SURFACTANTS - EMULSIFIERS

An emulsion is a mixture of two or more immiscible (un-blendable)

liquids.
q
Emulsions are p
part of a more g
general class of two-phase
p
systems
y
of matter called colloids.
Although the terms colloid and emulsion are sometimes used
interchangeably, emulsion tends to imply that both the dispersed and the
continuous phase are liquid. In an emulsion, one liquid (the
dispersed phase) is dispersed in the other (the continuous phase)

A. Two immiscible liquids, not yet

emulsified.
emulsified
B. An emulsion of Phase II dispersed in
Phase I.
C. The unstable emulsion progressively
separates.
D The
D.
Th surfactant
f t t (purple
(
l outline
tli around
d
particles) positions itself on the
interfaces between Phase II and
Phase I, stabilizing the emulsion

Emulsions are made up of a dispersed and a continuous phase;

the boundary between these phases is called the interface.
Emulsions tend to have a cloudy appearance, because the
many phase interfaces scatter light that passes through the
emulsion. Emulsions are unstable and, thus, do not form
spontaneously.
The basic color of emulsions is white. If the emulsion is dilute, the
Tyndall
y da effect
e ect will scatte
scatter tthe
e light
g ta
and
dd
distort
sto t tthe
e co
color
o to b
blue;
ue; if
it is concentrated, the color will be distorted toward yellow.

Microemulsions and nanoemulsions tend to appear clear due to the small size
of the disperse phase.
Energy input through shaking, stirring, homogenizing, or spray processes is
needed to initially form an emulsion.
Over time, emulsions tend to revert to the stable state of the phases
comprising
p
g the emulsion,, an unstable emulsion that will quickly
q
y separate
p
unless
shaken continuously.
Whether an emulsion turns into a water-in-oil
water in oil emulsion or an oil
oil-in-water
in water
emulsion depends on the volume fraction of both phases and on the type of
emulsifier.
In general, the Bancroft rule applies: Emulsifiers and emulsifying particles tend
to promote dispersion of the phase in which they do not dissolve very well; for
example,
l proteins
t i dissolve
di l better
b tt in
i water
t than
th in
i oilil and
d so tend
t d to
t form
f
oil-inil i
water emulsions (that is they promote the dispersion of oil droplets throughout
a continuous phase of water).

There are three types of instability:

flocculation, creaming, and coalescence.
Flocculation describes the process by which the dispersed phase comes out of
suspension in flakes.
Coalescence is another form of instability, which describes when small droplets
combine to form progressively larger ones.
E l i
Emulsions
can also
l undergo
d
creaming,
i
th migration
the
i ti off one off th
the substances
b t
to the top (or the bottom, depending on the relative densities of the two
phases) of the emulsion under the influence of buoyancy orcentripetal
force when a centrifuge is used.
Orijinal Emlsiyon

Flokulasyon

Kremleme

Krlma

Koalesens

Surface active substances (surfactants) can increase the kinetic

stability of emulsions greatly so that, once formed, the
emulsion does not change significantly over years of storage.
Surfactants are compounds that lower the surface tension of
a liquid, the interfacial tension between two liquids, or that
between a liquid and a solid. Surfactants may act as
detergents,
wetting agents,
emulsifiers,
foaming agents,
agents
and dispersants.

Surfactants reduce the surface

tension of water by adsorbing at
the liquid-gas
liquid gas interface
interface. They
also reduce the interfacial
tension between oil and water by
adsorbing at the liquid
liquid-liquid
liquid
interface.

A micellethe
micelle the lipophilic tails of the
surfactant molecules remain on the inside
of the micelle due to unfavourable
interactions The polar "heads"
interactions.
heads of the
micelle, due to favourable interactions with
water, form a hydrophilic outer layer that in
effect protects the hydrophobic core of the
micelle. The compounds that make up a
micelle are typically amphiphilic in nature,
meaning that not only are micelles soluble
in protic solvents such as water but also in
aprotic solvents as a reverse micelle.

Surfactant classification
according to the composition of
their head:
nonionic,
anionic,
cationic,
Amphoteric (pH dependent).

Uses Of Surfactants

1. Emulsifiers

2.
2
3.
4.
5.
6.
7.
8.

Water In
W
I Oil - Low
L
Hlb
Oil In Water - High Hlb

Foam
F
St
Stabilizers
bili
Lipid Crystal Modifiers
Wetting Agents
Solubilizers
Starch Complexers
Protein
o
Modifiers
od
Detergents

IInteraction
i Of Surface
S f
A
Active
i Agents
A
With
Wi h
Food Components

1. Lipids
2. Water
3 Starch
3.
4. Protein
5. Air
6 Ions
6.
I

MOST SURFACTANTS
INVOLVE INTERACTONS
WITH LIPIDS

Why do we add surfactants to

foods ?

Orange Drink
Solublizer for colors
Stabilize orange oil
Possible cloud

Bread

Loaf volume
Entrap gas,
Soften
Soften,
Reduces staling
g

CSL, PS 60, DATEM

EMULSIFIERS IN BREAD
BAKING

During mixing

Improves wetability
Improves distribution of shortening
Interacts with starch, protein and fat

Results in:

Decreased mixing time

Decreased shortening
g usage
g
Improved mixing tolerance
Improved physical characteristics of the dough

EMULSIFIERS IN BREAD
BAKING

During fermentation

During baking

R
Results
l in
i better
b
gas retention
i
Improved
d gas retention
Improved loaf volume
D
Decreased
d water
t lloss
Finer, more uniform texture

During Storage

Increased softness
Less staling

Pudding

Emulsification
Wetting agent in powder
Texture modifier

Ice cream

Emulsion stability and destability,

Foam stability,

Candy Bar

Lecithin to stabilize fat crystals "bloom",

control viscosity and thus coating

Cookie

Control spread

protein and fat interaction

Note: altering sugar may be a bigger

factor

Surfactants 172

Listed Under Multipurpose Additives

Dioctyl Sodium Sulfosuccinate

Glyceryl Tristearate
Hydroxylated Lecithin
Methylglucoside- Coconut Oil Ester
Oxystearin
Sodium Lauryl Sulfate
Sodium Stearyl Fumarate

Surface Active Agents

Acetylated Monoglycerides
Succinylated Monoglycerides
Ethoxylated Mono And Diglycerides
Polysorbate 60 Polyoxyethylene (20) Sorbitan
Monostearate Aka Tween 60
P l
Polysorbate
b t 65 P
Polyoxyethylene
l
th l
(20) S
Sorbitan
bit
Tristearate
Polysorbate 80 Polyoxyethylene (20) Sorbitan
Monooleate

Surface Active Agents

Sorbitan Monostearate Aka Span

Calcium Stearoyl-2- Lactylate
Sodium Stearoyl-2-Lactylate
Lactylic
y Esters Of Fattyy Acids
Lactylated Fatty Acid Esters Of Glycerol And
Propyleneglycol
py
gy
Glyceryl-Lacto Esters Of Fatty Acids
Polyglycerol Esters Of Fatty Acids

Surface Active Agents

Propylene Glycol Mono- And Diesters Of

Fats And Fatty Acids
Propylene Glycol Alginate
Sucrose Fatty Acid Esters
Fatty Acids

Affirmed GRAS Emulsifiers

Diacetyl tartaric acid esters of mono- and

diglycerides.
diglycerides
Glyceryl monooleate.
Glyceryl
l
l monostearate.
Glyceryl behenate.
Lecithin
Mono- and diglycerides.
gy
Monosodium phosphate derivatives of monoand diglycerides
gy

Mono & diglycerides

Most commonly used

Generally as mono & di
Highly lipophilic with HLB values range from 1 to 10
produced byy transesterification of glycerol
p
gy
and triacylcerides
y
used in bakery products, frozen desserts, icings,
toppings, and peanut butter

Sources
Mono- and diglycerides occur naturally as food fat constituents,
Mono
constituents and are
also formed from triglycerides, being normal products of fat metabolism,
during the digestion and absorption of food.
As such, they are always found in conjunction with triglycerides, glycerol
and some free fatty acids subject to the manner in which they have been
roduced.
Theyy are p
produced commerciallyy byy a)) heating
g triglyceride
gy
fats with an
excess of glycerol, or b) direct esterification of glycerol with fatty acids.
The resulting composition is dependent upon the proportion of glycerol
and temperature conditions used. The mono-ester is usually in the range
3060%.
The composition of the product will vary according to conditions,
conditions but
glyceryl monostearate and glyceryl distearate are often major
components.

Function in Food
Emulsifiers are used to disperse fat droplets in water or water droplets in fat.
B
Because
they
h act at the
h surface
f
between
b
the
h fat
f and
d the
h water, they
h are also
l
known as surface-active agents or surfactants.
Monoglycerides and mixtures of mono- and diglycerides are by far the most
important commercially of all the food surfactants known; in Europe, they
represent
p
no less than 50% of the total food emulsifier market and,, in addition,,
the monoglycerides are important intermediates in the manufacture of DATEMs
(diacetyl tartaric acid esters of monoglycerides) and other emulsifiers.
Mono- and diglycerides are used widely in a great many products and are the
surfactant type most used in bread. Performance characteristics are controlled
by the skilful combining of alpha-mono-,
alpha mono beta-mono-,
beta mono didi and tri
tri-glyceryl
glyceryl esters
of mixtures of fatty acids. In bread, the effectiveness of the emulsifier is
dependent upon its total monoester content as, in this application, the
performance
f
off th
the alphal h and
d betafractions
b t f ti
are similar
i il and
d superior
i to
t either
ith
the di- or triglycerides.

Benefits
In the production of bread, the contribution made by the surfactant is to
enable the gluten in the dough to remain plastic and pliable so that,
that during
the kneading process, the strands of gluten can form a smooth extensible
film, ensuring that the correct texture is produced in the finished product.
As a general rule, volume and texture are of the utmost importance in
baking. For example, it can be shown that, in cake making, the air bubbles
in the batter that contribute to volume are enclosed in films of protein in
which the fat is dispersed.
The action of the surfactant is to improve the production of the initial air
bubbles, ensuring their uniformity and thereby an improved texture of the
finished baked product.
Typical Products
Bread, cakes and other baked goods; cereals, puddings; fresh pasta,
instant (mashed) potatoes; frozen desserts,
desserts ice cream and soft-serve;
confectionery, e.g. chewing gums, toffees, caramels; and fats, e.g.
margarines and shortenings.

Polysorbates

Polyoxyenthyene esters of sorbitan monoesters

Polysorbate 60

polyoxyethylene sorbitan monostearate or TWEEN 60 - HLB =

14.9

oil toppings, cake mixes, and cake icing

Polysorbate 65

polyoxyethylene sorbitan tristearate

Permitted in ice cream, frozen
custard

Polysorbate 80

polyoxyethylene sorbitan tristearate

Special dietetic foods, fat soluble vitamine

Sorbitan monostearate
sorbitan monostearate approved for food use
- HLB = 4.7
- used in conjunction with polysorbates in oil
t
toppings,
i
cake
k mixes,
i
etc.
t
-

Stearoyl Lactylates

an ionic, hyddophylic emulsifier

lactic acid ester of monoglyceride with sodium
or calcium
f
form
strong
t
complex
l with
ith gluten
l t
in
i starch
t
h and
d
especially valuable in baked products

Lecithin

A mixture of phospholipids including phosphatidyl

cholines phosphatidyl ethanolamines
cholines,
ethanolamines, inositol
phosphatides, etc
Can be chemically modified by provide a wide range of
HLB values
l
ffor various
i
applications
li ti
widely used in baked goods, low-fat baked goods, chocolate,
instant foods,, confectioneryy products,
p
, and cooking
g spray
p y

Sources
Lecithin is a mixture or fraction of phospholipids, which are obtained from
animal
i l or vegetable
bl foodstuffs
f d ff (mainly
( i l soya and
d egg)) by
b physical
h i l processes.
They also include hydrolysed substances obtained by the use of enzymes.
The finished product must not show any residual enzyme activity. A number of
different lecithins or lecithin fractions are available.

Function in Food
Phospholipids are the active ingredients of lecithin and have a two-part
molecular structure. One part is lipophilic (high affinity to fat/non-polar phase)
and the other is hydrophilic (high affinity to water/polar phase).
phase)
The phospholipids tend to dissolve in fat and disperse in water. This surface
activity
ti it iis th
the b
basis
i for
f th
the majority
j it off lecithin
l ithi applications
li ti
and
d allows
ll
the
th
formation of both water-in-oil and oil-in-water emulsions.
Besides nutritional benefits, phospholipids have the following functional
properties in food products: emulsification and stabilisation of oil-in-water or
water-in-oil emulsions;; release and anti-spattering
p
g effects;; adjustment
j
of the
flow properties in chocolate masses; improvement of the wettability of instant
products; as well as optimisation of the gluten network of baked goods.

