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Food Colloids
Dimitra Founta
Supervisor : Prof. George Petekidis
Course: Colloidal Dispersions | Department of Materials Science and Technology
UNIVERSITY OF CRETE
21/02/2019
2
1. Introduction
2. Experimental Measurements with Mayonnaise
OUTLINE
Studies in the LVE region
Studies in the NLVE region – yielding
3. Conclusions
Temperature effect ???
The term “colloid”—from the Greek words kolla, meaning “glue,” and eidos, meaning “like” —was first used in 1861 by
Thomas Graham
3
1.Colloids????
• Uniform mixtures that don't separate or settle out.
• Homogenous (but can appear as heterogeneous in microscopic scales)
• There are two parts to every colloid mixture: the particles and the dispersing medium.
Particles: Bigger than solutions , smaller than suspensions (~1nm-10μm)
size
1nm 10μm
Mixture Types
• Suspensions (>1 μm)
-Insoluble particles suspended in liquid or gas
-Separation after letting sit (exp. Sedimentation)
-Light can’t pass through completely
• Solutions(<1 nm)
-No separation of the particles and the solvent
-Light can pass through completely
4
Shake well
before useSand , Snow Ball , etc
Sugar in Water , Salt in Water, etc
Sugar-Technobyte-SEM
Is it colloidal?
Semipermeable membrane test
5
Tyndall effect test
Timberlake,Chemistry: An Introduction to General, Organic, and Biological
Chemistry, 7th Edition,1999,Pearson, Los Angeles Valley College
https://www.shutterstock.com/image-vector/tyndall-effect-436536265
1.Colloidal Dispersions in Foods
Emulsions
Liquid
Foams
6
Dispersed Phase-in-Dispersed Medium
Gas-in-Solid
Liquid-in-Liquid
Solid-in-Liquid
Gas-in-Liquid
Solid
Foams
Sols
Liquid-in-Solid
Solid
Emulsions
1.Interactions in Emulsions
7
DLVO theory
Repulsive
Attractive
r
V (r)
DLVO
Vtot = Vatt + Vrep
Secondary minimum
Binary minimum >>kBT
Energy Barrier
1.Typical instabilities of Emulsions
8
Creaming Sedimentation Flocculation Coalescence
Stable
Emulsion
Too strong repulsions Too strong attractions
Phase
separation
With medium Between particles
1.Emulsions Emulsifiers
9
Molecules that encourage the suspension of one immiscible phase to another
Lecithin (Soy, Egg Yolk)
B-Casein (Milk)
Poly-Glycerol Ester (PGE)
…
Hydrophilic
Lyophilic
O/W W/O
Reduction of interfacial tension
between two phases
• Microscopy (distribution and dimensions of droplets)
• Rheology
• Texture tests
• Odor, Color , pH
• …
1.Food Analysis Tests – Emulsion stability
10Source: Anton Paar
Why Rheology?
11
– Deformation or movement that occurs in a material (-)
How much did the sample move?
– Force applied to a sample (Force/unit area)
How hard did I push /twist the sample?
- A sliding deformation that occurs when there is
movement between layers in a sample
– Shear stress/shear strain rate
How resistance is it to flow?
– Stress/Strain
How “strong” is it ?
Rheology is the science of the
flow and deformation behavior of
substances. When matter flows or
is deformed there are three factors
which must be considered: the
internal structure, the external
forces which act on the substance,
and the environmental conditions,
for example temperature.
Source: Anton Paar
1.Rheometer : The set up used
12
kinexus Pro +
PL20mm -
Serrated
Tools
used
1.Dynamic Strain Sweep (DSS)
13
Define the linear regionG’G”(Pa)
LVE NLVE
γ (%)
𝛾 =
𝐷𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡
𝐻𝑒𝑖𝑔ℎ𝑡
1.Dynamic Frequency Sweep (DFS)
14
Time-dependent behavior of a sample in the non-destructive deformation range(LVE)G’G”(Pa)
ω (rad/s)
G″
G′
G′>G″ Solid-like
G″>G′ Liquid-like
G″ = viscous response
G′ = elastic response
Sol-Gel Transition
1.Flow Curve
15
Graphical description of the flow behavior
Shearstressσ(F/A)
Shear Rate γ (s-1)
Viscosityη(Pa*s)
Shear Rate γ (s-1)
Newtonian
Pseudoplastic
Dilatant
Newtonian Fluids- Time independent
2.Sample of study
Regular Mayonnaise
Oil phase 65%
16
2.DSS test : System rejuvenation
17
0.01 0.1 1 10
101
102
103
104
1 rad/s
1 rad/s
10 rad/s
10 rad/s
100 rad/s
100 rad/s
G',G''(Pa)
Strain (%)
Define
the LVE
DFS test: Linear Regime
18
G′>G″
Solid-like
10-2
10-1
100
101
102
101
102
103
104
0.5%-Load1
0.5%-Load1
0.1%-Load2
0.1%-Load2
0.05%-Load3
0.05%-Load3
G'G"(Pa)
Frequency (rad/s)
19
50 100 150 200 250 300
10-1
100
101
102
103
104
105
106
107
1
2
Viscosity(Pa*s)
Stress (Pa)
Slip effect
Regular Plate
Serrated Plate
2.Flow Curves
20
10-5
10-4
10-3
10-2
10-1
100
101
102
103
10-1
100
101
102
103
104
105
106
107 Load 1
Load 2
Load 3
n(Pa*s)
𝜸 η
Shear Thinning
10-5
10-4
10-3
10-2
10-1
100
101
102
103
100
101
102
103
104 Load 1
Load 2
Load 3
stress(Pa)
Yield Stress Fluid
Apparent yield stress
21
10-5
10-4
10-3
10-2
10-1
100
101
102
103
10-1
100
101
102
103
104
105
106
107
1rad/s
1rad/s
10rad/s
10rad/s
100rad/s
100rad/s
n(Pa*s)
shear strain (s-1
)
Thixotropy?
No hysteresis
Not thixotropic
22
10-2
10-1
100
101
101
102
103
104
G'(Pa)G"(Pa)
Strain (%)
G' -Rejuv1
G"-Rejuv1
G' -Rejuv2
G"-Rejuv2
DSS-MAYO T=15o
C , w = 1rad/s
10-2
10-1
100
101
102
103
104
G'(Pa)G"(Pa)
Strain (%)
G'- Rejuv1
G"-Rejuv1
G'- Rejuv2
G"-Rejuv2
G'- Rejuv3
G"-Rejuv3
DSS-MAYO T=15o
C , w = 10rad/s
10-2
10-1
101
102
103
104
G'(Pa)G"(Pa)
Strain (%)
G'-Rejuv1
G"-Rejuv1
G'-Rejuv2
G"-Rejuv2
DSS-MAYO T=15o
C , w = 100rad/s
2.DSS – Reproducibility Tests
Frequency Independent Strain Sweep Tests (Minor hysteresis)
23
2.DFS – Reproducibility Tests
γ = 0,5% γ = 0,1% γ = 0,05%
Solid like behavior observed in every load (in LVE)
10-2
10-1
100
101
102
100
101
102
103
104
Frequency (rad/s)
G'-Rejuv1
G"-Rejuv1
G'-Rejuv2
G"-Rejuv2
DFS-MAYO T=15o
C
10-2
10-1
100
101
102
101
102
103
104
Frequency (rad/s)
G'- Rejuv1
G"-Rejuv1
G'-Rejuv2
G"-Rejuv2
G'-Rejuv3
G"-Rejuv3
DFS-MAYO T=15o
C
10-2
10-1
100
101
102
101
102
103
104
G'(Pa)G"(Pa)
Frequency (rad/s)
G'-Rejuv1
G"-Rejuv1
G'-Rejuv2
G"-Rejuv2
DFS-MAYO T=15o
C
10-2
10-1
100
101
102
103
104
Steadyviscosity(Pa*s)
Shear rate (s-1
) 24
2.Step rate tests : Steady state viscosity
𝜸 ηs
Shear Thinning
0.1 1 10 100
101
102
103
104
γ=s-1
0.01
0.03
0.05
0.1
0.2
0.3
0.5
1.0
2.0
3.0
n(Pa*S)
t(s)
MAYO - T=15o
C
.
Viscoelastic behavior
25
0.01 0.1 1
80
100
120
140
Stress(Pa)
Shear rate (s-1
)
n = 0,21<1
Herschel-Buckley model
σ = σο + Κ* 𝛾n
Shear thinning behavior
σο=41,86 Pa
26
10-3
10-2
10-1
100
101
102
103
104
5
10
15
20
25
30
35
40
viscosity(Pa*s)
shear strain (s-1
)
Τ (οC)
2.Temperature effect on viscosity
3.Conclusions • Non-Newtonian fluid
• Yield Stress Fluid – Thixotropic X
• Solid-like behavior
• Shear thinning is observed
• No strong effect of Temperature
27
Mayonnaise Characterization
Thank You!
28

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Food Colloids Characterization with Rheology

  • 1. Food Colloids Dimitra Founta Supervisor : Prof. George Petekidis Course: Colloidal Dispersions | Department of Materials Science and Technology UNIVERSITY OF CRETE 21/02/2019
  • 2. 2 1. Introduction 2. Experimental Measurements with Mayonnaise OUTLINE Studies in the LVE region Studies in the NLVE region – yielding 3. Conclusions Temperature effect ???
  • 3. The term “colloid”—from the Greek words kolla, meaning “glue,” and eidos, meaning “like” —was first used in 1861 by Thomas Graham 3 1.Colloids???? • Uniform mixtures that don't separate or settle out. • Homogenous (but can appear as heterogeneous in microscopic scales) • There are two parts to every colloid mixture: the particles and the dispersing medium. Particles: Bigger than solutions , smaller than suspensions (~1nm-10μm) size 1nm 10μm
  • 4. Mixture Types • Suspensions (>1 μm) -Insoluble particles suspended in liquid or gas -Separation after letting sit (exp. Sedimentation) -Light can’t pass through completely • Solutions(<1 nm) -No separation of the particles and the solvent -Light can pass through completely 4 Shake well before useSand , Snow Ball , etc Sugar in Water , Salt in Water, etc Sugar-Technobyte-SEM
  • 5. Is it colloidal? Semipermeable membrane test 5 Tyndall effect test Timberlake,Chemistry: An Introduction to General, Organic, and Biological Chemistry, 7th Edition,1999,Pearson, Los Angeles Valley College https://www.shutterstock.com/image-vector/tyndall-effect-436536265
  • 6. 1.Colloidal Dispersions in Foods Emulsions Liquid Foams 6 Dispersed Phase-in-Dispersed Medium Gas-in-Solid Liquid-in-Liquid Solid-in-Liquid Gas-in-Liquid Solid Foams Sols Liquid-in-Solid Solid Emulsions
  • 7. 1.Interactions in Emulsions 7 DLVO theory Repulsive Attractive r V (r) DLVO Vtot = Vatt + Vrep Secondary minimum Binary minimum >>kBT Energy Barrier
  • 8. 1.Typical instabilities of Emulsions 8 Creaming Sedimentation Flocculation Coalescence Stable Emulsion Too strong repulsions Too strong attractions Phase separation With medium Between particles
  • 9. 1.Emulsions Emulsifiers 9 Molecules that encourage the suspension of one immiscible phase to another Lecithin (Soy, Egg Yolk) B-Casein (Milk) Poly-Glycerol Ester (PGE) … Hydrophilic Lyophilic O/W W/O Reduction of interfacial tension between two phases
  • 10. • Microscopy (distribution and dimensions of droplets) • Rheology • Texture tests • Odor, Color , pH • … 1.Food Analysis Tests – Emulsion stability 10Source: Anton Paar
  • 11. Why Rheology? 11 – Deformation or movement that occurs in a material (-) How much did the sample move? – Force applied to a sample (Force/unit area) How hard did I push /twist the sample? - A sliding deformation that occurs when there is movement between layers in a sample – Shear stress/shear strain rate How resistance is it to flow? – Stress/Strain How “strong” is it ? Rheology is the science of the flow and deformation behavior of substances. When matter flows or is deformed there are three factors which must be considered: the internal structure, the external forces which act on the substance, and the environmental conditions, for example temperature. Source: Anton Paar
  • 12. 1.Rheometer : The set up used 12 kinexus Pro + PL20mm - Serrated Tools used
  • 13. 1.Dynamic Strain Sweep (DSS) 13 Define the linear regionG’G”(Pa) LVE NLVE γ (%) 𝛾 = 𝐷𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡 𝐻𝑒𝑖𝑔ℎ𝑡
  • 14. 1.Dynamic Frequency Sweep (DFS) 14 Time-dependent behavior of a sample in the non-destructive deformation range(LVE)G’G”(Pa) ω (rad/s) G″ G′ G′>G″ Solid-like G″>G′ Liquid-like G″ = viscous response G′ = elastic response Sol-Gel Transition
  • 15. 1.Flow Curve 15 Graphical description of the flow behavior Shearstressσ(F/A) Shear Rate γ (s-1) Viscosityη(Pa*s) Shear Rate γ (s-1) Newtonian Pseudoplastic Dilatant Newtonian Fluids- Time independent
  • 16. 2.Sample of study Regular Mayonnaise Oil phase 65% 16
  • 17. 2.DSS test : System rejuvenation 17 0.01 0.1 1 10 101 102 103 104 1 rad/s 1 rad/s 10 rad/s 10 rad/s 100 rad/s 100 rad/s G',G''(Pa) Strain (%) Define the LVE
  • 18. DFS test: Linear Regime 18 G′>G″ Solid-like 10-2 10-1 100 101 102 101 102 103 104 0.5%-Load1 0.5%-Load1 0.1%-Load2 0.1%-Load2 0.05%-Load3 0.05%-Load3 G'G"(Pa) Frequency (rad/s)
  • 19. 19 50 100 150 200 250 300 10-1 100 101 102 103 104 105 106 107 1 2 Viscosity(Pa*s) Stress (Pa) Slip effect Regular Plate Serrated Plate
  • 20. 2.Flow Curves 20 10-5 10-4 10-3 10-2 10-1 100 101 102 103 10-1 100 101 102 103 104 105 106 107 Load 1 Load 2 Load 3 n(Pa*s) 𝜸 η Shear Thinning 10-5 10-4 10-3 10-2 10-1 100 101 102 103 100 101 102 103 104 Load 1 Load 2 Load 3 stress(Pa) Yield Stress Fluid Apparent yield stress
  • 22. 22 10-2 10-1 100 101 101 102 103 104 G'(Pa)G"(Pa) Strain (%) G' -Rejuv1 G"-Rejuv1 G' -Rejuv2 G"-Rejuv2 DSS-MAYO T=15o C , w = 1rad/s 10-2 10-1 100 101 102 103 104 G'(Pa)G"(Pa) Strain (%) G'- Rejuv1 G"-Rejuv1 G'- Rejuv2 G"-Rejuv2 G'- Rejuv3 G"-Rejuv3 DSS-MAYO T=15o C , w = 10rad/s 10-2 10-1 101 102 103 104 G'(Pa)G"(Pa) Strain (%) G'-Rejuv1 G"-Rejuv1 G'-Rejuv2 G"-Rejuv2 DSS-MAYO T=15o C , w = 100rad/s 2.DSS – Reproducibility Tests Frequency Independent Strain Sweep Tests (Minor hysteresis)
  • 23. 23 2.DFS – Reproducibility Tests γ = 0,5% γ = 0,1% γ = 0,05% Solid like behavior observed in every load (in LVE) 10-2 10-1 100 101 102 100 101 102 103 104 Frequency (rad/s) G'-Rejuv1 G"-Rejuv1 G'-Rejuv2 G"-Rejuv2 DFS-MAYO T=15o C 10-2 10-1 100 101 102 101 102 103 104 Frequency (rad/s) G'- Rejuv1 G"-Rejuv1 G'-Rejuv2 G"-Rejuv2 G'-Rejuv3 G"-Rejuv3 DFS-MAYO T=15o C 10-2 10-1 100 101 102 101 102 103 104 G'(Pa)G"(Pa) Frequency (rad/s) G'-Rejuv1 G"-Rejuv1 G'-Rejuv2 G"-Rejuv2 DFS-MAYO T=15o C
  • 24. 10-2 10-1 100 101 102 103 104 Steadyviscosity(Pa*s) Shear rate (s-1 ) 24 2.Step rate tests : Steady state viscosity 𝜸 ηs Shear Thinning 0.1 1 10 100 101 102 103 104 γ=s-1 0.01 0.03 0.05 0.1 0.2 0.3 0.5 1.0 2.0 3.0 n(Pa*S) t(s) MAYO - T=15o C .
  • 25. Viscoelastic behavior 25 0.01 0.1 1 80 100 120 140 Stress(Pa) Shear rate (s-1 ) n = 0,21<1 Herschel-Buckley model σ = σο + Κ* 𝛾n Shear thinning behavior σο=41,86 Pa
  • 27. 3.Conclusions • Non-Newtonian fluid • Yield Stress Fluid – Thixotropic X • Solid-like behavior • Shear thinning is observed • No strong effect of Temperature 27 Mayonnaise Characterization