CONFERENCIA INTERNACIONAL DE

REOLOGIA Y EXTRUSION
Osvaldo H. Campanella
Biological Engineering and Whistler
Carbohydrate Research Center
Temas específicos que serán cubiertos:
• Aplicaciones de Reologia en la ciencia y la ingeniería de alimentos
• Reologia de Biomateriales – Principios Básicos
• Tipos de fluidos y métodos para su caracterización
• Aplicaciones de Reologia para caracterizar alimentos y biomateriales los cuales
incluyen cereales y productos lácteos
• Caracterización de la estructura de materiales y su relación a su textura
• Reología de productos conteniendo nano partículas
• Transición vítrea. Caracterización and principios básicos
• Efecto de la transición vítrea en el procesamiento y la textura de productos • Efecto de la transición vítrea en el procesamiento y la textura de productos
alimenticios
• Extrusión, clasificación and descripción del proceso y tipos de tecnología
• Conceptos de extrusión reactiva
• Rol de Reología en el proceso de extrusión
• Extrusión de cereales
• Tecnología de Extrusión
• Efectos de Extrusión en las propiedades del material desde un punto de vista
textural y nutricional
Mechanical Properties
of Materials ?
“SCIENCE THAT STUDY THE DEFORMATION
AND FLOW OF MATERIALS”
RHEOLOGY
“SCIENCE THAT STUDY THE DEFORMATION
AND FLOW OF MATERIALS”
RHEOLOGY
lactose α −
α
Crystal Growth
-hydrate line
anhydrous β-
40
60
80
100

o
C
)
MATERIAL CHANGES DURING PROCESSING
e.g. MILK POWDER or Spray Drying of Pharmaceuticals
Evaporation
Spray Drying
Glassy
State
Solution
(Emulsion)
Lactose crystals
and solution
0 10 20 30 40 50 60 70 80 90 100
-60
-40
-20
0
20
40

T
e
m
p
e
r
a
t
u
r
e

(
o
Total Solids (%)
Ice and solution
Spraydried Lactose α−
Lactose α−
MATERIAL CHANGES DURING PROCESSING
Spray Drying of Lactose
Micro and Nano-Structures
Macro -Structures
Emulsions
Air Pockets
Powder
Foam
FOOD PRODUCT
STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide

Spraydried Lactose α−
Lactose α−
MATERIAL CHANGES DURING PROCESSING
Spray Drying of Lactose
Expansion
+ Water and other ingredients
EXTRUSION
In a very short time (less than a minute) the flour mixed with
water (plus shear and temperature) undergone a complete
transformation from a glassy material to a rubbery material
(called melt). That transformation is needed for expansion
Glass Transition – Concept
G
l
a
s
s

t
r
a
n
s
i
t
i
o
n

t
e
m
p
e
r
a
t
u
r
e

o
C
RUBBERY STATE
“Viscoelastic material”
Increasing temperature
G
l
a
s
s

t
r
a
n
s
i
t
i
o
n

t
e
m
p
e
r
a
t
u
r
e

Moisture Content (%)
GLASSY STATE
“Solid”
Increasing temperature
Increasing moisture
T
E
M
P
E
R
A
T
U
R
E
TRANSFORMATIONS OF RAW
MATERIALS DURING EXTRUSION
LIQUID
(AMORPHOUS)
Heating
Expansion
Glass Transition
MOISTURE
T
E
M
P
E
R
A
T
U
R
E
GLASS
Wetting and Mixing Dry Material
Expansion
Glass Transition
Temperature
USE OF RHEOLOGICAL DATA
Study of Material Microstructure (Texture)
T
e
x
t
u
r
e
Alignment of Particles
Stress
V
i
s
c
o
s
i
t
y
USE OF MECHANICAL PROPERTIES – RHEOLOGICAL- DATA
Textural Evaluation of Foods

C
r
i
s
p
n
e
s
s

M
e
a
s
u
r
e
d

a
s

s
o
u
n
d
p
r
o
d
u
c
e
d

w
h
e
n

c
r
u
s
h
i
n
g
a
n

e
x
t
r
u
d
e
d

s
a
m
p
l
e
Extrudate
Gluten
Waxy Starch
Wheat Starch
Relative Humidity (Water Activity)
M
e
a
s
u
r
e
d

a
s

s
o
u
n
d
p
r
o
d
u
c
e
d

w
h
e
n

c
r
u
s
h
i
n
g
a
n

e
x
t
r
u
d
e
d

s
a
m
p
l
e
Air Cells
Cell Walls
E
l
a
s
t
i
c

P
r
o
p
e
r
t
i
e
s
% Moisture
Gluten
Waxy Starch
Wheat Starch
“Crispness” is related to the
rheology of the cell wall material
and the microstructure of the
sample
RHEOLOGICAL PHENOMENA
• Occur in different scales of length and time
• Drastic changes are observed on the mechanical
properties of biomaterials during processing
• Drastic changes on mechanical properties of
biomaterials affecting their function (e.g. texture in
foods, stickiness in a glue, gelling agents, viscosity I
enhancers as stabilizers, etc ) are associated
to transitions, e.g. glass transition, gelling.
RHEOLOGICAL PHENOMENA
Low Molecular Weight
Solutions (monomer)
Liquid Behavior
Newtonian Behavior
High Molecular Weight
Solutions
Viscoelastic Liquids
Non-Newtonian Behavior
Very High Molecular
Weight Solutions
Viscoelastic Solids
Macrostructural Materials
Colloidal Suspensions
Structure Dependent
Response, Structure
Recovery and Breaking
Fundaments on Rheometry – Steady Shear
Shear Stress
Shear Rate
V
F
h
Velocity Profile u(y)
Ideal Shear Test
F
= σ
V
= γ
ɺ
A
= σ
h
= γ
ɺ
σ
γ
ɺ
Flow Curve
Newtonian
Shear
Thickening
Shear thinning
“Plastic”
0
σ
Yield Stress
µ
Newtonian Liquids – Definition of Viscosity Units
S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
s Pa
s
Pa
Rate Shear
Stress Shear
.
/ 1
= = = =
γ
σ
µ
ɺ
cP 1 Pa.s 10 mPa.s 1
3
= =

• Water
• Sucrose Solutions (up to concentrations of 60%)
• Skim milk
• Oil
• Glucose Solutions (not very concentrated)
• Diluted Juices
(1/s) Rate Shear γ
ɺ
S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
cP 1 Pa.s 10 mPa.s 1
3
= =

Flow Curves in terms of Viscosity
or shear
thinning) thinning)
shear
Thickening or
n
k γ σ
ɺ
=
k : Consistency Index (Pa.s
n
)
Power-Law Model
Rheological Models
Flow Curve
σ
Shear thinning
Shear thickening
Newtonian liquid
k : Consistency Index (Pa.s
n
)
n : Flow Index (-)
• If n < 1 liquid is shear thinning (or pseudoplastic)
• If n > 1 liquid is shear thickening (or dilatant)
• If n = 1 liquid is Newtonian
γ
ɺ
What are “plastic” liquids ?
• Tomato Paste
• Ketchup
• Toothpaste
• How do they behave?
We need to squeeze or push them so that the material flow
o
If σ σ <
The material will not flow, it behaves as a solid
o
If σ σ > The material flows, it behaves as a liquid
• A “yield” stress can be defined and compare
it with the applied stress
o
σ
σ
Plastic Fluid Materials
S
h
e
a
r

S
t
r
e
s
s Plastic shear thinning
Plastic Newtonian
“Binghan fluid”
Plastic shear thickenning
Shear Rate
S
h
e
a
r

S
t
r
e
s
s
o
σ
n
o
k σ σ γ = +
ɺ
Herschel-Bulkley Model
Other Models used to describe the
rheology of inelastic “plastic” fluids
Model Equation
1
5 0 5 0
5 0
1
5 0 5 0
1
n
o
o
K
K
+ =
+ =
+ =
. .
. . .
σ σ γ
γ σ σ
γ σ σ
ɺ
ɺ
ɺ
Casson
Modified Casson
Ellis
[ ]
2
1
2
1
0
1
2 1
1
2 1 1
1
n
n n
o
n
n
K
K
K K



+

+ =
+ =
+ =
) ( γ
η η
η η
γ σ σ
σ σ γ
ɺ
ɺ
ɺ
Ellis
Generalized
Herschel-Bulkley
Carreau
σ
σ
“Plastic” Materials – Yield Stress
o
σ
Liquid Medium
“Plastic” Medium
o
σ
γ
ɺ
g d
Y
part medium
o
) ( ρ ρ
σ

=
Yield Parameter
Diameter
Droplet Density
Medium Density
Culture B
Ropy
Un-stirred
Stirred
Confocal Microscopy
Green – Polysaccharides
Red – Protein
Black - Whey
60

Plastic Materials – Presence of Yield Stress
Yoghurt Rheology
n
o
kγ σ σ
ɺ
+ =
Culture C
Non-Ropy
Culture D
Ropy
0 20 40 60 80 100 120 140
0
10
20
30
40
50
60

S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Shear Rate (1/s)
Culture B. Ropy S.Thermophilus
Culture C - Non-Ropy
Culture D - Ropy S.Thermophilus
Hassan, A.N. et al. 2003. J. Dairy Sci., 86, 1632-1638
σ
γ η τ τ
ɺ
+ =
o
n
o
kγ τ τ
ɺ
+ =
Summary of Rheological Behavior
γ
ɺ
n
k γ τ
ɺ
=
o
σ
A More Extended Flow Curve
(logarithmic coordinates.)
Low shear
range
V
i
s
c
o
s
i
t
y
High Shear
range
Shear Rate
V
i
s
c
o
s
i
t
y
Interpretation of Rheological behavior
Low Shear Rates
shear is not enough to align the particles
thermal motion (k
B
T) will “randomize”
the orientation of the particles
Low V
Particles
Fluid serum
Intermediate Shear Rates
shear is enough to align the particles
Intermediate V
High Shear Rates
Intermediate V
High Shear Rates
High V
Low shear
range
High Shear
range
Flow Curve (log coord.)
Shear Rate
V
i
s
c
o
s
i
t
y
Time dependent liquids
Rheological Behavior of Liquids with Structures
Thixotropic Materials
Yoghurt made with
Ropy Strain B
Yoghurt made with
Un-stirred
Un-stirred
Stirred
Stirred
0
10
20
30
40
50
60
70

Up curve


S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Down curve
Ropy Strain B
40
50
60
70

S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Non-ropy Strain C
Yoghurt made with
Non-ropy Strain C
Yoghurt made with
Ropy Strain D
Un-stirred Stirred
0
10
20
30
40

Down curve

S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Up curve
0 20 40 60 80 100 120 140
0
10
20
30
40
50
60
70
Up Curve


S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Shear Rate (1/sec)
Ropy Strain D
Down Curve
Hassan, A.N. et al. 2003. J. Dairy Sci., 86, 1632-1638
Other Thixotropic Behavior Studies
0
o
γ
ɺ
Rest
Period
Time
o
γ
ɺ
o
γ
ɺ
Complete Recovery
Partial Recovery
No Recovery
Time
Time
η
σ
or
0
Traditional Rotational Viscometry
Sample
M , Ω
Sample
M , Ω
How do we measure these “liquid” properties?
Concentric Cylinders
Sample
Sample
Parallel Plates
M , Ω
m) - (N Torque : M
rad/s Speed, Rotational : Ω
Cone and Plate
h
Capillary Viscometer
Rheology Testing
“Mixer” Geometry
Pulse Shear Test
Interfacial
Rheology
Effect of Temperature on the
viscosity of “liquids”
V
i
s
c
o
s
i
t
y
T
B
e A T = ) ( µ
Arrhenius-type of equation
: " Viscosity"
A and B are parameters determined from data
µ
T
Applications of Stabilizers (Low Shear Viscosity)
Stabilize coalescence
and creaming
Used in frozen foods and beverages
(it creates pleasant texture, e.g. ice creams)
Ostwald Ripening (Low Shear Viscosity)
Stablizer Uses (Low Shear Viscosity)
Fluid Medium
Other Uses of Stabilizers (Low Shear Viscosity)
Xanthan gum: Binder in food products – gluten free bread
(acting as gliadin)
Binder in non-food products (e.g. toothpaste)
Stabilizer Uses (Low Shear Viscosity)
Thickener (e.g. xanthan gum in yoghurt)
25
30

