Stability of Food Emulsions (1)

David Julian McClements

Biopolymers and Colloids Laboratory
Department of Food Science
Definition and Importance of
Emulsion Stability
Definition: "Ability to resist
changes in properties over
time
Importance: Determines the
shelf-life and processing of
food emulsions
May be desirable or undesirable
Arcocolors.com
Emulsion Stability: Kinetic
versus Thermodynamic Stability
G
G*
Separated Phases
Emulsion
Kinetically
Stable
Kinetically
Unstable
G
i
G
f
Thermodynamically
Stable
Thermodynamically
Stable
Physical stability:
Ability to resist changes in spatial distribution
of ingredients over time
- e.g., creaming, flocculation, coalescence..
Chemical stability:
Ability to resist changes in chemical structure
of ingredients over time
- e.g., -3 oxidation, citral degradation
Physical Stability Mechanisms
Flocculation
Stable
Emulsion
Coalescence
or
Ostwald
Ripening
Gravitational
Separation
Phase
Separation
Importance of Identification of
Major Instability Mechanisms
Every food emulsion is unique!
There is no single strategy that can be used to
generally improve food emulsion stability
It is therefore crucial to identify the major
instability mechanism for the specific food
emulsion of interest
Knowledge of emulsion science and technology
facilitates problem solving
Emulsion Stability Testing:
Diagnostic Approach
Phase separation
Oiling off
Rancidity
Creaming
Flocculation
Coalescence
Ostwald Ripening
Process
Ingredient
Storage
+ +
Ca
2+
Macroscopic Properties
Physicochemical Origin
Instability Mechanism
Solution
Determine instability
mechanism(s)
Characterize product
defect
Identify physicochemical
origin
Gravitational Separation
Principles
U
U
=
=
-
-
2
2
r
r
2 2
(
(

2 2
-
-

1 1
)g/9
)g/9

1 1
Stokes Law:
Stokes Law:
Methods of Retarding Gravitational Separation
Methods of Retarding Gravitational Separation
:
:

Reduce density difference (

Reduce density difference (

)
)

Reduce droplet size (r)

Reduce droplet size (r)

Increase continuous phase viscosity (

Increase continuous phase viscosity (

1 1
)
)
F
G
F
V
Gravitational Separation
Influence of Density Difference
-0.5
-0.3
-0.1
0.1
0.3
0.5
-100 0 100 200
Density Difference (kg m
-3
)
U
/
r
2

x

1
0
6

(
m
-
1
s
-
1
)
Sunflower oil-in-water emulsions containing weighting agents:
Ester gum, Damar Gum, SAIB or BVO
Density Matching
Gravitational Separation
Influence of Droplet Size
0
20
40
60
80
100
0 0.5 1 1.5 2 2.5 3
r
( m)
U

(
m
m
/
d
a
y
)
Sunflower oil-in-water emulsions
Without thickening agent,
O/W emulsions are unstable
to creaming once r > 0.5 m.
U r
2
Gravitational Separation
Influence of Continuous Phase Viscosity
0
5
10
15
20
25
30
0 0.005 0.01 0.015 0.02 0.025 0.03
Biopolymer Concentration (wt%)
U

(
m
m
/
d
a
y
)
Predictions: R
V
= 1000; CFC = 0.004 wt%;
r = 0.5 m, r
floc
= 1.5 m
Thickening agents may
promote creaming instability
if they cause flocculation!
Floc
Non-Floc
Gravitational Separation
Influence of Droplet Concentration
0
0.2
0.4
0.6
0.8
1
0 0.1 0.2 0.3 0.4

U
/
U
0
Hexadecane oil-in-water emulsions (SDS)
Strategies to Reduce Gravitational
Separation
Quality, sensory Add thickening
or gelling agent
Increase
Cost, quality Homogenize Reduce r
Stability, quality,
nutrition
Alter SFC
Regulations, cost Add weighting
agent
Reduce
Problems Method Principle
Food Emulsions Susceptible to
Gravitational Separation
High Susceptibility
High Susceptibility

Beverages
Beverages

Infant formulae
Infant formulae

Salad Dressings
Salad Dressings

Soups & Sauces

Soups & Sauces
Low Susceptibility
Low Susceptibility

Margarine & Butter

Margarine & Butter

Mayonnaise
Mayonnaise
Low droplet concentration
Low continuous phase viscosity
High droplet concentration
Gelled continuous phase
Experimental Characterization of
Gravitational Separation
Indirect Methods (Prediction)
Stokes Law: U = -2gr
2
/9
Measure PSD, ,
Direct Methods (Measurement)
Visual observation
Physical sectioning
Droplet profiling

0
5
10
15
20
25
30
35
0.1 1 10 100
Diameter ( m)
V
o
l
u
m
e

F
r
e
q
u
e
n
c
y

(
%
)
Stable
Unstable
Measuring Creaming Stability
Visual Observation
H
M
H
L
H
U
Upper
Creamed
Lower
Serum
Middle
Emulsion
Creaming Index: CI = 100 H
L
/ H
E
H
E
Long-term storage tests or accelerated (centrifugation) tests
Measuring Creaming Stability
Visual Observation
Two-layer
System
Three-layer
System
One-layer
System
0
5
10
15
20
25
30
35
40
45
50
0 20 40 60 80
Time (h)
C
I

(
%
)
CI
final
v = dCI /dt
CI
Cream
Emulsion
Cream
Serum
Emulsion
Measuring Creaming Stability
Visual Observation
Observation Problems:
Where is the boundary?
Which layer is which?
Subjective analysis
Container Requirements:
Flat bottomed
Graduated
Material (Glass/Plastic)
(TurbiScan MA images from http://www.sci-tec-inc.com/)
Measuring Creaming Stability
Optical Imaging
0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 40
Height (mm)
B
a
c
k

S
c
a
t
t
e
r

(
%
)
0.9 hr.
5.7 hr.
8.7 hr.
13.8 hr.
24 hr.
46.1 hr.
70.3 hr.
123.7 hr.
Cream
Layer
Serum
Layer
Emulsion
Layer
Measuring Creaming Stability
Optical Imaging
Radial Position
T
r
a
n
s
m
i
s
s
i
o
n
NIR Light
Source
Sample
Time
Colour Coded
Transmission
Profiles
CCD Sensor
t
i
5 - 2300 g
Space and Time resolved Extinction Profiles
STEP
TM
- Technology
Time
Space
Measuring Creaming Stability:
Accelerated Optical Imaging
Measuring Creaming Stability
Ultrasonic Scanning / NMR Imaging
Quantitative
Concentrated Systems
0 hrs 0 hrs
24 hrs 24 hrs
Droplet Flocculation

Aggregation of two or more droplets into a floc

Aggregation of two or more droplets into a floc
where the droplets retain their individual identities
where the droplets retain their individual identities

Stable Flocculated
Fraction
Size
Strength
Shape
E
R
R
O
R
:

s
t
a
c
k
u
n
d
e
r
f
l
o
w
O
F
F
E
N
D
I
N
G

C
O
M
M
A
N
D
:

~
S
T
A
C
K
: