Stability of Food Emulsions (2)

David Julian McClements Biopolymers and Colloids Laboratory Department of Food Science

Droplet Coalescence

Oiling Off

Coalescence

Aggregation due to fusing together of two or more individual droplets to form a bigger droplet

Droplet Coalescence
Oil

A few nms

Water Oil

Droplet coalescence depends on precise molecular details of droplet interfaces - difficult to predict!

Factors Influencing Droplet Coalescence

Relative magnitude of forces between droplets Resistance of interface to disruption Duration of contact between droplets Shearing and tearing of interfaces

Evolution of Coalescence
Homogeneous Coalescence
Coalescence rate independent of droplet size

Heterogeneous Coalescence

Coalescence rate increases with droplet size

Factors Influencing Droplet Coalescence: Ingredient Interactions

Without chitosan (1-month old emulsion)

0.01 wt. % chitosan (the same magnification)

Factors Influencing Droplet Coalescence: Freezing & Thawing

0 wt% sucrose

20 wt% sucrose

Hydrogenated palm oil-in-water emulsions stabilized by WPI (-40 C/40C) sucrose modifies ice crystal formation

Factors Influencing Droplet Coalescence: Dehydration

0 wt% sucrose

20 wt% sucrose

Oil-in-water emulsions stabilized subjected to freeze-drying

Droplet Coalescence: Influence of

Interfacial Membranes
1 Highly Unstable 2 Stable to Coalescence Only 3 Stable to Coalescence, Flocculation & Creaming
% Coalescence
100 80 60 40 20 0 1 2 3
-10 -40

Emulsion

3 Cycles: -10C/30C

Features of Coalescence
35 30 25 20 15 10 5 0
0.1 1

(%)

0 hours 24 hours

10

100

Diameter ( m)

Bimodal PSD Evolution Oiling off

Strategies to Reduce Coalescence

Principle (1). Reduce Attraction Method Avoid depletion Avoid bridging Avoid hydrophobicity Alter pH or I (E/S) Increase thickness (S) Add thickening or gelling agent Use polymeric emulsifier

(2). Increase Repulsion (3). Decrease droplet contact (4). Increase resistance of membrane to rupture

Measurement of Coalescence
Techniques & Protocols
Instrumental Techniques
Microscopy Particle Sizing Creaming stability/Oiling Off

Experimental Protocols
Storage Tests Accelerated Storage Tests Environmental Stress Tests

Characterization of Coalescence:
Microscopy Methods

Particle Size Distribution, Flocculation vs. Coalescence (Image Analysis Software)

Characterization of Coalescence:
Particle Size Analysis
14 12
37 0 -20

Volume%

10 8 6 4 2 0 0.01

37 C : All liquid -0 C: Fat crystallizes -20 C: Water crystallizes

100

Particle Diameter ( m)

Potential Problems: Sampling, Distinguishing from flocculation

Characterization of Coalescence:
Distinguishing from Flocculation
4 3.5 3

Volume%

2.5 2 1.5 1 0.5 0 0.01 0.1 1 10 100

Emulsion to Be Tested

Particle Diameter ( m)

12 10

Add Deflocculant (e.g., surfactant)

Volume%
0.1 1 10 100

4 3.5 3 2.5 2 1.5 1 0.5 0 0.01 0.1 1 10 100

Volume%

8 6 4 2 0 0.01

Particle Diameter (m)

Particle Diameter (m)

Initially Flocculated

Initially Coalesced

Measurement of Oiling Off

Stable Emulsion Coalescence Oiling Off

Extensive droplet coalescence can lead to the formation of a thin layer of oil on top of a product (sometimes with little change in PSD of bulk emulsion)

Oiling Off:
Solvent Extraction Method

Petroleum ether Emulsion shake

Measure amount of oil that can be extracted by an organic solvent

Oiling Off:
Dye Dilution Method

Add Dye

Mix

Centrifuge

Absorbance

Cuvette Emulsion

Measure dilution of dye solution by free oil

Characterization of Coalescence:
Coalescence/Oiling-off by DSC
0 -0.05 -10

Fat Crystallization
0 10 20 30 40

0 -0.05 -10

Water & Fat Crystallization

0 10 20 30 40

Heat Flow

-0.1 -0.15 -0.2 -0.25 -0.3

Heat Flow Temperature (C)

-0.1 -0.15 -0.2 -0.25 -0.3

Temperature (C)

Fat crystallization behavior of oil-in-water emulsions

Characterization of Coalescence:
Coalescence/Oiling-off by DSC
100

Oiling Off (%)

80 60 40 20 0 -40 -20
Water Crystaln

Fat Crystaln
Tween 20

Casein

20

40

Temperature (C)

Characterization of Coalescence:
Centrifugation Methods
Centrifuge Time Speed

Oil

Cream

Serum

HReleased

HC

CR OSM

g (VTotal VReleased ) = A

Partial Coalescence
Aggregation Fusion

Clumping of partially crystalline droplets due to penetration of fat crystal from one droplet into another droplet

SEM Images of Partial Coalescence

40C (Liquid droplets)

0C (Partially Crystalline Droplets)

O/W Emulsions viewed by SEM (John Coupland, Penn State)

Influence of Droplet SFC on Partial Coalescence

100 80 60 40 20 0 0 20 40 60 80 100

E C (%)

SFC (%)

Influence of Interfacial Membrane on Partial Coalescence

Oiling Off (%)
Thin Membrane -Prone to PC - e.g., Tween 20
100 80 60 40 20 0 -10 0 10 20
Casein Tween 20

Thick Membrane -Resistant to PC - e.g., casein

Temperature (C)

Case Study: Ice Cream Manufacture

Add Surfactant & Age Fat globules covered with thick milk protein membrane Fat globules covered with thin surfactant membrane

Partial Coalescence in Ice Cream

Partially coalesced droplets in continuous phase Air bubble Partially coalesced droplets around air bubble

Ice cream viewed by cryo-SEM (Douglas Goff. Guelph)

Methods of Controlling Partial Coalescence

Aggregation Fusion

Control droplet crystallization (SFC) Control thickness & viscoelasticity of membranes Control droplet-droplet interactions Control droplet collision frequency or contact time

Measurement of Partial Coalescence: Techniques & Protocols

Instrumental Techniques
Microscopy Particle Sizing Creaming stability/Oiling Off Solid fat content versus temperature

Experimental Protocols
Storage Tests Accelerated Storage Tests Environmental Stress Tests

Ostwald Ripening

Growth of large droplets at the expense of small droplets due to molecular diffusion of oil molecules through the aqueous phase driven by differences in Laplace pressure

Ostwald Ripening

Time

Growth of large droplets at the expense of small droplets due to molecular diffusion of oil molecules through the aqueous phase driven by differences in Laplace pressure

Features of Ostwald Ripening

35 30 25 20 15 10 5 0
0.1 1

(%)

0 hours 24 hours 48 hours

10

100

Diameter ( m)
0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 0 200 400 600

d 3 ( m 3 )

Monomodal PSD Evolution d3 proportional to time

Time (hours)

Influence of Oil Type on Ostwald Ripening

4

d 3 ( m 3 )

3 2

Decane

Hexadecane

1 0 0 25 50 75 100

Time (hours)

Food Emulsions Susceptible to Ostwald Ripening

High Susceptibility Emulsions containing oils with high water solubility, e.g., flavor oils, essential oils, SCFA Emulsions containing alcohol in the aqueous phase, e.g., cream liqueurs Low Susceptibility Emulsions containing oils with low water solubility, e.g., TAGS

Ostwald Ripening
<r>3/ t = 8 Vm S D / 9 R T
Methods of Retarding Ostwald Ripening:
Reduce oil solubility in water Reduce interfacial tension Incorporate low solubility oil into droplets Use membrane resistant to deformation

Measurement of Partial Coalescence: Techniques & Protocols

Instrumental Techniques
Microscopy Particle Sizing

Experimental Protocols
Storage Tests Accelerated Storage Tests Environmental Stress Tests

Conclusions
Many different physicochemical processes contribute to the instability of food emulsions For a particular food product it is necessary to identify the dominant instability mechanism Emulsion science can then be used to improve food emulsion stability