Benefits
Lecithin allows the production of fine,
fine stable emulsions with little
aggregation or coalescence. It is also used in chocolate
manufacture to modifyy the flow characteristics of liquid
q
chocolate
for both blocks and coating. Lecithin is used on the surface of
powders to improve instant properties. In bakery applications,
l ithi is
lecithin
i used
d to
t increase
i
the
th extensibility
t
ibilit off the
th gluten
l t in
i bread
b d
making, and in batters to improve the overall distribution of
ingredients in cakes and to assist the release of wafers from hot
iron moulds.
Typical Products
Margarines, dressings, chocolate and confectionery items, instant
po de s and bakery
powders
bake goods.
goods

Emulsifier Usage in U.S.

(millions of pounds)

Emulsifier

Bread Cake mix

M,SD,S *

Total

Mono&Di
Lecithins
MG
Polysorb.
CSL/SSL
SorbMS
PG ester

116

30.5
10
2.5
.75
.25
2
1.8

200
42.5
25
8
30

13.2
1.5
27

23
1
0.5
1
.75
.1
10

*Margarine, salad dressings, shortenings

Sorbitan Monostearate
Calcium Stearoyl-2- Lactylate
Sodium Stearoyl-2-Lactylate

14.3

Emulsifier Usage

Product
% of total US
Bread and Rolls
49
Cake Mixes
11
Cookies and crackers
7
Sweet g
goods and icings
g
3
Margarine, dressings, shortenings
14
Confectionaries
6
Deserts and toppings
3
Dairy products
3

The Hydrophilic-lipophilic balance of a surfactant is a measure

of the degree to which it is hydrophilic or lipophilic,
lipophilic determined
by calculating values for the different regions of the molecule
All surfactants must have an oil loving portion and a water
loving portion or they would not have surface activity
The ratio of the oil loving
gp
portion to the water loving
gp
portion
is what we call its balance
We
W measure this
thi b
balance
l
b
based
d on molecular
l
l weight
i ht
HLB
HLB stands for
HYDROPHILE / LIPOPHILE / BALANCE

Hydrophillic Lipophillic Balance

Hydrophillic-Lipophillic
(HLB)

This is a concept for choosing

emulsifiers.
The value of HLB ranges from 1-20
1-20.
Low HLB emulsifiers are soluble in oil
while high HLB emulsifiers are soluble
in water..

Bancroft's Rule
The type of emulsion (i.e. oil in water or
water in oil) is dictated by the emulsifier
and that the emulsifier should be
soluble in the continuous phase.
Low HLB emulsifier
emulsifier'ss are soluble in oil and
give rise to water in oil emulsions

Wh is
What
i the
h HLB
H B system

story
The system
system was created as a tool to make it easier to use
nonionic surfactants
In g
general it applies
pp
to nonionic surfactants only
y
The basic principle of the system is:
Surfactants have an HLB value
Applications
A li ti
for
f surfactants
f t t have
h
an HLB requirement
i
t
Matching the requirement with the value saves time and
money

What is the chemistry of a nonionic surfactant ?

Each surfactant has a hydrophilic
y
p
group
g
p and a lipophilic
p p
group
must have both or it would not be surface active
the
th hydrophilic
h d
hili group is
i usually
ll a polyhydric*
l h d i * alcohol
l h l or
ethylene oxide
the lipophilic group is usually a fatty acid or a fatty
alcohol
* p
polyhydric-an
y y
alcohol with OHs attached
The relationship ( or balance ) between the hydrophilic
portion of the nonionic surfactant to the lipophilic
p
p p
portion
p
is what we call
HLB
All nonionic surfactants have an HLB Value

How do we determine the HLB value of a surfactant ?

We calculate the water loving portion of thesurfactant on a
molecular
l
l weight
i ht basis
b i and
d then
th divide
di id that
th t number
b by
b 5
this keeps the HLB scale smaller and more manageable
the working scale is from 0
0.5
5 to 19
19.5
5
this number is then assigned to the nonionic surfactant

HLB VALUES OF SOME FOOD

EMULSIFIERS
EMULSIFIER
HLB VALUE
Oleic acid *
1.0
Acetylated monoglycerides
1.5
Sorbitan trioleate
1.8
Glycerol
y
dioleate
1.8
Sorbitan tristearate
2.1
Propyleneglycol monostearate
3.4
Glycerol Monoleate
3.4
Glycerol monostearate
38
3.8