Milk - No XG
Milk - 0.005% XG
Milk - 0.01% XG
Xanthan Gum Network
0 20 40 60 80 100 120
0
5
10
15
20

V
i
s
c
o
s
i
t
y

(
c
P
)
Incubation Time (minutes)
El-Sayed et al., (2002)
Eur Food Res Technol (2002)
RHEOLOGICAL PHENOMENA
Low Molecular Weight
Solutions (monomer)
Liquid Behavior
Newtonian Behavior
High Molecular Weight
Solutions
Viscoelastic Liquids
Non-Newtonian Behavior
Solutions
Non-Newtonian Behavior
Very High Molecular
Weight Solutions
Viscoelastic Solids
Macrostructural Materials
Colloidal Suspensions
Structure Dependent
Response, Structure
recovery and Breaking
VISCOELASTICITY
A viscoelastic material, depending on time, may be behave either as
solid or liquid. At short times it behaves as a solid, at long times it
behaves as a liquid
SHORT TIMES
41
LONG TIMES
VISCOELASTIC PHENOMENA
CONCEPT OF VISCOELASTICITY
Maxwell: Viscous flow is the manifestation of the decay of
elastically stored energy
High Energy (Stored “elastic” energy)
Low Energy
Low Energy
exp
R
D
t
t
e =
exp
R
De Deborah nu
t
t
mber =
1 De
Solidlike
>>
(1) De Order
Viscoelastic
∼ 1 De
Liquid
<<
Times involved on the rheological phenomena
0
6
B
k T
D
a πη
=
• Diffusion of “spherical” molecules (radius “a”)
Stokes/Einstein Equation
k
B
: Boltzman constant
T : Temperature
0
: FluidViscosity η
0
6 a πη
0
2 2 3
0
2
( ) 6
(sec)
( )
D
B
a m a
t
m k T
D
s
πη
= =
• Diffusion time t
D
(sec) – Einstein/Smoluchowski Equation
u (m/s)
x
z
y
h

(
m
)
exp
( ) 1
( / )
h meters
t
u meters s γ
= =
ɺ
exp
( / )
t
u meters s γ
= =
ɺ
Peclet Number
D
B
t a
Pe
t k T
πη γ
= =
ɺ
3
0
exp
(sec) 6
(sec)
1E-4
0.01
1
100
10000
Colloids

D
i
f
f
u
s
i
o
n

T
i
m
e

t
d

(
s
e
c
o
n
d
s
)
Molecules
Macromolecules
T
i
m
e

S
c
a
l
e

i
n

L
a
b
o
r
a
t
o
r
y
Time Scales
0.1 1 10 100 1000 10000
1E-12
1E-10
1E-8
1E-6
D
i
f
f
u
s
i
o
n

T
i
m
e

t
Molecule/Particle Radius (nm)
T
i
m
e

S
c
a
l
e

i
n

L
a
b
o
r
a
t
o
r
y
F
F
F proportional to the
Rate of Deformation
" DASHPOT" ~ LIQUID
L
LIQUID
ELASTIC SOLID
L
F proportional
to Deformation
" SPRING " ~ SOLID
Viscoelastic Measurements
• DEFORMATION DOES NOT
FOLLOW THE FORCE
TIME
to
t1
Permanent
Deformation
TIME
L
t1 to
• FORCE AND DEFORMATION
ARE “ OUT OF PHASE ”
• DEFORMATION FOLLOWS
THE FORCE
• FORCE AND DEFORMATION
ARE “ IN PHASE “
L
TIME
TIME
δ = Angle Phase
Traditional Viscoelastic Measurements
Torque bar
Sample
Cup
Bob
0
cos
) ( '
γ
δ σ
ω
o
G =
Storage Modulus
sinδ σ
Loss Modulus
) ( '
) ( ' '
tan
ω
ω
δ
G
G
=
Loss Tangent
Liquid Viscous
Material ic Viscoelast
Solid Elastic Hookean
o
o
90
90 0
0
=
< <
=
δ
δ
δ
Strain γ γγ γ
Stress σ σσ σ
o
σ
o
γ
Oscillator
Phase Angle δ δδ δ
0
sin
) ( ' '
γ
δ σ
ω
o
G =
Pulse Shear Test
Viscoelasticity Testing
Concentric Cylinders
Sample
M , Ω
Sample
Cone and Plate
M , Ω
Sample
Parallel Plates
M , Ω
h
“Mixer” Rheology
CONTROLLED STRESS INSTRUMENTS
t sin
o
ω τ τ =
Stress Amplitude
(fixed by the user)
Frequency
(fixed by the user)
Input
Output
) ( sin δ ω γ γ + = t
o
Strain Amplitude
(measured)
-15
-10
-5
0
5
10
15
0 2 4 6 8
Time
S
t
r
e
s
s

o
r

S
t
r
a
i
n
Stress
Strain
) ( sin δ ω γ γ + = t
o
o
γ
o
σ
δ
Measured
Measured
Phase Angle
(measured)
CONTROLLED STRAIN INSTRUMENTS
Input
t
o
ω γ γ sin =
) t ( sin δ ω τ τ + =
Output
Strain Amplitude
(fixed by user)
Frequency
(fixed by user)
Stress Amplitude
(measured)
) t ( sin
o
δ ω τ τ + =
(measured)
Phase Angle
(measured)
) t ( sin
o
δ ω τ τ + =
) ( ) ( " ) ( ) ( ' ω γ ω γ ω σ
ɺ
G t G + =
Solid Behavior Liquid Behavior
) ( ) ( " G ) t ( ) ( ' G ) t ( ω γ ω γ ω τ
ɺ
+ =
Solid Behavior
Liquid Behavior
Oscillatory Testing
δ
γ
τ
ω cos ) ( ' G
o
=
Storage Modulus
δ
γ
τ
ω sin ) ( " G
o
o
=
γ
cos ) ( ' G
o
Loss Modulus
tan (Phase Angle)
) ( '
) ( "
tan
ω
ω
δ
G
G
=
Oscillatory Testing
Other Viscoelastic Parameters
2 2 *
" ' ) ( G G G + = ω • Complex Modulus
• Complex Viscosity
ω ω
ω
η
2 2 *
*
" ' ) ( G G G +
= =
ω ω
η = =
• Dynamic Viscosity
• Out of Phase Viscosity
ω
ω
η
) (
'
"
G
=
ω
ω
η
) (
"
'
G
=
Oscillatory Testing
Other Viscoelastic Parameters (from Controlled Stress)
2 2
*
*
" '
1 1
) (
G G
G
J
+
= = ω
• Complex Compliance
• Storage Compliance
2 2
" '
'
) ( '
G G
G
J
+
= ω
• Storage Compliance
2 2
" '
) ( '
G G
J
+
= ω
• Loss Compliance
2 2
" '
"
) ( '
G G
G
J
+
= ω
VISCOELATIC MATERIALS
Solid (elastic) and Liquid (viscous) Behavior !!!!
τ
τ
µ γ
ɺ
Spring
γ τ G =
Dashpot
γ µ τ
ɺ
=
G
γ
µ γ
ɺ
VISCOELATIC MATERIALS
Maxwell Element
G
τ
s
γ
γ µ
τ
τ
ɺ
= +
dt
d
t
R
Rheological Model
µ
d
γ
s
γ
G
t
R
µ
=
Relaxation Time
Maxwell Element
G
τ
s
γ
What happens if a Maxwell
Element is oscillated ?
2 2
2 2
1
'
R
R
t
t G
G
ω
ω
+
= • Storage Modulus
• Loss Modulus
2 2
1
"
R
R
t
t G
G
ω
ω
+
=
µ
d
γ
s
γ
" ' G or G
ω
Solid Behavior
' G
" G
1 =
R
t ω
Materials are more complex than
a single Maxwell
G
1
G
2
1
µ
2
µ
1
1
1
G
t
R
µ
=
2
2
2
G
t
R
µ
=
2
2
2
2
2
2
2
2
1
2
2
1
2
1
1 1
'
R
R
R
R
t
t G
t
t G
G
ω
ω
ω
ω
+
+
+
=
2
2
2
2 2
2
1
2
1 1
1 1
"
R
R
R
R
t
t G
t
t G
G
ω
ω
ω
ω
+
+
+
=
Four Element
Generalized Maxwell
G
1
1
µ
G
2
G
3
2
µ
3
µ
G
n
n
µ

=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
2 2
1
'
ω
ω

=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
1
"
ω
ω
i
i
Ri
G
t
µ
=
" G
or
' G
Viscoelastic Properties Determination
" G
' G
Frequency Sweep Tests

=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
2 2
1
'
ω
ω

=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
1
"
ω
ω
µ
" G
ω
i
i
Ri
G
t
µ
=
Xanthan Gum Uses (What rheology is required?)
Drilling Fluids (CaCO
3
and Xanthan Gum)
- Highly shear thinning properties and rapidly structure forming
(high viscosity at low shear rates and ability to form gels)
Required Rheological
Functionality
0.01 0.1 1 10 100 1000
0.01
0.1
1
10
100


V
i
s
c
o
s
i
t
y

(
P
a
.
s
)
Shear Rate (1/s)
Drilling Mud - CaCO
3
and Xanthan Gum
1 10 100
1
10


G" (Loss Modulus)
G' (Storage Modulus)
G
'
,

G
"

(
P
a
)
Frequency, ω (1/s)
Drilling Mud
Viscoelastic Properties
“Liquid” Properties
Xanthan Gum Uses (what rheology is required?)
Combining Steady Shear and Oscillatory Tests
1
10

V
i
s
c
o
s
i
t
y

(
P
a
.
s
)

o
r

G
"
/
ω

(
P
a
.
s
)
Drilling Fluids
Cox-Merz Rule
1 −

'
"
n
G
ω
1 10 100
0.01
0.1
1

Shear Viscosity (Pa.s)
Dynamic Viscosity (Pa.s)
V
i
s
c
o
s
i
t
y

(
P
a
.
s
)

o
r

G
"
/
Shear Rate γ or Frequency ω
Shifting Data
1 −

' n
ω
ω
1 −

n
γ η
ɺ
10

S
t
o
r
a
g
e

M
o
d
u
l
u
s

G

(
P
a
)
Xanthan Gum Uses (what rheology is required?)
Drilling Fluids (CaCO3 and Xanthan gum)
Fluid Temperature Stability
It is important that the drilling
mud has a large Tm, the
temperature at which xanthan
gum in solution has a transition
from a multi to a single
stranded molecule
20 30 40 50 60 70 80
1

S
t
o
r
a
g
e

M
o
d
u
l
u
s

G

(
P
a
)
Temperature (
o
C)
Tm
stranded molecule
Measurements
• Unsteady Shear testing
Oscillatory Testing (small deformation)
Transient Testing (small and large deformation)
1. Start-up Flow Test
2. Cessation of Steady Shear Flow
3. Step Strain (Relaxation experiment)
4. Creep Test
5. Recoil Test
Data Generated using Transient Methods Data Generated using Transient Methods
• Shear Stress Growth Function
• Shear stress decay function
• Shear stress relaxation Function or Relaxation Modulus
• Shear Creep
• Recoil Function (Strain)
) t (
) t (
) t ( or ) t (
o
γ
τ
µ τ
ɺ
=
) t ( τ
o
) t (
) t ( G or ) t (
γ
τ
τ =
o
) t (
) t ( J or ) t (
τ
γ
γ =
) t ( γ
3. Step Strain or Relaxation Test
(not the same than start-up flow)
o
γ
) t ( γ
t
o
) t (
) t ( G
γ
τ
=
Relaxation Modulus
t
) t ( τ
t
o o
Gγ τ =
o
t
o
t
Relaxation stresses
for materials with
different relaxation
times
Residual stress
Different t
R
1. Start-up Flow
o
γ
ɺ
t
t
exp
R
t
t
De =
• Large Deborah Number
Elastic Behavior
• Small Deborah Number
Viscous Behavior
1
1. Unsteady Shear testing
t
o
t
) t ( τ
t
o
t
o
τ
Increasing shear rates
o
γ
ɺ
o
exp
1
t
γ
ɺ

