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emulsification by surfactants
2006.4.19.
1. Introduction
1. Emulsion immiscible liquid phase, multiphase
dispersion, thermodynamics unstable system (from
a few minutes to a few years) e.g. milk , soybean
milk, bearnaise, finishing oil etc.
2. Formation
(1) Emulsification one fluid dispersed in a second
dispersephase , inner phase , discontinuous phase
dispersion medium outer phase continuous
phase
Three types: o/w, w/o, and w/o/w or o/w/o
two immiscible, pure liquids cannot form emulsion.
3. Properties
(1) Size and aspect of particles
Macroemulsions: d>400nm, creamy white
Miniemulsions: 400nm>d>100nm, blue-white
Microemulsions: 100nm>d>50nm, translucence
Nanoemulsions: 50nm<d, transparence
(2) Viscosity Einsteins eq.
= 0 (1 + 2.5)
0 viscosity of outer phase
- volume fraction of inner phase
OW
vapor
oil
liquid
SV
SL
O
SO
water
SW
Spreading SW = SO - SW - OW = OW (cosW1) 0
or SO = SW - SO - OW = OW
(cosO-1) 0
If so ow + sw then W 0, the powder
is in water phase
If sw ow + so then o 0, the powder
is in oil phase
Else the powder is adsorbed at O/W
interface
0 < W < 180 or 0 < O < 180
2. HLB value
1~3
3~6
7~9
8 ~ 18
13 ~15
15 ~18
&
application
anti-foaming agent
w/o emulsifying agents
wetting agents
o/w emulsifying agents
detergents
solubilizing agents
e.g. C17H35COOCH2CH(OH)CH2OH
S=161, A=198, then HLB = 3.7
(b) Nonionics of POE & polyol
HLB = (E + P)/5
E the weight percentage of oxyethylene content
P the weight percentage of polyol content
e.g. C16H33(OC2H4)10OH
E = (44 10+17)/(44 10+17+225) = 67.0%;P = 0
HLB = (E+P)/5 = 67.0/5 = 0.67 20 = 13.4
(c) Logarithm: HLB=7+11.7ln(MW/MO)
MW or MO- molecular weight of hydro- or lipo-philic
group: MW=441, MO=225, then HLB=14.9
(3) Mensuration
(a) behavior in water
no dispersibility
poor dispersion
milky dispersion after
vigorous agitation
stable milky dispersion
(upper end almost translucent)
from translucent to clear
clear solution
HLB Range
14
36
68
8 10
10 13
13 +
2. The creaming( ),
flocculation( ),and
coalescence( ) the
reversible prelude of
emulsion breaking
(a) Creaming difference
in gravitational
(b) Flocculation - attractive
force between droplets
(c) Coalescence irreversible
- breaking, phase separation
(2) Mechanism
(a) Displacing emulsifying agents are displaced
by de-emulsifying agent
(b) Wetting powder emulsifying agents
(c) Flocculating cross-linking agents
(d) Collision - deemulsification
(e) Make the interface film to distortion( ) and
tendering( )
(3) Factor affecting de-emulsification
(a) pH value e.g. carboxylate surfactant is
unstable at low pH.
(b) Electrolyte
Concentration I , , stability.
Valenta value polyvalent ion , stability
(c) Temperature - T, solubility of surfactants,
intensity of film
(d) Phase volume ratio volume fraction > 74.02%
(h) Stirring Reynolds number ( ) - 3500
6. Micro-emulsion
Generally : surfactants & cosurfactants and etc
In 1986,the cosurfactant-free microemulsion
have been prepared
The differentia with macro-emulsion
2. Mechanism of formation
(1) Negative interfacial tension theory Schulman
and co-workers: 0 spontaneous process
it may be a transient phenomenon( ), and at
equilibrium must be zero or slightly positive.
is macroscopy property and made no sense in
micro-emulsion
oil
(2 ) (duplex film?)
surfactants + co-surfactants
Mixed film
+ auxiliary agent( )
water
mo
mw