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... ( )

Physicochemistry of Interfacial Phenomena Laboratory INEOS RAS

-,
:
, ,

..
e-mail: babak@ineos.ac.ru : 135-65 02

« - » ?
Biliquid foams High internal phase ratio emulsions Aphrons Hydrocarbon gels
10

3

= 80 99 % , G' ~103 , * ~ 10 -10 , ~ 0.1-1 /
2 3

5

-

- H.M.Princen, M.P.Aronson, J.C.I.S., 1980 ; - M.P.Aronson, J.C.I.S., 1989 ; - M.P.Aronson,M.F.Petko, Langmuir,1993

- O.Sonneville-Aubrun, V.Bergeron, et al. Langmuir, 2000

- T.G.Mason, J.Bibette, et al., Phys.Rev., 1997

M.P.Aronson, J.C.I.S., 1989 ; T.G.Mason, J.Bibette, Phys.Rev.Letters, 1997; Langmuir, 1997; C.Mabille, V.Schmitt, et al., 2000; P.Perrin, Langmuir, 2000)

osm

- J.Bibette, J.C.I.S., 1991; - J.Bibette, D.Roux, F.Nallet, J.Phys.II France, 1992

/ (

()

/ (

- () H(CH2)m(OCH2CH2)nOH CmEn

H(CH2)mSO4

-

Na

+

CmSO4- Na

+

«»

( )

~107 c f

1

P(t)

-

0.5

r

0

0 1 2 3 4 5

f

log t [c]

6

7

C12E5

f ~1 c

C12E5

f >> 1 c

T=25°C : (C8H17)
C12E4

C12E4

f ~1 c f >> 1 c

C12E5
T=25°C : (C8H17)

C12E4

C10E4
7 6 5 4 3 2 1 0 0 10 20 30 40 50

C8H17
~25°C /; ~25°C

log f [c]

/

/

~25°C /; C8H17 C14H29 ~35°C

, [ C°]

-

* *

(f ~107 c) - : , , , , . , . - ( ), - .

* *

H.T. Davis, 1994

T
2

--

b a b

II

L2

3

c III a b

L3

2
a

I

L
1

-- M.Kahlweit, R.Strey, 1985 T
2
«» Om+W

T T
3

( II )

T
u

u

T

W+M+O
HLB ( III )

T
2

l

T T

l

Wm+O
( I )

M.Kahlweit, R.Strey, 1985

2

b a b

T T T
u

R.Strey, 1996

ab

T T

u

bc

3

c a

m

ab

ab+

+

ab

T
b 2 a

ac

l

T

l

ab

T

,

T
Tu Tm Tl
ab

H1 <0 H2 <0 H2 <0

H<0 K>0 H=0

bc

ab ac

ab++

ab

H1 > 0
ab

K 0 H>0 K>0

H1 > 0 H2 > 0 H=(H1+H2)/2 K= H1H2

,

Tm=(Tu+Tl)/2 Tm -

T
Tu

bc T.Sottman, R.Strey (1997)
J.Chem.Phys., 106, 8606.

T < Tl

ab

ab= bc

ac =

o , ac

B.Widom (1987) Langmuir, 3, 12

Tl - T T l

µ

Tl < T < Tl,w ab ac + bc Tl,w -

ab

µ=1, 26

Tm

ab+

+

«-»

ab

T

l,w

< T < Tm

ab < ac + bc
R.Strey (1994)
Colloid Polymer Sci., 272, 1005.

Tl,w Tl

ac

ab 2 kT
ab

,

H c(T - Tm

)
-1

- , ,

Tm=(Tu+Tl)/2 c ~ 10-3 е-1 K

H l - H u c(Tu - Tl Hl -H
u

)

m Tu Tl .

Helfrich WA (1973)
Elastic properties of lipid bilayers: theory and possible experiments. Z.Naturforsch C 8, 693-705

T
K
Tu

bc

ab ab ac ab++
ab

g c = 2 (H - H
J.Chem.Phys., 106, 8606.