Extremely low shear rate
Non-elastic
fluid
De is small
o
o o
( t ) ( t )
for t
and
τ µ γ
τ µ γ
=
→ ∞
=
ɺ
ɺ
2. Cessation of Steady Shear Flow
o
γ
ɺ
) t ( γ
ɺ
t
1
t
t
) t ( τ
1
t
1
t
o
σ
t
4. Creep Test
) t ( τ
t
) t ( γ
t
G
o
o
τ
γ =
5. Recoil Test
) t ( τ
t
1
t
o
t
t
t
G
o
o
τ
γ =
1
t
o
Partial Recoil
permanent
deformation
No Recoil
Full Recoil
G
σ
s
γ
γ µ
τ
τ
ɺ
= +
dt
d
t
R
VISCOELASTIC FLUIDS - MODELING
σ
σ µγ + =
ɺ
d
t
µ
d
γ
σ µγ + =
ɺ
R
t
dt
v
v v ρ τ ρ

| |
+ ⋅∇ =−∇ +∇⋅ +
|

\ ¹
p g
t
τ
τ µγ + =
ɺ
R
d
t
dt
t
t G t t t dt ( ) ( ') ( ') ' τ γ
−∞
= −

ɺ
Generalized Linear
Viscoelastic Model
Strain-rate tensor
G
σ
µ
d
γ
s
γ
t t '
µ


Strain-rate tensor
“depending on flow”
Material Dependent
R
t t
t
R
G t t e
t
'
( ')
µ


− =
This equation is good for small strain, small strain rates
Many industrial applications applied large strains,
large strain rates, and the strain and the strain rate
histories are important
CONCLUSIONS
• Food and Biomaterials encompass a range of rheological
properties that cannot be fully evaluated by only one method.
A number of methods to characterize the rheology of liquid
and viscoelastic materials (including semisolid and solid
materials) have been described.
• Mainly fundamental tests were described. Fundamental
versus empirical methods are continuously revaluated for
testing. Empirical methods are simpler and less expensive
than fundamental tests but they have more limitations.
• Length and time scales need to be evaluated to interpret
and analyze rheological data from viscoelastic materials if
they intended to study structure-function material behavior.
GLASS TRANSITION PHENOMENON
Formation of Amorphous Materials

CRYSTAL LIQUID SOLUTION
(Structure Disruption) (Energy Removal) (Solvent Removal)
• Milling
• Granulation
• Compression
• Grinding
• Dehydration
• Rapid Cooling
• Nucleation
• Stop polymerization
reaction
• Extrusion
• Freeze Drying
• Spray Drying
• Precipitation
• Polymerization
• Reaction • Dehydration
• Irradiation
• Extrusion
(solid liquid solid
• Reaction
AMORPHOUS MATERIAL or AMORPHOUS STATE
Unintentional
Intentional
300
400
Amorphous Novobiocin

A
b
s
o
r
b
a
n
c
e
SOLUBILITY ENHANCEMENT OF AMORPHOUS MATERIALS
0 1 2 3 4
0
100
200

A
b
s
o
r
b
a
n
c
e
Time (hours)
Crystalline Novobiocin
SOME DIFFERENCES BETWEEN CRYSTAL
AND AMORPHOUS MATERIALS
Material Specific Volume (ml/g)
Crystal Amorphous
Indomethacin 0.72 0.75
Sucrose 0.63 0.70 Sucrose 0.63 0.70
Lactose 0.62 0.68
Trehalose 0.63 0.67
Dextran - 1.09
PVP - 0.80
SOME DIFFERENCES BETWEEN CRYSTAL
AND AMORPHOUS MATERIALS
Material Hardness
x 10
7
(Pa)
Bending Strength
x 10
4
(Pa)
Mechanical Properties of Metal Oxides
(Phenobarbitone Forms)
x 10
7
(Pa) x 10
4
(Pa)
Form II
42 187
Form III
28 567
Amorphous
6.5 1,056
Kopp et al., 1989
SUMMARY
• Drugs, excipients and formulations can exist as
amorphous forms
Some materials are naturally amorphous
Some materials becomes intentionally amorphous
during processing
Some materials are changed to amorphous intentionally
• Advantages of amorphous versus crystalline Materials
Improved dissolution Improved dissolution
Higher solubility
Higher bioavailability
Unique mechanical properties
• Disadvantages of amorphous versus crystalline materials
Chemically unstable
Physically unstable
Hygroscopic
PROPERTIES OF AMORPHOUS MATERIALS
• Non-equilibrium solid state
• Randomly arranged molecules
• Occupy larger volume than crystals of the same material
• Formed by rapid cooling processes
• Structure dependent on cooling rate
• Different cooling rates rates in different glasses of the • Different cooling rates rates in different glasses of the
same material
Crystal
Amorphous/
Glass
How are glasses formed?
V
o
l
u
m
e
Slow
Rapid
Cooling
Temperature
V
o
l
u
m
e
Slow
Cooling
Crystal
Amorphous
T
g
T
m
/ T
f
Why do we care about glass transition?
• Glass transition is an important phenomena in processing
of biomaterials, foods and pharmaceuticals
• Glass transition is a key factor in determining the stability • Glass transition is a key factor in determining the stability
and quality of foods and pharmaceuticals. Shelf life of
foods is associated to glass transition
• Glass transition can affect other thermal properties and
processes such as crystallization
HOW DO WE MEASURE GLASS TRANSITION?
• Changes in specific volume with temperature
• Changes in conductivity with temperature
• Changes in heat capacity (DSC) with temperature • Changes in heat capacity (DSC) with temperature
• Changes in mechanical properties with temperature
Glass Transition and Rheological Properties
“Rheological
Property”
For Example
Amorphous
“Glassy” Material
Glass transition region
“Rubbery” Material
the Elastic Modulus
Temperature
T
g
High Solid Content
(low solvent)
Low Solid Content
(high solvent)
Glass
transition
region
T
g
Dynamic Mechanical Analysis
(DMA)
• DMA tablet preparation:
– Disadvantages:
• Compress sample under
5,000 lb force
• May cause changes in
amorphous sample amorphous sample
• DMA Powder cell
– Advantages:
• No preparation is required
• Loose sample can be
used
• No alteration in structure
of the sample due to
excessive compression
Oscillatory Squeezing Flow (OSF)
• The oscillatory squeezing flow is
based on a well known rheological
technique called squeezing flow with
added technological improvements added technological improvements
• It involves oscillations at random
frequencies up to 10 kHz (10,000 Hz)
compared with existing instruments
whose oscillation frequency is 10-20 Hz
Instrument Set-up
Concept
Elasticity
Damping
Application
Oscillatory Squeezing Flow (OSF) Theory

+ + = dt t u s t Ru t u m t F ) ( ) ( ) ( ) (
ɺ
Acceleration
Velocity
) (
ˆ
ˆ
ˆ
ω
ω
s
m i R
u
F
Z − + = =
Displacement
Mechanical Impedance
Viscous Component
Elastic Component
Oscillatory Squeezing Flow (OSF) Theory
o
eff
a :Diameter of the topplate
h :Gapbetweenplates
:Frequency
m :Effectivemass
ω ωω ω
Oscillating
Plate
Rigid
Surface
R
S
h
o
Sample
m
eff
ω
Stefan Equation Squeezing Flow
Elastic “Storage” Modulus
Viscous “Loss” Modulus
*
sample
o
a
ˆ
Z
h
π ππ π
η ηη η = == =
4 44 4
3 33 3
3 33 3
2 22 2
( (( ( ) )) )
2 3
2 4
3 2
ˆ
20 3
eff o
sample
o
m a h
Im Z
a
G
h
ω ω ω ω ω ω ω ω
π ππ π
= + ⋅ = + ⋅ = + ⋅ = + ⋅
′ ′′ ′
( ( ( (
( ( ( (
¸ ¸ ¸ ¸ ¸ ¸ ¸ ¸
( (( ( ) )) )
ˆ
3
o
sample
4
2h ω
Real Z × G
3 a π ππ π
′′ ′′ ′′ ′′
= == =
Pharmaceutical Materials
• Polyethylene Oxide
– 200,000 Da, MW
– 900,000 Da, MW
– 2,000,000 Da, MW
• Indomethacin
• Felodipine
• Griseofulvin
Indomethacin, Felodipine and Griseofulvin samples were melt quenched
Melting of Polyethylene-oxide
0.4
0.6
0.8
1.0
-14
-12
-10
-8
-6
-4
-2
0
N
o
r
m
a
l
i
z
e
d

S
t
i
f
f
n
e
s
s

(
D
i
m
e
n
s
i
o
n
l
e
s
s
)
BBFSF Data

H
e
a
t

F
l
o
w

(
m
W
)
DSC Scan
Polyethylene Oxide 900,000 MW
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
-26
-24
-22
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
BBFSF Data
N
o
r
m
a
l
i
z
e
d

S
t
i
f
f
n
e
s
s

(
D
i
m
e
n
s
i
o
n
l
e
s
s
)
Polyethylene Oxide 200,000 MW
DSC Scan

H
e
a
t

F
l
o
w

(
m
W
)
30 40 50 60 70 80
0.5
0.6
0.7
0.8
0.9
1.0
1.1
-14
-12
-10
-8
-6
-4
-2
0
2
N
o
r
m
a
l
i
z
e
d

S
t
i
f
f
n
e
s
s

(
D
i
m
e
n
s
i
o
n
l
e
s
s
)
Temperature (
o
C)
BBFSF Data DSC Scan

H
e
a
t

F
l
o
w

(
m
W
)
Polyethylene Oxide 2,000,000 MW
30 40 50 60 70 80
Temperature (
o
C)
10 20 30 40 50 60 70 80 90 100
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
H
e
a
t

F
l
o
w

(
m
W
)
Temperature (
o
C)
PEO 200,000 Da PEO 900,000 Da PEO 2,000,000 Da
DSC Scan for Polyethylene Oxide
30 40 50 60 70 80
Temperature (
o
C)
Active Ingredients data summary
Drug Powders DSC DMA OSF
Felodipine
Range: 43 – 47
o
C Range: 45 – 47
o
C Range: 49 – 51
o
C
Average: 45
o
C Average: 46
o
C Average: 50
o
C
STD: 2.72
o
C STD: 1.25
o
C STD: 0.85
o
C
Indomethacin Indomethacin
Range: 44 – 47
o
C Range: 46 – 48
o
C Range: 50 – 52
o
C
Average: 45
o
C Average: 47
o
C Average: 51
o
C
STD: 1.66
o
C STD: 1.22
o
C STD: 0.70
o
C
Griseofulvin
Range: 80 – 83
o
C Range: 79 – 87
o
C Range: 75 – 85
o
C
Average: 81
o
C Average: 83
o
C Average: 80
o
C
STD: 0.41
o
C STD: 3.73
o
C STD: 7.78
o
C
PRODUCTION OF CORN FLAKES
RHEOLOGY IN FOOD PROCESSES
Materials
Corn grits
Final Product
Cooking
PROCESS
Dry
Milling
Drying
Tempering
Cooking
Flaking
PROCESS
Dry
Milling
Drying
Tempering
Tosting
FINAL PRODUCT QUALITY
Intermediate and
Low Molecular Weight
Region
Fragmented Amylopectin
and Amylose
Range: 10
4
- 10
6
Da
Sugars and
Non-iodine
Binding Material
Chromatographic profile of corn flakes
High Molecular Weight
Amylose
Range: 10
4
- 10
6
Da
Elution Volume (Ml)
High Molecular Weight
Region
Amylopectin
Range: 10
7
- 10
8
Da
Amylopectin
6.50
7.00
7.50
8.00
8.50
R
e
l
a
t
i
v
e

F
r
a
g
m
e
n
t
a
t
i
o
n
FINAL PRODUCT QUALITY
6.00
6.50
5.0 7.0 9.0 11.0 13.0 15.0 17.0 19.0
Can Weight (oz/gal)
R
e
l
a
t
i
v
e

F
r
a
g
m
e
n
t
a
t
i
o
n
Gap
volume
weight
Density =
Gap Density ≡
Gap
40
45
50
55
60
T
g

(
°
C
)

