s u r e d in t h e s p i n n i n g d r o p t e n s i o m e t e r . )
T h e interfacial t e n s i o n b e h a v i o u r o f c r u d e o i l / c a r b o x y b e t a i n e s o l u t i o n s
can thus be e x p l a i n e d by t h e f o l l o w i n g m e c h a n i s m . I m m e d i a t e l y a f t e r t h e
f o r m a t i o n o f t h e interface, t h e t e n s i o n b e t w e e n t h e small micelles in t h e
z w i t t e r i o n i c s u r f a c t a n t s o l u t i o n a n d c r u d e oil is relatively high (0.3 m N
m - I ). S u r f a c t a n t s f r o m t h e c r u d e oil d iffu se r a p i d l y t o t h e i n t e r f a c e a n d t h e
m i c e l l a r size increases. As t h e pha s e b o u n d a r y is a p p r o a c h e d , t h e s u r f a c t a n t
m i x t u r e b e c o m e s m o r e oil s ol ubl e e n h a n c i n g t h e l i k e l i h o o d o f t h e forrnatiozz
o f small a m o u n t ~ o f t hi r d pha s e a t t h e i n t e r f a c e . S u c h t h i r d phases
are k n o w n t o be associated with u l t r a - l o w t e n s i o n s [ 2].
S u b s e q u e n t l y , t h e s u r f a c t a n t s o f t h e t y p e originating in c r u d e oil m a y
d i f f u s e a w a y f r o m t he interracial l a y e r i n t o t h e b u l k a q u e o u s s o l u t i o n w h e r e
t h e y are solubilised b y t h e large excess o f s u r f a c t a n t r e m a i n i n g there.
C o n s e q u e n t l y , t h e t e n s i o n rises f r o m u l t r a - l o w values b u t r e m a i n s a t 1 m N
m - ' c o m p a r e d with 28 m N m - l for d e c a n e against s eaw ater. This In-
dicates t h a t a substantial a m o u n t o f s u r f a c t a n t n : m a i n s at t h e interface.
T h e o c c u r r e n c e o f interracial t e n s i o n m i n i m a at i n t e r f a c e s has b e e n dis-
c u s s e d in t e r m s o f mass t r a n s f e r a n d a d s o r p t i o n / d e s o r p t i o n barriers b y R u b i n
a n d R a d k e [ 1 3 ] . T h e s e a u t h o r s e m p h a s i s e t h a t t h e high w a t e r : o i l p h as e
v o l u m e ra t i o in t h e s p i n n i n g d r o p t e n s i o m e t e ~ m a y a c c e n t u a t e o b s e r c e d
t e n s i o n m i n i m a . Nevertheless, e x p e r i m e n t s have s h o w n t h a t these effects are
m a n i f e s t e d in sand p a c k oil d i s p l a c e m e n t tests f o r this s u r f a c t a n t system.
I t is i m p o r t a n t t o n o t e t h a t this p a p e r r e p o r t s phase b e h a v i o u r in t h e
a b s e n c e o f h y d r o c a r b o n . Solubilised h y d r o c a r b o n s w o u l d increase micelle
size a n d possibly c a us e t h e pha s e s e p a r a t i o n t o o c c u r a t a l o w e r d e c a n o i c
acid c o n c e n t r a t i o n .
 136

CONCLUSIONS " +

S t u d i e s w i t h m o d e l c r u d e oil s u r f a e t a n t s have s h o w n t h a t t r a n s i e n t min-

i m a in c r u d e o H / a q u e o u s s u r f a c t a n t interfaeial t e n s i o n s c a n b e a t t r i b u t e d t o
c o m i c e l l i s a t i o n o f s u r f a c t a n t s f r o m b o t h phases a n d s u b s e q u e n t f o r m a t i o n
o f large c y l i n d r i c a l micelles. R h e o l o g i c a l a n d p h a s e - b e h a v i o u r m e a s u r e m e n t s
h a v e s h o w n t h a t a t w o , p h a s e r e g i o n exists a b o v e a critical r a t i o o f c r u d e oil
s u r f a c t a n t t o a q u e o u s s u r f a c t a n t . H o w e v e r , t h e laxge micelles r e m a i n i n g in
o n e o f t h e s e phases m a i n t a i n t h e l o w tension. S u b s e q u e n t d i f f u s i o n o f c n t d e
oil s u r f a c t a n t s f r o m t h e i n t e r f a c e i n t o t h e a q u e o u s s u r f a c t a n t b u l k r e d u c e s
t h e mi c e l l e size. I t is t h o u g h t t h a t t h e o c c u r r e n c e o f l o w t e n s i o n s d e p e n d s o n
t h e ability o f t he a q u e o u s s u r f a c t a n t t o solubilise h y d r o c a r b o n s . This will be
d i r e c t l y r e l a t e d t o m i c e l l e size.

ACKNOWLEDGEMENTS

T h e authors wish to a c k n o w l e d g e T h e British Petroleum C o m p a n y pie for

permission to publish this paper and Dr E.J. T i n l e y for preparing the carb+
oxybetaine . . . .

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