K = H1 H 2 < 0
2

o

) +
2

T.Sottman, R.Strey (1997)

Tm Tl,w Tl

m

ab

= 2 H ( + ) + K

T=Tm

ab ,

m = + K m = - H1 H

2m

=

2(T - Tm ) (Tu - Tl )

=- 2
m

* = ab /
= -
*

= (
*

*2

)

+1

2 = c(Tu - Tl

)

2 +

Helfrich WA (1973)
Elastic properties of lipid bilayers: theory and possible experiments. Z.Naturforsch C 8, 693-705

Babak VG (1993)
Thermodynamic of Free and of Interacting Curved Interfaces in Liquid FIlms. Russian Chemical Reviews 62, 703-727.

g c = 2 (H - H

o

)2 +

K
Winsor I Winsor III Winsor II
2 o

g c (H o ) H

2 o

g c (0) 2H
o

H = H1 = H 2 > 0

o = + g c ( 0) - g c ( H
o =
min

)

K = H1H 2 = H 2 > 0

+ (2 - )H

2 o

log C
Winsor I Winsor III Winsor II

=

min

+ (2 - )H
2 o

2 o

(2 - )H

Ho

1 rmic

-- TPIT ?
CmEn CH
7 6 5 4 3 2 1 0 0 10 20 30 40 50
2+1

log f [c]

/

/
«»

, [ C°]

( )

Oil Water O/W/O film

2r

Oil
h

T < PIT
Oil Direct micelle

hf

h
Oil

h

f

(hole) rh

Wh = 2 rh - rh2

f

«» rh* W*

f - hf

f = o + (h

f = 2 f + h
1 2
f

f
f

r=
* h

Wh rh

f

)

W* = f

T ,µ

2

i

=0

h f << f

W* 2

2

(h f ) = (h )dh
h

h

o

«» Ak

T < PIT
hf

Ah 2 rh

h

2r

Oil
h

f

~

2

2 h f rh

h

f

W* «»
2 2 hf W* 2 o o 2 h

h Ah ~ A hf 2 rh
hf 2

Oil
h

r

h

*

H 0, h o
De Vries (1958)

W * h 2 f
h f ~ 10 nm

o

rh*

h

W*

o

o ~ 1 mN / m

W * 50 kT

W*

T
H1 -

1 rh 1 1 H = ( H1 + H 2 ) / 2 - + h f 2rh H2 +

2 hf

Oil Water
O/W/O film

Oil

T > PIT
h
f

Reverse micelle

Reverse micelles Oil

h

min

<<

o

rh*

hf 2

Oil
h

<< h

f

o

2 H + H 2 H1 1 - H= 1 hf 2 2 hf W* H1 -

1 H2 + rh

1 Ho - rmic

W
*

h2 f

2 min

o

o ~ 1 mN / m
h f ~ 10 nm
W*

min

~ 10 -3 mN / m
- 25

h2 f

2 min

10

J << kT

T>PIT // /

o

Oil Water
W/O/W film

Water

Direct micelle

Direct micelles Water

h

f

Water

1 Ho hf
H= H1 + H 2 H1 1 + 2 2 hf
min

T < PIT

2 H1 + hf
W* h2 f
2 min

H2 -
10
- 25

1 rh

h

<<

min

o

J << kT

o

o ~ 1 mN / m

~ 10 -3 mN / m

h f ~ 10 nm

T

PIT --. W* . . W* (, ) , ,

-
Interfacial tension [mN/m]
10 1 10
-1 -2

L
' 3

10 10

-3

L1
Temperature

L2
Water

Water

Oil
H.Kunieda, Y.Fukui, H.Uchiyama, C.Solans, Langmuir, 1996

Oil

H2O - -C12E4

Spontaneous formation of gel-emulsions by PIT route
10

Interfacial tension, [mN/m]

RE

82 PFD

C8E3 tetradecane

1 10
-1

C12E4

octane

C10E6
deca ne

10

-2

C12E5

octane

*

T

10

-3

min
10
-4 0 10 20 30 40

tetradeca ne
50 60

C8E3

Region of spontaneous emulsification

70

80

90

4 R 2 * ~ kT
R~10 *~10-2 / H2O - decane - C12E4 L1 -phase W/O gel-emulsion
H.Kunieda, Y.Fukui, H.Uchiyama, C.Solans, Langmuir, 1996

Temperature, T [°C]

H2O tetradecane - C12E5 L2 -phase O/W gel-emulsion

LTaisne, B.Cabane, Langmuir, 1998

-
Water Water

Oil
Interfacial tension [mN/m] 10

Oil

Oi l

1 10
-1 -2

Oil

10 10

-3

L1
Temperature

L2

L1

L2 Water Surfactant

Water

Surfactant

osm

f

osm

= ( R

)
c

f R 2r

c

H.M.Princen, J.C.I.S., 1986

f

osm

=

osm

1

( R )
2

= 0,584

1

3

1-

5,0 4,0 3,0

osm

osm

osm

1,6 ( -
0,72 < < 0,9

c

)
-1

~

1

3

1-

osm

B

2

( - c )

2,0 1,0 0

osm

~ 2 ( -

c

)

-1

where the constants B, c and 2 are adjustable parameters depending on the geometry of the droplet packing.