190
210
230
250
270
290
310
330
350
W
a
t
e
r

U
p
t
a
k
e

(
%
,

3

m
i
n
.
)

FINAL PRODUCT QUALITY
Products obtained under several processing conditions
35
40
5 7 9 11 13 15
Density (oz/gal)
Gap
150
170
35 40 45 50 55 60
Tg (°C)
Cooking
Drying
PROCESS
Dry
Milling
Drying
Tempering
Rheological Properties of corn flake grits
Concept
Design
Elasticidad
Damping
Model

+ + = dt t u s t Ru t u m t F ) ( ) ( ) ( ) (
ɺ
Acceleration Acceleration
Velocity Velocity
Displacement Displacement
) (
ˆ
ˆ
ˆ
ω
ω
s
m i R
u
F
Z − + = =
Mechanical Impedance
Application
Mert, B. and Campanella, O.H. 2004. Viscoelastic properties of liquids
and semisolids materials using squeezing theory and impedance measurements
from forced vibrations. US Provisional Patent
RESULTS
0.06
0.08
0.1
|
M
o
b
i
l
i
t
y
|


m
/
s
.
N
60 min
30 min
15 min
Raw
Rheology of the kernel during
the cooking process
0.06
0.08
0.1


|
M
o
b
i
l
i
t
y
|

(
m
/
s



N
)
0 min
120 min
30 min
dried
60 min
cooked
cooking
drying
Rheology of the kernel during
the drying process
1000 3000 5000 7000 9000
0.02
0.04
ω (rad/s)
|
M
o
b
i
l
i
t
y
|


m
/
s
.
N
7 min
2 min
1000 3000 5000 7000 9000 11000 13000
0.02
0.04
ω (rad/s)


|
M
o
b
i
l
i
t
y
|

(
m
/
s

120 min
dried
60 min
dried
dried
) (
ˆ
ˆ
ˆ
ω
ω
s
m i R
u
F
Z − + = =
2 2
1 1
) (
ˆ
ω
ω
s
m R
Z
Mobility
− +
= =
m
s
peak
= ω
At Resonance Peak
peak
ω
Zein Structure
• Crystallization
GLUTEN FREE PRODUCTS
α −
• Small Angle X-Ray Scattering
• Molecular Simulation
Momany et al, 54(2), 543-547, 2006. J. Ag and Food Chem.
• Dough Rheology
• Transitions: Glass Transition, Starch Gelatinization
• Texture
GLUTEN FREE PRODUCTS
Starch-zein
Wheat
zein-glutenin
(ratio 10:1)
zein-casein
(ratio 10:1)
• 87% Starch-13%protein
• Mixed at 25
o
C
• Conditioned at 25
o
C
• 87% Starch-13%protein
• Mixed at 25
o
C
• Conditioned at 35
o
C
Wheat
Starch-zein
zein-glutenin
(ratio 10:1)
zein-casein
(ratio 10:1)
Why wheat proteins have such as exceptional characteristics
to produce viscoelastic dough and quality bread ?
Disulfide Interchange Model
1. Gluten’s prolamin constituent, Gliadin, responsible for
viscous behavior, due non-covalent forces (hydrogen
bonding, van der Waal’s forces)
1. Polymeric Glutenins (High Molecular Weight, HMWand Low
CURRENT MODELS
1. Polymeric Glutenins (High Molecular Weight, HMWand Low
Molecular Weight (LMW) linked through intermolecular
disulfide bonds contribute to dough elasticity
2. Dough strength and elasticity associated with the
development of gluten’s polymeric matrix, comprised of
HMW and LMW linked through intermolecular disulfide
bonds
GLUTEN FREE PRODUCTS
Hypothesis on Protein Fibril Formation in Zein
Loop and Train Model for Gluten Functionality
i
ii
iii
Loop Region
Train Region
(A)
(B)
Molecule of High Molecular Weight Glutenin
Shewry et al, 2002, Belton, 2005
Hypothesis on Protein Fibril Formation in Zein
Erickson et al, 2011. Trends in Food Science and technology
Helix Structur
FTIRTechn ue
e
iq
α −
Zein Gluten Zein-HMW glutenin
GLUTEN FREE PRODUCTS
0min 3min 6min
0.0
10.0
20.0
30.0
40.0
50.0
60.0
Relaxation time (min)
F
r
a
c
t
i
o
n

s
e
c
o
n
d
a
r
y

s
t
r
u
c
t
u
r
e

(
%
)
A
a
A
a
A
a
B
b
B
b
B
b
B
b
B
b
B
b
0min 3min
6min
0.0
10.0
20.0
30.0
40.0
50.0
60.0
Relaxation time (min)
F
r
a
c
t
i
o
n

s
e
c
o
n
d
a
r
y

s
t
r
u
c
t
u
r
e

(
%
)
Aa
Bc
Bce
Bce
Ab
Bde
Ab
Bce
Be
Sheet Structur
FTIRTechn ue
e
iq
β −
Mejia et al., 2011 (Accepted)
GLUTEN FREE PRODUCTS
Standard Rheological Technique
Instrument Set-up
GLUTEN FREE PRODUCTS
Novel Rheological Techniques
Mert et al, Review of Scientific Instruments, 2005
Mert and Campanella, Rheologica Acta, 2007
Mert and Campanella, Journal of Food Engineering, 2008
Concept
F( t ) mu( t ) Ru( t ) s u( t )dt = + +

ɺ
Acceleration
Velocity
Displacement
R : Dissipation – “viscosity” of sample
s: Stifness – “Elasticity” of sample
Concept
Novel Rheological Techniques
Sample
Standing Waves
Gonzalez et al. 2010. Journal of Food Engineering, 100(2), 187-193
Mert, B. and Campanella, O.H. 2008. Rheologica Acta, 47, 727-737
Mert et al. 2007. Journal of Cereal Science, 46(1), 32-38
GLUTEN FREE PRODUCTS
Novel Rheological Techniques
Micro and Nano-Structures
Macro -Structures
Emulsions
STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide

Fibers in Foods
JUSTIFICATION
• The Food and Nutrition Board of the Institute of
Medicine has set recommendations at 38 and 25
g/day of fiber for men and women, respectively.
• Breakfast cereals and snacks contain low fiber • Breakfast cereals and snacks contain low fiber
content because incorporation of fibers into these
extruded products limits their puffing ability and
reduces crispness.
• Aim: Identify and/or modify fibers for incorporation
at high levels in extruded products with acceptable
textural and sensory characteristics.
The development of high fiber, high quality
extruded products. Modification of fibers, their
role on product expansion
+ Water and other ingredients
EXTRUSION PROCESS
Expansion
In a very short time (less than a minute) the flour mixed with water (plus
shear and temperature) undergone a complete transformation from a
glassy material to a rubbery material (called melt). That transformation
is needed for expansion
Hypothesis
Schematic of corn fiber structure
• Fibers have a compact structure
that do not interact well with the
starch “amorphous” phase during
extrusion.
Starch “amorphous phase
Schematic of corn fiber structure
(Saulnier and Thibault, 1999)
Melt Extrudate
(two-phase system)
• Fiber modification that produce molecular dispersion of the fiber
into the starch phase would favor the interaction with that phase.
Fiber
Molecules
Expansion
Expansion
ARABINOXYLAN (AX) MOLECULE
Arabino
Arabino
Schematic of corn fiber structure
(Saulnier and Thibault, 1999)
Corn Bran Modification
Alkaline Extraction and Neutralization
Ethanol Fractionation
Extrusion of Fiber Enriched Cereals
Cornmeal 50%
Fiber 25%
(Bran or Modified bran)
Extrusion
Water (20-25%)
Bran
Modified
Bran
Control – no
Fibers
Pai et al. 2009. Journal of Cereal Science, 50 (2), 227-234.
Kale et al. 2010. Journal of Cereal Science, 52(3), 368-372
Kale et al. 2011. Incorporation of Fibers in Foods: A Food Engineering Challenge. In “Food Engineering Interfaces”, Springer
• The soluble arabinoxylan (modified bran) component
will have a larger possibility of interacting with the
starch than the unmodified bran
CONCLUSIONS BASED ON FOOD PROCESSING
• The interaction between the starch and the modified
fiber favors the expansion and structural and textural
quality of the extruded product
What is Laser Light Scattering?
In the lab…
How could we measure the functionality of
the polymeric fiber molecules (modified bran)
i
I
Multi Angle Light Scattering (MALS)
s
I ( ) θ
s
I ( ) θ
Principle 1
The amount of light scattered is directly
proportional to the product of the polymer molar
mass and concentration.
Principle 2
The angular variation of the scattered light is
directly related to the size of the molecule.
conformation plot
Fraction 40-60%.vaf (0.39±0.02)
gfedcb
Fraction 20-40%.vaf (0.44±0.01)
gfedcb
r
m
s

r
a
d
i
u
s

(
n
m
)
How could we measure branching of
the polymeric fiber macromolecules
Linear Molecules
Molecular
Mass
Radius
molar mass (g/mol)
6
1.0x10
7
1.0x10
r
m
s

r
a
d
i
u
s

(
n
m
)
100.0
Molecular
Mass
Radius
Branched Molecules
Micro and Nano-Structures
Macro -Structures
Emulsions
STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide

COULD WE “SEE” SMALLER SCALE THAN NANOMETERS (10
-9
m)?
NEUTRON SCATTERING (OR NOT)
Courtesy from Elliot Paul Gilbert
Australian Nuclear Science and Technology Organization (ANSTO)
Neutrons and Foods Workshop
SMALL ANGLE NEUTRON SCATERING (SANS)
Courtesy from Elliot Paul Gilbert
Australian Nuclear Science and Technology Organization (ANSTO)
Neutrons and Foods Workshop
Australian Nuclear Science and Technology Organization (ANSTO)
SANS - HIGH PENETRATING RADIATION
Courtesy from Elliot Paul Gilbert
Australian Nuclear Science and Technology Organization (ANSTO)
Neutrons and Foods Workshop
EMULSION STRUCTURE and SANS
AGGREGATION OF POLYMERIC MATERIAL UNDER SHEAR
Courtesy of John Katsaras – Neutrons and Foods
Neutron Scattering Science Division
Oak Ridge National Laboratory - Tenesse
Nutritional Aspects of Arabinoxylans
In vitro fermentation of corn bran vs. pectin
Bruce Hamaker at Purdue
Titgemeyer et al., Am. J. Clin. Nutr. 19911418-1424.
Nutritional Aspects of Arabinoxylans
C
o
n
c
e
n
t
r
a
t
i
o
n

B
u
t
i
r
a
t
e
C
o
n
c
e
n
t
r
a
t
i
o
n
Benefits of Arabinoxylans
S
o
l
u
b
i
l
i
t
y

a
z
o
b
e
n
c
n
e D
e
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f

p
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f

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f

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l

p
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p
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s


e
l
a
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c
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t
r
a
t
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o
f

G
e
l
l
i
n
g

A
g
e
n
t
Janado et al. (1980). Solubilities of water-insoluble dyes in internal water of swollen sephadex gels
J. Biochemistry, 87, 57-62
S
o
l
u
b
i
l
i
t
y

Less Porous
D
e
c
r
e
a
s
e

o
f

p
o
r
e

s
i
z
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n
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t
Benefits of Arabinoxylans
Arabinoxylan
molecule
Some ferulic acid dimers
which crosslink the
arabinoxylan molecules
to give gels
Benefits of Arabinoxylans
Arabinoxylan
Gels
Benefits of Arabinoxylans (targeted release)
Arabinoxylans withstand digestive system conditions
Micro and Nano-Structures
Macro -Structures
Emulsions
STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide

• Interest: assembly of molecules/components to
create nanosystems with properties different than or
improved from those of the individual components.
Specifically, we are interested on interactions
between carbohydrates, proteins and lipids
• Overall Aim:
FOOD NANOTECHNOLOGY
• Overall Aim:
Understanding mechanisms involved in
interactions to manipulate and improve structure,
texture and nutrient delivery
To develop new ingredients and foods designed
for targeted delivery of functional micronutrients
and bioactive compounds
Example Conjugated linoleic acid (CLA)
Health Benefits
• anti-carcinogenic
• antioxidant
• slow atherosclerosis
Challenges for incorporation in foods
FOOD NANOTECHNOLOGY
Challenges for incorporation in foods
• Unstable molecules
• Stability can be improved by complexation with
amylose – very insoluble compound
Amylose molecule
Cavity in where a fatty acid
molecule can be complexed
Identification of a 3-component soluble nanocomplex
formed by starch, fatty acid and protein
High Pressure Size Exclusion
Chromatography
2.5
Radius of giration (nm) of complex
systems determined using multiangle
laser scattering
Dynamic Light Scattering (DLS)
Existence of the Nanocomplex
0
0.5
1
1.5
2
5.5 6.5 7.5 8.5
Log(Mw)
L
o
g
(
R
z
)
nm Giration of
Radius
70 20 − ≈
Viscosity profiles: A) starch control (S1), B) starch+protein (SP1), C) starch+FFA
(S1F2), D) starch+protein+FFA(SP1F2)
1 - First cycle of rheometer operation
2 - Second cycle of rheometer operation
HPSEC results of viscosity change with the addition of each component: A) starch control (S1), B)
starch + protein (SP1), C) starch + FFA (S1F2), and D) starch + protein + FFA (SP1F2).
D
C
A
B
Comparison of rheology results for changes in viscosity-pasting profiles: A) S1, B) SP1,
C) S1F2 and D) SP1F2
Mechanism of Complex Formation
Viscosity Measurements
Amylose + Free Fatty Acid
Viscosity Measurements
Nano Complex formation
Differential Scanning Calorimetry
Existence of the Nanocomplex
coo
-
Insoluble nanocomplex
Soluble nanocomplex
Solubilization
CLA
Molecule
Starch
(Amylose) Molecule
Protein
Inclusion of a model hydrophobic compound
(α-napthol) in ternary complex
FOOD NANOTECHNOLOGY - Encapsulation
HPSEC profile (UV and RI ) of ternary complex containing α-napthol through
inclusion process (arrow indicate complex peak)
FOOD NANOTECHNOLOGY - Encapsulation
Iodine binding measured by
potentiometric titration
Amylose + Free Fatty Acid
Amylose
Amylose + Free Fatty Acid
Nanocomplex
+ Naphtol
Inclusion of a model hydrophobic drug (5-Flurouracil) in ternary complex
FOOD NANOTECHNOLOGY
Encapsulation and Solubilization
Inclusion of a model hydrophobic dye (fluorescein) in ternary complex
Micro and Nano-Structures
Macro -Structures
Emulsions
STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
1 nm 10 nm 100 nm 1 µm 10 µm 100 µm 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide

Computational/Molecular
1
Computational/Molecular
Modeling
Polymeric Systems
• Most foods contain one or more biopolymers;
• Commonly used as thickener, emulsifier, stabilizer and gelling
ingredients;
• All characteristics and properties of the solution or gel may depend
on the nature of the solvent, nature and type of polymer,
concentration, temperature and others;
1
concentration, temperature and others;
• The mechanical behaviour (rheology) results from the combination
of individual components with additional interaction effects;
Knowing their rheology is of great importance in
developing and designing food formulations
Computational Modelling
Initial State
Time
Time
Final State
Initial State
Final State
1
Particulate Gels
Polymeric Gels
Interaction Potential
In both cases a model for the interaction
between the particles forming the system
is necessary
Molecular Dynamics
(based on Newton’s equations)
m
d
2
r
i
= F
d
2
r dr
Brownian Dynamics
(Langevin equation)
Solvent effects:
friction random noise
Computational Modeling
1
m
d r
i
dt
2
= F
i m
d
2
r
i
dt
2
= F
i
+ γ
i
dr
i
dt

i
Interparticle force:
model potential
Particulate/Colloidal Gels
Rheology – Viscoelastic Properties
Gel Formation
Experimental Simulation
Torque bar
Sample
Cup
Bob
Impose a sinusoidal strain
Measure the stress
Input (stress)
Output (strain)
Phase Angle
* Santos et al. (2010), J. Phys. Chem. B, 114, 13052-13058.
Cup
Strain γ γγ γ
Stress σ σσ σ
o
σ
o
γ
Oscillator
Phase Angle δ δδ δ
System:
• 64 chains of 400 beads;
• Small volume fraction = 2.6 %
• Non-Bonding: R-shifted L-J (R=1, σ=1)
• Bonding: FENE (Finite Extensible Non-linear Elastic) +
Harmonic angular
Polymeric Systems
1
k=1
k=10
k=100
Flexible molecules k=1
Molecular Dynamics
Polymeric Systems
Small energetic penalty for the chain to fold back:
The system collapses
k=10 k=100
Increasing stiffness …
Molecular Dynamics
Polymeric Systems

Temas específicos que serán cubiertos:
• Aplicaciones de Reologia en la ciencia y la ingeniería de alimentos • Reologia de Biomateriales – Principios Básicos • Tipos de fluidos y métodos para su caracterización • Aplicaciones de Reologia para caracterizar alimentos y biomateriales los cuales incluyen cereales y productos lácteos • Caracterización de la estructura de materiales y su relación a su textura • Reología de productos conteniendo nano partículas • Transición vítrea. Caracterización and principios básicos • Efecto de la transición vítrea en el procesamiento y la textura de productos alimenticios • Extrusión, clasificación and descripción del proceso y tipos de tecnología • Conceptos de extrusión reactiva • Rol de Reología en el proceso de extrusión • Extrusión de cereales • Tecnología de Extrusión • Efectos de Extrusión en las propiedades del material desde un punto de vista textural y nutricional

.

RHEOLOGY “SCIENCE THAT STUDY THE DEFORMATION AND FLOW OF MATERIALS” Mechanical Properties of Materials ? .

RHEOLOGY “SCIENCE THAT STUDY THE DEFORMATION AND FLOW OF MATERIALS” α − lactose .

anhydrous Evaporation α -hydrate line Crystal Growth Temperature ( C) 60 40 20 0 -20 Ice and solution o Solution (Emulsion) Lactose crystals and solution -40 -60 0 10 20 30 40 50 60 70 80 Glassy State 90 100 Total Solids (%) .MATERIAL CHANGES DURING PROCESSING e. MILK POWDER or Spray Drying of Pharmaceuticals 100 80 Spray Drying β .g.

MATERIAL CHANGES DURING PROCESSING Spray Drying of Lactose α − Lactose Spray dried α − Lactose .

STRUCTURES IN FOODS AND BIOMATERIALS .SIZE Macro -Structures Foam Air Pockets Powder FOOD PRODUCT Micro and Nano-Structures Emulsions Gels Casein Micelles Starch Granules Molecular Structures Polysaccharide Sugar Water Protein 1Å 1 nm 10 nm 100 nm 1 m 10 m 100 m 1mm 1cm .

MATERIAL CHANGES DURING PROCESSING Spray Drying of Lactose α − Lactose Spray dried α − Lactose .

EXTRUSION + Water and other ingredients Expansion In a very short time (less than a minute) the flour mixed with water (plus shear and temperature) undergone a complete transformation from a glassy material to a rubbery material (called melt). That transformation is needed for expansion .

Glass Transition – Concept Glass transition temperature oC RUBBERY STATE “Viscoelastic material” Increasing temperature Increasing moisture GLASSY STATE “Solid” Moisture Content (%) .

TRANSFORMATIONS OF RAW MATERIALS DURING EXTRUSION LIQUID (AMORPHOUS) TEMPERATURE Expansion Glass Transition Temperature Heating GLASS Dry Material Wetting and Mixing MOISTURE .

USE OF RHEOLOGICAL DATA Study of Material Microstructure (Texture) Texture Alignment of Particles Viscosity Stress .

DATA Textural Evaluation of Foods Extrudate “Crispness” Measured as sound produced when crushing an extruded sample Gluten Waxy Starch Wheat Starch Relative Humidity (Water Activity) Gluten Elastic Properties Waxy Starch Air Cells Cell Walls Wheat Starch “Crispness” is related to the rheology of the cell wall material and the microstructure of the sample % Moisture .USE OF MECHANICAL PROPERTIES – RHEOLOGICAL.

etc ) are associated to transitions. gelling agents.g. gelling.RHEOLOGICAL PHENOMENA • Occur in different scales of length and time • Drastic changes are observed on the mechanical properties of biomaterials during processing • Drastic changes on mechanical properties of biomaterials affecting their function (e. stickiness in a glue. e. viscosity I enhancers as stabilizers. glass transition.g. texture in foods. .

RHEOLOGICAL PHENOMENA Low Molecular Weight Solutions (monomer) High Molecular Weight Solutions Very High Molecular Weight Solutions Macrostructural Materials Colloidal Suspensions Liquid Behavior Newtonian Behavior Viscoelastic Liquids Non-Newtonian Behavior Viscoelastic Solids Structure Dependent Response. Structure Recovery and Breaking .

Fundaments on Rheometry – Steady Shear
Ideal Shear Test
F h V Velocity Profile u(y)

Shear Rate
γɺ =

Shear Stress
σ
= F A

Flow Curve

V h

σ
σ0
Yield Stress

“Plastic” Shear thinning Newtonian Shear Thickening

γɺ

Newtonian Liquids – Definition of Viscosity Units
Shear Stress (Pa)

µ

µ=

Shear Stress σ Pa = = = Pa.s Shear Rate γɺ 1 / s

1 mPa.s = 10 −3 Pa.s = 1 cP

• Water

Shear Rate γɺ (1/s)

• Sucrose Solutions (up to concentrations of 60%) • Skim milk • Oil • Glucose Solutions (not very concentrated) • Diluted Juices

Flow Curves in terms of Viscosity

or shear thinning) shear Thickening or

sn) n : Flow Index (-) • If n < 1 liquid is shear thinning (or pseudoplastic) • If n > 1 liquid is shear thickening (or dilatant) • If n = 1 liquid is Newtonian γɺ .Rheological Models Power-Law Model σ = k γɺ n σ Flow Curve Shear thinning Newtonian liquid Shear thickening k : Consistency Index (Pa.

it behaves as a liquid . it behaves as a solid The material flows.What are “plastic” liquids ? • Tomato Paste • Ketchup • Toothpaste • How do they behave? We need to squeeze or push them so that the material flow • A “yield” stress σ o can be defined and compare it with the applied stress σ If σ < σ o If σ > σ o The material will not flow.

Plastic Fluid Materials Shear Stress Plastic shear thinning Plastic Newtonian “Binghan fluid” Plastic shear thickenning σo Herschel-Bulkley Model Shear Rate σ = σ o + kγɺ n .

5 1 1 γɺ = K 1 σ + K n1 σ 1 Generalized σ Herschel-Bulkley Carreau = σ ∞ n1 o + K γɺ n 2 η =η + η0 − η [ 1 ∞ 2 + ( K 1 γɺ ) ] 1 − n 2 .5 o + K + K 2 1 γɺ 0 γɺ n n1 .Other Models used to describe the rheology of inelastic “plastic” fluids Model Casson Equation σ 0 .5 o 0 .5 Modified Casson σ Ellis 0 .5 = σ = σ 0 .

“Plastic” Materials – Yield Stress σ Liquid Medium σo “Plastic” Medium σo γɺ Yield Parameter Diameter Medium Density Y= d ( ρ medium − ρ part ) g σo Droplet Density .

Non-Ropy Culture D .. J.Thermophilus 0 20 40 60 80 100 120 140 0 Shear Rate (1/s) Hassan. et al. Ropy S. Dairy Sci. 2003.N.Plastic Materials – Presence of Yield Stress Un-stirred Stirred Confocal Microscopy Green – Polysaccharides Red – Protein Black .Ropy S. 86. A.Thermophilus Culture C .Whey Culture B Ropy Yoghurt Rheology σ = σ o + kγɺ n 60 Culture C Non-Ropy Shear Stress (Pa) 50 40 30 20 Culture D Ropy 10 Culture B. 1632-1638 .

Summary of Rheological Behavior σ ɺ τ =τo + k γ n τ =τ o +η γɺ τ = k γɺ σo γɺ n .

) Low shear range Viscosity High Shear range Shear Rate .A More Extended Flow Curve (logarithmic coordinates.

) Viscosity Low shear range High Shear range Shear Rate .Interpretation of Rheological behavior Low Shear Rates shear is not enough to align the particles thermal motion (kBT) will “randomize” the orientation of the particles Low V Particles Intermediate Shear Rates shear is enough to align the particles Intermediate V High Shear Rates Fluid serum High V Flow Curve (log coord.

Rheological Behavior of Liquids with Structures Time dependent liquids .

Dairy Sci. A..N. J. 2003. et al. 86.Thixotropic Materials Shear Stress (Pa) 70 Ropy Strain B 60 Un-stirred Stirred Yoghurt made with Ropy Strain B 50 40 30 20 10 0 70 Up curve Down curve 60 Non-ropy Strain C Un-stirred Stirred Shear Stress (Pa) 50 Yoghurt made with Non-ropy Strain C 40 30 20 Down curve 10 0 70 Up curve Un-stirred Stirred Shear Stress (Pa) 60 50 Ropy Strain D Up Curve Yoghurt made with Ropy Strain D 40 30 20 10 0 Down Curve Hassan. 1632-1638 0 20 40 60 80 100 120 140 Shear Rate (1/sec) .

Other Thixotropic Behavior Studies ɺ γo 0 Time ɺ γo Rest Period ɺ γo σ η or 0 Complete Recovery Partial Recovery No Recovery Time .

How do we measure these “liquid” properties? Traditional Rotational Viscometry .m) h Parallel Plates . M Sample Sample Cone and Plate Concentric Cylinders Ω .M Ω.M Sample : Rotational Speed. rad/s M : Torque (N .

Rheology Testing “Mixer” Geometry Capillary Viscometer Pulse Shear Test Interfacial Rheology .

Effect of Temperature on the viscosity of “liquids” Viscosity T µ (T ) = A e µ : " Viscosity" B T Arrhenius-type of equation A and B are parameters determined from data .

Applications of Stabilizers (Low Shear Viscosity) Stabilize coalescence and creaming .

ice creams) Ostwald Ripening (Low Shear Viscosity) Fluid Medium . e.Stablizer Uses (Low Shear Viscosity) Used in frozen foods and beverages (it creates pleasant texture.g.

g.Other Uses of Stabilizers (Low Shear Viscosity) Xanthan gum: Binder in food products – gluten free bread (acting as gliadin) Binder in non-food products (e. toothpaste) .

xanthan gum in yoghurt) 30 Xanthan Gum Network 25 Milk .0.No XG Milk .g.01% XG 20 Viscosity (cP) 15 10 5 0 0 20 40 60 80 100 120 El-Sayed et al.005% XG Milk .. (2002) Eur Food Res Technol (2002) Incubation Time (minutes) .0.Stabilizer Uses (Low Shear Viscosity) Thickener (e.

Structure recovery and Breaking .RHEOLOGICAL PHENOMENA Low Molecular Weight Solutions (monomer) High Molecular Weight Solutions Very High Molecular Weight Solutions Macrostructural Materials Colloidal Suspensions Liquid Behavior Newtonian Behavior Viscoelastic Liquids Non-Newtonian Behavior Viscoelastic Solids Structure Dependent Response.

At short times it behaves as a solid. at long times it behaves as a liquid SHORT TIMES LONG TIMES 41 .VISCOELASTICITY A viscoelastic material. may be behave either as solid or liquid. depending on time.

VISCOELASTIC PHENOMENA .

CONCEPT OF VISCOELASTICITY Maxwell: Viscous flow is the manifestation of the decay of elastically stored energy High Energy (Stored “elastic” energy) tR De = texp Low Energy Low Energy tR De = texp Deborah number De << 1 Liquid De ∼ Order (1) Viscoelastic De >> 1 Solid like .

Times involved on the rheological phenomena • Diffusion of “spherical” molecules (radius “a”) Stokes/Einstein Equation kBT D= 6πη0a η0 : Fluid Viscosity kB : Boltzman constant T : Temperature • Diffusion time tD (sec) – Einstein/Smoluchowski Equation a 2 (m2 ) 6πη0a 3 tD (sec) = = 2 m kBT D( ) s .

y x z
u (m/s)

h (m)

h (meters) 1 texp = = u (meters / s) γɺ
Peclet Number

tD (sec) 6πη0a γɺ Pe = = texp (sec) kBT
3

Time Scales
Molecules 10000 100 Macromolecules Colloids Time Scale in Laboratory 1 10 100 1000 10000

Diffusion Time td (seconds)

1 0.01 1E-4 1E-6 1E-8 1E-10 1E-12 0.1

Molecule/Particle Radius (nm)

Viscoelastic Measurements
ELASTIC SOLID LIQUID

" SPRING " ~ SOLID

L

" DASHPOT" ~ LIQUID

L
F proportional to the Rate of Deformation

F proportional to Deformation

F TIME L TIME
• DEFORMATION FOLLOWS THE FORCE • FORCE AND DEFORMATION ARE “ IN PHASE “

F to L t1
TIME

Permanent Deformation to t1
TIME

• DEFORMATION DOES NOT FOLLOW THE FORCE

• FORCE AND DEFORMATION
ARE “ OUT OF PHASE ”

Traditional Viscoelastic Measurements Torque bar Bob Sample Cup Storage Modulus G ' (ω ) = σ o cos δ γ0 Phase Angle = δ Oscillator γo Loss Modulus σ o sin δ G ' ' (ω ) = γ0 σo Phase Angle δ Strain γ Stress σ Loss Tangent G ' ' (ω ) tan δ = G ' (ω ) δ = 0 Hookean Elastic Solid 0 < δ < 90o Viscoelast ic Material δ = 90o Viscous Liquid .

M h “Mixer” Rheology Parallel Plates Sample . M Sample Cone and Plate Ω .Viscoelasticity Testing .M Pulse Shear Test Sample Concentric Cylinders Ω.

CONTROLLED STRESS INSTRUMENTS Input τ =τ o sin ωt Frequency (fixed by the user) Stress Amplitude (fixed by the user) Output γ = γ o sin (ωt + δ ) 15 10 Stress or Strain 5 0 0 -5 -10 -15 Strain Amplitude (measured) Phase Angle (measured) γo σo 2 4 6 8 Stress Strain Measured δ Time Measured .

CONTROLLED STRAIN INSTRUMENTS Input γ = γ o sin ωt Output Frequency (fixed by user) Strain Amplitude (fixed by user) Stress Amplitude (measured) Phase Angle (measured) τ =τ o sin (ωt + δ ) τ =τ o sin (ωt + δ ) σ = G ' (ω ) γ (t ) + G" (ω ) γɺ (ω ) Solid Behavior Liquid Behavior .

Oscillatory Testing τ (t ) = G' (ω )γ (t ) + G" (ω )γɺ(ω ) Solid Behavior Liquid Behavior Storage Modulus Loss Modulus tan (Phase Angle) τo G' (ω ) = cos δ γo τo G" (ω ) = sin δ γo G" (ω ) tan δ = G ' (ω ) .

Oscillatory Testing Other Viscoelastic Parameters • Complex Modulus • Complex Viscosity G (ω ) = G ' +G" * 2 2 η* = G * (ω ) ω " = G ' 2 + G" 2 ω • Dynamic Viscosity η' = G (ω ) ω G (ω ) ' • Out of Phase Viscosity η" = ω .

Oscillatory Testing Other Viscoelastic Parameters (from Controlled Stress) • Complex Compliance 1 1 J (ω ) = * = G G ' 2 + G" 2 * • Storage Compliance G' J ' (ω ) = 2 G ' + G" 2 G" J ' (ω ) = 2 G ' + G" 2 • Loss Compliance .

VISCOELATIC MATERIALS Solid (elastic) and Liquid (viscous) Behavior !!!! τ γ G τ γɺ µ Spring τ =G γ Dashpot τ = µ γɺ .

VISCOELATIC MATERIALS Maxwell Element Rheological Model τ γs γd G dτ τ + tR = µ γɺ dt tR = Relaxation Time µ µ G .

What happens if a Maxwell Element is oscillated ? Maxwell Element τ γs γd G • Storage Modulus • Loss Modulus 2 Gω 2 t R G' = 2 1 + ω 2tR Gω t R G" = 2 1 + ω 2tR G ' or G" Solid Behavior µ G' G" ω tR = 1 ω .

Materials are more complex than a single Maxwell Four Element t R1 = 2 2 G1ω 2tR1 G2ω 2tR 2 G' = + 2 2 2 1 + ω t R1 1 + ω 2 t R 2 µ1 G1 G1 G2 t R 2 = µ 2 µ1 µ2 G2 G1ω tR1 G2ω tR 2 G" = + 2 2 2 1 + ω t R1 1 + ω 2 t R 2 Generalized Maxwell 2 Giω 2tRi G' = ∑ 2 1 + ω 2tRi i =1 n G1 G2 G3 Gn µ1 µ2 µ3 µn G" = ∑ Giω tRi 2 1 + ω 2tRi i =1 n tRi = µi Gi .

Viscoelastic Properties Determination Frequency Sweep Tests 2 Giω 2tRi G' = ∑ 2 1 + ω 2tRi i =1 n G' or G" G' G" Giω tRi G" = ∑ 2 1 + ω 2tRi i =1 n tRi = µi Gi ω .

01 0.1 G" (Loss Modulus) G' (Storage Modulus) 0.s) 10 G'. G" (Pa) 10 1 0.1 1 10 100 1000 1 1 10 100 Shear Rate (1/s) Frequency. ω (1/s) .Highly shear thinning properties and rapidly structure forming (high viscosity at low shear rates and ability to form gels) Required Rheological Functionality “Liquid” Properties 100 Drilling Mud .01 0.Xanthan Gum Uses (What rheology is required?) Drilling Fluids (CaCO3 and Xanthan Gum) .CaCO3 and Xanthan Gum Viscoelastic Properties Drilling Mud Viscosity (Pa.

s) or G"/ω (Pa.1 Shear Viscosity (Pa.01 1 10 100 Shear Rate γ or Frequency ω .Xanthan Gum Uses (what rheology is required?) Combining Steady Shear and Oscillatory Tests Cox-Merz Rule Viscosity (Pa.s) 0.s) 10 Drilling Fluids 1 Shifting Data G" ω n −1 η ∝ γɺ ∝ω n' −1 0.s) Dynamic Viscosity (Pa.

the temperature at which xanthan gum in solution has a transition from a multi to a single stranded molecule Storage Modulus G (Pa) 10 1 20 30 40 50 60 o Tm70 80 Temperature ( C) .Xanthan Gum Uses (what rheology is required?) Drilling Fluids (CaCO3 and Xanthan gum) Fluid Temperature Stability It is important that the drilling mud has a large Tm.

Recoil Test Data Generated using Transient Methods • Shear Stress Growth Function • Shear stress decay function τ (t ) τ (t ) τ (t ) or µ(t ) = γɺo (t ) τ (t ) τ (t ) or G(t ) = γo • Shear stress relaxation Function or Relaxation Modulus • Shear Creep γ (t ) or J(t ) = • Recoil Function (Strain) γ(t ) γ (t ) τo . Step Strain (Relaxation experiment) 4.Measurements • Unsteady Shear testing Oscillatory Testing (small deformation) Transient Testing (small and large deformation) 1. Cessation of Steady Shear Flow 3. Start-up Flow Test 2. Creep Test 5.

γ(t ) 3. Step Strain or Relaxation Test (not the same than start-up flow) γo Relaxation Modulus τ (t ) G(t ) = γo to t Relaxation stresses for materials with different relaxation times Different tR Residual stress τ (t ) τ o = Gγ o to t .

1. Unsteady Shear testing 1. Start-up Flow γɺo tR De = texp • Large Deborah Number Elastic Behavior • Small Deborah Number Viscous Behavior to t Increasing shear rates τ (t ) γɺo texp 1 ∝ γɺo τo Non-elastic fluid τ ( t ) = µ ( t ) γɺo Extremely low shear rate for t → ∞ De is small and τ o = µ γɺo to t .

2. Cessation of Steady Shear Flow γɺ( t ) γɺo t1 τ (t ) t σo t1 t .

4. Creep Test τ (t ) t γ(t ) γo = τo G t .

5. Recoil Test τ (t ) to γo = τo G t1 t Partial Recoil No Recoil Full Recoil permanent deformation t .

MODELING σ γs G dτ τ + tR = µ γɺ dt dσ dt γd µ σ + tR = µ γɺ  ∂v  ρ  + v ⋅∇ v  = − ∇p + ∇ ⋅τ + ρ g  ∂t  .VISCOELASTIC FLUIDS .

and the strain and the strain rate histories are important .τ + tR Generalized Linear Viscoelastic Model dτ dt t = µ γɺ σ γs γd G µ τ (t ) = −∞ ∫ G(t − t ') γɺ (t ') dt ' G(t − t ') = µ tR e − t −t ' tR Material Dependent Strain-rate tensor “depending on flow” This equation is good for small strain. large strain rates. small strain rates Many industrial applications applied large strains.

CONCLUSIONS • Food and Biomaterials encompass a range of rheological properties that cannot be fully evaluated by only one method. Empirical methods are simpler and less expensive than fundamental tests but they have more limitations. • Length and time scales need to be evaluated to interpret and analyze rheological data from viscoelastic materials if they intended to study structure-function material behavior. . • Mainly fundamental tests were described. Fundamental versus empirical methods are continuously revaluated for testing. A number of methods to characterize the rheology of liquid and viscoelastic materials (including semisolid and solid materials) have been described.

GLASS TRANSITION PHENOMENON Formation of Amorphous Materials CRYSTAL (Structure Disruption) • • • • • • Milling Granulation Compression Grinding Dehydration Irradiation LIQUID (Energy Removal) • Rapid Cooling • Nucleation • Stop polymerization reaction • Extrusion (solid liquid solid SOLUTION (Solvent Removal) • Freeze Drying • Spray Drying • Precipitation • • Polymerization • Reaction Unintentional Intentional AMORPHOUS MATERIAL or AMORPHOUS STATE .

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SOLUBILITY ENHANCEMENT OF AMORPHOUS MATERIALS 400 Amorphous Novobiocin 300 Absorbance 200 100 Crystalline Novobiocin 0 0 1 2 3 4 Time (hours) .

72 0.SOME DIFFERENCES BETWEEN CRYSTAL AND AMORPHOUS MATERIALS Material Indomethacin Sucrose Lactose Trehalose Dextran PVP Specific Volume (ml/g) Crystal 0.80 .67 1.63 0.68 0.62 0.75 0.09 0.63 Amorphous 0.70 0.

5 Bending Strength x 104 (Pa) 187 567 1.056 . 1989 Hardness x 107 (Pa) 42 28 6..SOME DIFFERENCES BETWEEN CRYSTAL AND AMORPHOUS MATERIALS Mechanical Properties of Metal Oxides (Phenobarbitone Forms) Material Form II Form III Amorphous Kopp et al.

excipients and formulations can exist as amorphous forms Some materials are naturally amorphous Some materials becomes intentionally amorphous during processing Some materials are changed to amorphous intentionally • Advantages of amorphous versus crystalline Materials Improved dissolution Higher solubility Higher bioavailability Unique mechanical properties • Disadvantages of amorphous versus crystalline materials Chemically unstable Physically unstable Hygroscopic .SUMMARY • Drugs.

PROPERTIES OF AMORPHOUS MATERIALS • Non-equilibrium solid state • Randomly arranged molecules • Occupy larger volume than crystals of the same material • Formed by rapid cooling processes • Structure dependent on cooling rate • Different cooling rates rates in different glasses of the same material Crystal Amorphous/ Glass .

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How are glasses formed? Rapid Cooling Volume Amorphous Slow Cooling Crystal Tg Temperature Tm / Tf .

Why do we care about glass transition? • Glass transition is an important phenomena in processing of biomaterials. Shelf life of foods is associated to glass transition • Glass transition can affect other thermal properties and processes such as crystallization . foods and pharmaceuticals • Glass transition is a key factor in determining the stability and quality of foods and pharmaceuticals.

HOW DO WE MEASURE GLASS TRANSITION? • Changes in specific volume with temperature • Changes in conductivity with temperature • Changes in heat capacity (DSC) with temperature • Changes in mechanical properties with temperature .

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Glass Transition and Rheological Properties Glass transition region “Rheological Property” For Example the Elastic Modulus “Rubbery” Material Amorphous “Glassy” Material Glass transition region High Solid Content (low solvent) Low Solid Content (high solvent) Tg Tg Temperature .

• DMA tablet preparation: – Disadvantages: • Compress sample under 5.000 lb force • May cause changes in amorphous sample Dynamic Mechanical Analysis (DMA) • DMA Powder cell – Advantages: • No preparation is required • Loose sample can be used • No alteration in structure of the sample due to excessive compression .

Oscillatory Squeezing Flow (OSF) • The oscillatory squeezing flow is based on a well known rheological technique called squeezing flow with added technological improvements • It involves oscillations at random frequencies up to 10 kHz (10.000 Hz) compared with existing instruments whose oscillation frequency is 10-20 Hz .

Instrument Set-up .

Oscillatory Squeezing Flow (OSF) Theory Concept Application Damping Elasticity Acceleration Velocity Displacement Mechanical Impedance ɺ F ( t ) = mu( t ) + Ru( t ) + s ∫ u( t ) dt ˆ ˆ = F = R + i ( ωm − s ) Z Elastic Component ˆ u ω Viscous Component .

Oscillatory Squeezing Flow (OSF) Theory ω meff ho S Sample Rigid Surface Oscillating Plate a ho : Diameter of the top plate :Gap between plates : Frequency R ω meff : Effective mass 2 3 3 meff ω a  2ho ω  ˆ G ′ =  Im ( Z sample ) + 2  ⋅ 3π a4 20ho   Elastic “Storage” Modulus Viscous “Loss” Modulus ˆ G ′′ = Real Z sample × ( ) 2ho ω 3π a 4 3 4 3 Stefan Equation Squeezing Flow ˆ Z sample = 3π a 2 ho η * .

000 Da.000 Da.000. MW • Indomethacin • Felodipine • Griseofulvin Indomethacin.Pharmaceutical Materials • Polyethylene Oxide – 200. MW – 900. MW – 2. Felodipine and Griseofulvin samples were melt quenched .000 Da.

000 MW BBFSF Data 1.000 Da Normalized Stiffness (Dimensionless) 1.85 0.75 0.00 -4 BBFSF Data DSC Scan 0 -2 Polyethylene Oxide 900.70 0.65 30 40 50 60 o -6 -8 -10 -12 -14 -16 -18 -20 -22 -24 -26 70 80 Normalized Stiffness (Dimensionless) Heat Flow (mW) 0.Melting of Polyethylene-oxide Polyethylene Oxide 200.000.5 30 40 50 60 o -2 -4 Heat Flow (mW) Heat Flow (mW) 0.05 1.6 -10 -12 0.7 -10 0.0 DSC Scan 0 -2 -4 Normalized Stiffness (Dimensionless) 0.80 0.000 Da PEO 900.6 -12 0.90 0.000 MW 1.1 DSC Scan for Polyethylene Oxide 2 0 2 0 BBFSF Data DSC Scan PEO 200.000 Da PEO 2.000.8 -6 -8 0.4 30 40 50 60 o -14 70 80 Temperature ( C) Temperature ( C) Polyethylene Oxide 2.9 -6 -8 -10 -12 -14 -16 -18 10 20 30 40 50 60 o -14 70 80 70 80 90 100 Temperature ( C) Temperature ( C) Heat Flow (mW) .0 -2 -4 0.95 0.8 -6 -8 0.000 MW 1.

78oC .72oC Indomethacin DMA Range: 45 – 47oC Average: 46oC STD: 1.Active Ingredients data summary Drug Powders Felodipine DSC Range: 43 – 47oC Average: 45oC STD: 2.41oC Range: 79 – 87oC Average: 83oC STD: 3.25oC OSF Range: 49 – 51oC Average: 50oC STD: 0.70oC Griseofulvin Range: 80 – 83oC Average: 81oC STD: 0.73oC Range: 75 – 85oC Average: 80oC STD: 7.66oC Range: 46 – 48oC Average: 47oC STD: 1.85oC Range: 44 – 47oC Average: 45 oC STD: 1.22oC Range: 50 – 52oC Average: 51oC STD: 0.

RHEOLOGY IN FOOD PROCESSES PRODUCTION OF CORN FLAKES Materials Corn grits Final Product .

PROCESS Cooking Drying Dry Milling Tempering .

PROCESS Flaking Cooking Drying Dry Milling Tempering Tosting .

FINAL PRODUCT QUALITY Amylose Chromatographic profile of corn flakes Intermediate and Low Molecular Weight Region Fragmented Amylopectin and Amylose Range: 104 .108 Da Amylopectin Elution Volume (Ml) .106 Da Sugars and Non-iodine Binding Material High Molecular Weight Region Amylopectin Range: 107 .

0 13.50 6.0 Can Weight (oz/gal) Gap Gap weight Density = volume Density ≡ Gap .0 9.0 11.50 7.0 17.50 Relative Fragmentation 8.0 7.00 5.FINAL PRODUCT QUALITY 8.00 6.00 7.0 19.0 15.

3 min.FINAL PRODUCT QUALITY Products obtained under several processing conditions 60 350 330 Water Uptake (%.) 55 310 290 270 250 230 210 190 170 50 Tg (°C) 45 40 35 5 7 9 11 13 15 150 35 40 45 50 55 60 Density (oz/gal) Tg (° C) Gap .

PROCESS Cooking Drying Dry Milling Tempering .

H. Viscoelastic properties of liquids and semisolids materials using squeezing theory and impedance measurements from forced vibrations. and Campanella. B. O. US Provisional Patent . 2004.Rheological Properties of corn flake grits Concept Design Damping Elasticidad Model Acceleration Velocity Displacement Application ɺ F ( t ) = mu( t ) + Ru( t ) + s ∫ u( t ) dt ˆ ˆ = F = R + i ( ωm − s ) Z ˆ u ω Mechanical Impedance Mert.

04 7 min 2 min 0.02 60 min dried 1000 3000 5000 ω (rad/s) 7000 9000 1000 3000 5000 7000 ω (rad/s) 9000 11000 13000 ˆ ˆ = F = R + i( ω m − s ) Z ˆ u ω At Resonance Peak Mobility = 1 1 = ˆ Z R2 + ( ω m − s ) 2 ω peak ω peak = s m ω .08 0.RESULTS Rheology of the kernel during the cooking process 0.06 30 min dried 120 min dried 0 min 0.02 0.08 |Mobility| (m/s ⋅ N) |Mobility| m/s.1 60 min Rheology of the kernel during the drying process 0.06 15 min Raw 0.04 0.N drying 30 min 0.1 60 min cooked cooking 0.

Ag and Food Chem.GLUTEN FREE PRODUCTS α− Zein Structure • Crystallization • Small Angle X-Ray Scattering • Molecular Simulation Momany et al. 2006. 54(2). Starch Gelatinization • Texture . 543-547. J. • Dough Rheology • Transitions: Glass Transition.

GLUTEN FREE PRODUCTS • 87% Starch-13%protein • Mixed at 25oC • Conditioned at 25oC Wheat Starch-zein zein-glutenin zein-casein (ratio 10:1) (ratio 10:1) Wheat • 87% Starch-13%protein • Mixed at 25oC • Conditioned at 35oC Starch-zein zein-glutenin (ratio 10:1) zein-casein (ratio 10:1) .

van der Waal’s forces) 1. Polymeric Glutenins (High Molecular Weight. Gluten’s prolamin constituent. responsible for viscous behavior. Dough strength and elasticity associated with the development of gluten’s polymeric matrix. Gliadin. comprised of HMW and LMW linked through intermolecular disulfide bonds . due non-covalent forces (hydrogen bonding.Why wheat proteins have such as exceptional characteristics to produce viscoelastic dough and quality bread ? CURRENT MODELS Disulfide Interchange Model 1. HMW and Low Molecular Weight (LMW) linked through intermolecular disulfide bonds contribute to dough elasticity 2.

Belton.GLUTEN FREE PRODUCTS Loop and Train Model for Gluten Functionality (A) (B) Shewry et al. 2002. Trends in Food Science and technology . 2005 i ii Molecule of High Molecular Weight Glutenin iii Loop Region Train Region Hypothesis on Protein Fibril Formation in Zein Erickson et al. 2011.