HLB VALUES OF SOME FOOD

EMULSIFIERS
EMULSIFIER
HLB VALUE
Acetylated monoglycerides (stearate) 3.8
38
Sorbitan monooleate
4.3
Propylene glycol monolaurate
45
4.5
Sorbitan monostearate
4.7
Calcium stearoxyl
stearoxyl-2-lactylate
2 lactylate *
51
5.1
Glycerol monolaurate
5.2
Sorbitan monopalmitate
6.7
Soy lecithin
8.0
Diacetylated
y
tartaric acid esters

of monoglycerides
8.0

HLB VALUES OF SOME FOOD

EMULSIFIERS
EMULSIFIER

Sodium Stearoyl lactylate *

Sorbitan monolaurate )
Polyoxyethylene (20)
sorbitan tristearate
Polyoxyethylene (20)
sorbitan trioleate
Polyoxyethylene (20)
sorbitan monostearate
Sucrose monolaurate
Polyoxyethylene (20)
sorbitan monooleate

HLB VALUE
8.3
86
8.6
10 5
10.5
11.0
14.9
15.0
15.0

HLB VALUES OF SOME FOOD

EMULSIFIERS
EMULSIFIER

Sodium Stearoyl lactylate *

Sorbitan monolaurate )

Polyoxyethylene (20) sorbitan

Polyoxyethylene (20) sorbitan

Polyoxyethylene (20) sorbitan

Sucrose monolaurate

Polyoxyethylene (20) sorbitan

Polyoxyethylene (20) sorbitan

HLB VALUE
83
8.3
8.6
tristearate
10.5
trioleate
11.0
monostearate
14.9
15.0
monooleate
15.0
monopalmitate
15.6

Stokes' Law

Creaming or sedimentation is
proportional
i
l to:

1. Diameter of the particle squared

2. Difference in density between the
particle and the continuous phase

And inversely proportional to:

3 Viscosity of the continuous phase

3.

Stokes Law

Rate = [Diameter squared x density

difference x g] / [16 x viscosity]
How can we change diameter?
How can we change density difference?
How can we change viscosity?

Amylose Complexing Index

Distilled Monoglycerides
From hydrogenated lard (65% MS, 30% MP)
From hydrogenated soy oil (85%Mono Stearate)
From unhydrogenated lard 45% Mono olein
From soy oil (55% mono olein)

92
87
35
28

Acetylated mono glycerides

Saturated Mono and Di glycerides (50% mono)
Steroyl-2-lactylate
Sodium Steroyl-2-lactylate
Calcium Steroyl-2-lactylate

0
42
79
72
65

Lactylated
y
monoglycerides
gy
Diacetyltartaric esters of monoglycerides

22
49

Basic Rules
1. For emulsions, if you don't have A clue,
use At 5% Of The fat.
2 Use unsaturated emulsifiers with
2.
unsaturated fats.
3. Mixtures work better than a single
g foams And
emulsifier when stabilizing
emulsions.

Basic Rules
4. Bancroft's Rule
Emulsion
E
l i Stability
S bili Is
I Favored
F
d By
B Solubility
S l bili In
I The
Th
Continuous Phase i.e. High HLB----> oil/water
Low HLB-----> water/oil

5. HLB and most other rules go out the window

when protein and (sometimes)
polysaccharides enter the system.
6 Only saturated monoglycerides complex with
6.
starch.

Basic Rules

4. Bancroft's Rule

Emulsion
E
l i Stability
S bili Is
I Favored
F
d By
B Solubility
S l bili In
I The
Th
Continuous Phase i.e. High HLB----> oil/water
Low HLB-----> water/oil

5. HLB and most other rules go out the

window when protein and (sometimes)
polysaccharides enter the system.
6 Only saturated monoglycerides complex
6.
with starch.

Basic Rules

7. Emulsifier forms affect functionality.

fl k vs powder
flakes
d vs hydrates
h d
vs gels
l

8. Many functions are due to affects on

polymorphism.
l
hi
9. Emulsifier preparations frequently contain
unsaturation
nsat ation and may
ma be an important
impo tant
contributor to off flavors.
10 Emulsifier preparations are seldom pure
10.
and thus variation from manufacturer to
manufacturer may be substantial.
substantial

Basic Rules
11. When you find a non-obvious usage of
emulsifiers the function is often related to
emulsifiers,
interaction with starch or protein.
12 Order of addition may be very important.
12.
important
13. Processing steps like homogenization may
substantially change the function of
emulsifiers.