T.G.Mason, et al., Phys.Rev.E, 1997 M.-D.Lacasse, et al., Phys.Rev.E, 1996

0,7

0,8

0,9

Volume fraction,

1,0

:
H.M.Princen, J M.P.Aronson, J.C.I.S., 1986 ; M.P.Aronson, Langmuir, 1989 ; J.Bibette, D.Roux et al., J.Phys.II France, 1992

M.P.Aronson, H.M.Princen, Nature, 1980

()
A.Langenfeld, Ph Dissertation, 1998

:
- - , Cs - , Cel - , R - , T
H.M.Princen, J M.P.Aronson, J.C.I.S., 1986 ; M.P.Aronson, Langmuir, 1989 ; J.Bibette, D.Roux et al., J.Phys.II France, 1992
2r R 2r
d

R

2
Depletion region

2

, Cs, Cel, R, T
H.M.Princen, J M.P.Aronson, J.C.I.S., 1980 ;

fd

2r R 2r
d

R

2
Depletion region

fd
Cm = (Cs - cmc ) / N
2rm
ag

f d = m ad 2 ad = rd 2 (R + )rm
m Cm RT

: s=5.10-2 / cmc=5.10-3 / Nag50 rm 3
m 2500 R= 1 R = 0.1

Wd f d rm

Wd 20 kT Wd 2 kT

z z
mol

d

h

f

-os

,

m

f

ad

R ad
m < Pc

ad =

mol

= dh
h
f

mol

+ d

mol

<< d

d = - m ( - h f )

m o

(

-h

f

)

5,0 4,0 3,0 2,0 1,0 0 0,1 0,2 0,3 0,4 0,5

fad /f

Ю

Force

Pc [kPa] osm [kPa]
2,0 1,5 2,0 1,5 1,0 0,5

Pc
osm

V.G.Babak, M.J.Stebe, J.D.S.T., 2002, N°1-2

fad

1,0 0,5

0,6

Salt NaCl, [mol/l]

fad

CNaCl=0 CNaCl > 0,4 M

s= 7,5 mN/m Pc =

osm

Cm RT 0,9 kPa

2 o 1,5 kPa R 2 o < 0,9 kPa R

osm

< Pc
collapse

s= 4,5 mN/m Pc =

osm

Cm RT > 0,9 kPa

osm

> Pc

A.Langenfeld, Ph Dissertation, 1998
1000

G' [Pa]

100

v 0.77 0.81 0.88 x 0.96 0.94 + 0.97

1000 100 10 1 0.1 0.01

G', G" [Pa]

G' exp

-

G" exp G' Maxwell G" Maxwell

10

1 0.1 1 10 100 1000 10000

0.001 10
-6

10

-4

0.01

1

100

% deformation

Frequency [Hz]

G' T G' v

zz

f

a

- (b) (max)

fa K

zz E
o

K 2

2R
a
13 v

zz n f

z

n = S (

v

)

(2 R )
2

f

a

R

R1 R2

Deformation,
Adhesion force, fa*

f
R2

S ( v ) = C
c

( v - c )

E 3G

,

fo
rfo
r

f
rf

R1

f
rf

0

Force, f
max

Region of extension,

Region of compression,

fa< 0

fc> 0

1 G ' 1.77 o v / 3 ( v - c ) R

-

f
max a *

z
Laplace region

z
z(r)

f

H Rupture
r

Transition region

f

h
r
f

r
Water Oil

Disjoining pressure ,

b n f
a

* a

f * R
ad

= ( h ) dh
ad H
f

ad 2 o cos f -1

(

)
2

, b

, max

S( ) v ad b fa S( 2= (2R) 4 R
*

)

max

fa* 1 ad 4R o 4 o

max

2 1 sin f f 2 2

bG' sin2

f

* - ( , , ) , .

* , , -.