0 10.0 B b A a 40.0 0min 3min Relaxation time (min) 6min Zein Gluten Zein-HMW glutenin 60.0 10.0 B b A a B b B b A a B b B b 30.0 20.0 0.0 Fraction secondary structure (%) β − Sheet Structure FTIR Technique Mejia et al.0 Ab Ab 20. 2011 (Accepted) 40.0 Aa 30.0 Bce Bce Bde Bce Be Bc 50.0 Fraction secondary structure (%) α − Helix Structure FTIR Technique 50.GLUTEN FREE PRODUCTS 60..0 0.0 0min 3min Relaxation time (min) 6min .

GLUTEN FREE PRODUCTS Standard Rheological Technique .

2005 Mert and Campanella. Rheologica Acta. 2007 Mert and Campanella. Journal of Food Engineering. 2008 R : Dissipation – “viscosity” of sample s: Stifness – “Elasticity” of sample .GLUTEN FREE PRODUCTS Novel Rheological Techniques Instrument Set-up Concept Acceleration Velocity Displacement ɺ F( t ) = mu( t ) + Ru( t ) + s ∫ u( t )dt Mert et al. Review of Scientific Instruments.

Journal of Food Engineering. B.H. 47. Rheologica Acta. 32-38 Gonzalez et al. 727-737 Mert et al. 2008. 46(1). 100(2).Novel Rheological Techniques Concept Sample Standing Waves Mert. and Campanella. 2007. 2010. 187-193 . Journal of Cereal Science. O.

GLUTEN FREE PRODUCTS Novel Rheological Techniques .

STRUCTURES IN FOODS AND BIOMATERIALS .SIZE Macro -Structures Micro and Nano-Structures Emulsions Gels Casein Micelles Starch Granules Molecular Structures Polysaccharide Sugar Water Protein 1Å 1 nm 10 nm 100 nm 1 m 10 m 100 m 1mm 1cm .

Fibers in Foods .

• Breakfast cereals and snacks contain low fiber content because incorporation of fibers into these extruded products limits their puffing ability and reduces crispness. respectively.JUSTIFICATION • The Food and Nutrition Board of the Institute of Medicine has set recommendations at 38 and 25 g/day of fiber for men and women. . • Aim: Identify and/or modify fibers for incorporation at high levels in extruded products with acceptable textural and sensory characteristics.

That transformation is needed for expansion . high quality extruded products. Modification of fibers.The development of high fiber. their role on product expansion EXTRUSION PROCESS + Water and other ingredients Expansion In a very short time (less than a minute) the flour mixed with water (plus shear and temperature) undergone a complete transformation from a glassy material to a rubbery material (called melt).

Starch “amorphous phase Fiber Molecules Expansion Schematic of corn fiber structure (Saulnier and Thibault.Hypothesis • Fibers have a compact structure that do not interact well with the starch “amorphous” phase during extrusion. Melt Expansion . 1999) Extrudate (two-phase system) • Fiber modification that produce molecular dispersion of the fiber into the starch phase would favor the interaction with that phase.

ARABINOXYLAN (AX) MOLECULE Arabino Arabino .

Corn Bran Modification Alkaline Extraction and Neutralization Schematic of corn fiber structure (Saulnier and Thibault. 1999) Ethanol Fractionation .

2010. Springer .Extrusion of Fiber Enriched Cereals Cornmeal 50% Fiber 25% (Bran or Modified bran) Water (20-25%) Extrusion Modified Bran Control – no Fibers Bran Pai et al. Journal of Cereal Science. In “Food Engineering Interfaces”. Incorporation of Fibers in Foods: A Food Engineering Challenge. Journal of Cereal Science. 50 (2). 2011. 2009. 368-372 Kale et al. Kale et al. 227-234. 52(3).

CONCLUSIONS BASED ON FOOD PROCESSING • The soluble arabinoxylan (modified bran) component will have a larger possibility of interacting with the starch than the unmodified bran • The interaction between the starch and the modified fiber favors the expansion and structural and textural quality of the extruded product .

Principle 2 The angular variation of the scattered light is directly related to the size of the molecule. .How could we measure the functionality of the polymeric fiber molecules (modified bran) What is Laser Light Scattering? Multi Angle Light Scattering (MALS) In the lab… Ii Is( θ ) Is( θ ) Principle 1 The amount of light scattered is directly proportional to the product of the polymer molar mass and concentration.

vaf (0.How could we measure branching of the polymeric fiber macromolecules conformation plot b c d e f g Fraction 40-60%.44±0.0 Molecular Mass Branched Molecules 1.39±0.0x10 molar mass (g/mol) 7 .01) Linear Molecules Molecular Mass rm s radius (nm ) Radius Radius 100.02) g b c d e f Fraction 20-40%.vaf (0.0x10 6 1.

SIZE Macro -Structures Micro and Nano-Structures Emulsions Gels Casein Micelles Starch Granules Molecular Structures Polysaccharide Sugar Water Protein 1Å 1 nm 10 nm 100 nm 1 m 10 m 100 m 1mm 1cm .STRUCTURES IN FOODS AND BIOMATERIALS .

COULD WE “SEE” SMALLER SCALE THAN NANOMETERS (10-9m)?

NEUTRON SCATTERING (OR NOT)

Courtesy from Elliot Paul Gilbert Australian Nuclear Science and Technology Organization (ANSTO) Neutrons and Foods Workshop

SMALL ANGLE NEUTRON SCATERING (SANS)

Courtesy from Elliot Paul Gilbert Australian Nuclear Science and Technology Organization (ANSTO) Neutrons and Foods Workshop

Australian Nuclear Science and Technology Organization (ANSTO) .

SANS .HIGH PENETRATING RADIATION Courtesy from Elliot Paul Gilbert Australian Nuclear Science and Technology Organization (ANSTO) Neutrons and Foods Workshop .

EMULSION STRUCTURE and SANS .

Tenesse .AGGREGATION OF POLYMERIC MATERIAL UNDER SHEAR Courtesy of John Katsaras – Neutrons and Foods Neutron Scattering Science Division Oak Ridge National Laboratory .

Nutritional Aspects of Arabinoxylans In vitro fermentation of corn bran vs. J. pectin Bruce Hamaker at Purdue Titgemeyer et al. Clin. Nutr. 19911418-1424. Am. ..

Nutritional Aspects of Arabinoxylans “Butirate Concentration .

Solubilities of water-insoluble dyes in internal water of swollen sephadex gels J. Biochemistry.Increase of mechanical properties “elasticity” Increase of mechanical properties “elasticity” Janado et al. 87. 57-62 Increase of Solubility Increase of Solubility Decrease of pore size Decrease of pore size Benefits of Arabinoxylans Concentration of Gelling Agent Concentration of Gelling Agent Less Porous Solubility azobencne . (1980).

Benefits of Arabinoxylans Arabinoxylan molecule Some ferulic acid dimers which crosslink the arabinoxylan molecules to give gels .

Benefits of Arabinoxylans Arabinoxylan Gels .

Benefits of Arabinoxylans (targeted release) Arabinoxylans withstand digestive system conditions .

SIZE Macro -Structures Micro and Nano-Structures Emulsions Gels Casein Micelles Starch Granules Molecular Structures Polysaccharide Sugar Water Protein 1Å 1 nm 10 nm 100 nm 1 m 10 m 100 m 1mm 1cm .STRUCTURES IN FOODS AND BIOMATERIALS .

texture and nutrient delivery To develop new ingredients and foods designed for targeted delivery of functional micronutrients and bioactive compounds . Specifically.FOOD NANOTECHNOLOGY • Interest: assembly of molecules/components to create nanosystems with properties different than or improved from those of the individual components. proteins and lipids • Overall Aim: Understanding mechanisms involved in interactions to manipulate and improve structure. we are interested on interactions between carbohydrates.

FOOD NANOTECHNOLOGY Example Conjugated linoleic acid (CLA) Health Benefits • • • anti-carcinogenic antioxidant slow atherosclerosis Challenges for incorporation in foods • Unstable molecules • Stability can be improved by complexation with amylose – very insoluble compound Cavity in where a fatty acid molecule can be complexed Amylose molecule .

5 2 Log(Rz) 1.5 Log(Mw) 7. fatty acid and protein High Pressure Size Exclusion Chromatography Dynamic Light Scattering (DLS) Radius of giration (nm) of complex systems determined using multiangle laser scattering 2.5 Radius of Giration ≈ 20 −70 nm .Existence of the Nanocomplex Identification of a 3-component soluble nanocomplex formed by starch.5 8.5 6.5 1 0.5 0 5.

Viscosity profiles: A) starch control (S1). B) starch+protein (SP1). C) starch+FFA (S1F2).First cycle of rheometer operation 2 .Second cycle of rheometer operation . D) starch+protein+FFA (SP1F2) 1 .

HPSEC results of viscosity change with the addition of each component: A) starch control (S1). C) starch + FFA (S1F2). and D) starch + protein + FFA (SP1F2). . B) starch + protein (SP1).

C) S1F2 and D) SP1F2 .D C A B Comparison of rheology results for changes in viscosity-pasting profiles: A) S1. B) SP1.

Mechanism of Complex Formation Differential Scanning Calorimetry Viscosity Measurements Amylose + Free Fatty Acid Viscosity Measurements Nano Complex formation .

Existence of the Nanocomplex .

Solubilization Insoluble nanocomplex Soluble nanocomplex coo- CLA Molecule Protein Starch (Amylose) Molecule .

FOOD NANOTECHNOLOGY .Encapsulation Inclusion of a model hydrophobic compound (α-napthol) in ternary complex HPSEC profile (UV and RI ) of ternary complex containing α-napthol through inclusion process (arrow indicate complex peak) .

FOOD NANOTECHNOLOGY .Encapsulation Iodine binding measured by potentiometric titration Amylose + Free Fatty Acid Amylose Nanocomplex + Naphtol .

FOOD NANOTECHNOLOGY Encapsulation and Solubilization Inclusion of a model hydrophobic drug (5-Flurouracil) in ternary complex Inclusion of a model hydrophobic dye (fluorescein) in ternary complex .

STRUCTURES IN FOODS AND BIOMATERIALS - SIZE
Macro -Structures

Micro and Nano-Structures

Emulsions

Gels Casein Micelles Starch Granules

Molecular Structures
Polysaccharide Sugar

Water

Protein

1 nm

10 nm

100 nm

1 m

10 m

100 m

1mm

1cm

Computational/Molecular Modeling

1

Polymeric Systems
• Most foods contain one or more biopolymers; • Commonly used as thickener, emulsifier, stabilizer and gelling ingredients; • All characteristics and properties of the solution or gel may depend on the nature of the solvent, nature and type of polymer, concentration, temperature and others; • The mechanical behaviour (rheology) results from the combination of individual components with additional interaction effects;

Knowing their rheology is of great importance in developing and designing food formulations

1

Computational Modelling Initial State Final State Time Initial State Final State Time Polymeric Gels Particulate Gels Interaction Potential In both cases a model for the interaction between the particles forming the system is necessary 1 .

Computational Modeling Molecular Dynamics (based on Newton’s equations) Brownian Dynamics (Langevin equation) Solvent effects: friction random noise d ri m 2 = Fi dt 2 d 2 ri dri m 2 = Fi + γ i + ηi dt dt Interparticle force: model potential 1 .

(2010). Chem. B. 114. 13052-13058. Phase Angle . J. Phys.Particulate/Colloidal Gels Rheology – Viscoelastic Properties Gel Formation Experimental Torque bar Bob Sample Cup Simulation Impose a sinusoidal strain Measure the stress Oscillator Phase Angle δ γo σo Strain γ Stress σ Input (stress) Output (strain) * Santos et al.

6 % • Non-Bonding: R-shifted L-J (R=1. σ=1) • Bonding: FENE (Finite Extensible Non-linear Elastic) + Harmonic angular k=1 k=10 k=100 1 .Polymeric Systems System: • 64 chains of 400 beads. • Small volume fraction = 2.

Polymeric Systems Molecular Dynamics Flexible molecules k=1 Small energetic penalty for the chain to fold back: The system collapses .

Polymeric Systems Molecular Dynamics Increasing stiffness … k=10 k=100 .

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