Beruflich Dokumente
Kultur Dokumente
REOLOGIA Y EXTRUSION
Osvaldo H. Campanella
Biological Engineering and Whistler
Carbohydrate Research Center
Temas especficos que sern cubiertos:
Aplicaciones de Reologia en la ciencia y la ingeniera de alimentos
Reologia de Biomateriales Principios Bsicos
Tipos de fluidos y mtodos para su caracterizacin
Aplicaciones de Reologia para caracterizar alimentos y biomateriales los cuales
incluyen cereales y productos lcteos
Caracterizacin de la estructura de materiales y su relacin a su textura
Reologa de productos conteniendo nano partculas
Transicin vtrea. Caracterizacin and principios bsicos
Efecto de la transicin vtrea en el procesamiento y la textura de productos Efecto de la transicin vtrea en el procesamiento y la textura de productos
alimenticios
Extrusin, clasificacin and descripcin del proceso y tipos de tecnologa
Conceptos de extrusin reactiva
Rol de Reologa en el proceso de extrusin
Extrusin de cereales
Tecnologa de Extrusin
Efectos de Extrusin 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
Crystal Growth
-hydrate line
anhydrous -
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
Lactose
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 m 10 m 100 m 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide
1
Spraydried Lactose
Lactose
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
=
V
=
A
=
h
=
Flow Curve
Newtonian
Shear
Thickening
Shear thinning
Plastic
0
Yield Stress
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
S
h
e
a
r
S
t
r
e
s
s
(
P
a
)
cP 1 Pa.s 10 mPa.s 1
3
= =
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
n
o
k = +
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
+ =
+ =
+ =
. .
. . .
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
+ =
+ =
+ =
) (
Ellis
Generalized
Herschel-Bulkley
Carreau
Liquid Medium
Plastic Medium
o
g d
Y
part medium
o
) (
=
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
k
+ =
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
+ =
o
n
o
k
+ =
Summary of Rheological Behavior
n
k
=
o
Rest
Period
Time
o
Complete Recovery
Partial Recovery
No Recovery
Time
Time
or
0
Traditional Rotational Viscometry
Sample
M ,
Sample
M ,
How do we measure these liquid properties?
Concentric Cylinders
Sample
Sample
Parallel Plates
M ,
m) - (N Torque : M
rad/s Speed, Rotational :
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 = ) (
Arrhenius-type of equation
: " Viscosity"
A and B are parameters determined from data
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
=
Diffusion of spherical molecules (radius a)
Stokes/Einstein Equation
k
B
: Boltzman constant
T : Temperature
0
: FluidViscosity
0
6 a
0
2 2 3
0
2
( ) 6
(sec)
( )
D
B
a m a
t
m k T
D
s
= =
Diffusion time t
D
(sec) Einstein/Smoluchowski Equation
u (m/s)
x
z
y
h
(
m
)
exp
( ) 1
( / )
h meters
t
u meters s
= =
exp
( / )
t
u meters s
= =
Peclet Number
D
B
t a
Pe
t k T
= =
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
= Angle Phase
Traditional Viscoelastic Measurements
Torque bar
Sample
Cup
Bob
0
cos
) ( '
o
G =
Storage Modulus
sin
Loss Modulus
) ( '
) ( ' '
tan
G
G
=
Loss Tangent
Liquid Viscous
Material ic Viscoelast
Solid Elastic Hookean
o
o
90
90 0
0
=
< <
=
Strain
Stress
o
Oscillator
Phase Angle
0
sin
) ( ' '
o
G =
Pulse Shear Test
Viscoelasticity Testing
Concentric Cylinders
Sample
M ,
Sample
Cone and Plate
M ,
Sample
Parallel Plates
M ,
h
Mixer Rheology
CONTROLLED STRESS INSTRUMENTS
t sin
o
=
Stress Amplitude
(fixed by the user)
Frequency
(fixed by the user)
Input
Output
) ( sin + = 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 + = t
o
o
Measured
Measured
Phase Angle
(measured)
CONTROLLED STRAIN INSTRUMENTS
Input
t
o
sin =
) t ( sin + =
Output
Strain Amplitude
(fixed by user)
Frequency
(fixed by user)
Stress Amplitude
(measured)
) t ( sin
o
+ =
(measured)
Phase Angle
(measured)
) t ( sin
o
+ =
) ( ) ( " ) ( ) ( '
G t G + =
Solid Behavior Liquid Behavior
) ( ) ( " G ) t ( ) ( ' G ) t (
+ =
Solid Behavior
Liquid Behavior
Oscillatory Testing
cos ) ( ' G
o
=
Storage Modulus
sin ) ( " G
o
o
=
cos ) ( ' G
o
Loss Modulus
tan (Phase Angle)
) ( '
) ( "
tan
G
G
=
Oscillatory Testing
Other Viscoelastic Parameters
2 2 *
" ' ) ( G G G + = Complex Modulus
Complex Viscosity
2 2 *
*
" ' ) ( G G G +
= =
= =
Dynamic Viscosity
Out of Phase Viscosity
) (
'
"
G
=
) (
"
'
G
=
Oscillatory Testing
Other Viscoelastic Parameters (from Controlled Stress)
2 2
*
*
" '
1 1
) (
G G
G
J
+
= =
Complex Compliance
Storage Compliance
2 2
" '
'
) ( '
G G
G
J
+
=
Storage Compliance
2 2
" '
) ( '
G G
J
+
=
Loss Compliance
2 2
" '
"
) ( '
G G
G
J
+
=
VISCOELATIC MATERIALS
Solid (elastic) and Liquid (viscous) Behavior !!!!
Spring
G =
Dashpot
=
G
VISCOELATIC MATERIALS
Maxwell Element
G
= +
dt
d
t
R
Rheological Model
G
t
R
=
Relaxation Time
Maxwell Element
G
+
= Storage Modulus
Loss Modulus
2 2
1
"
R
R
t
t G
G
+
=
" ' G or G
Solid Behavior
' G
" G
1 =
R
t
Materials are more complex than
a single Maxwell
G
1
G
2
1
1
1
1
G
t
R
=
2
2
2
G
t
R
=
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
+
+
+
=
2
2
2
2 2
2
1
2
1 1
1 1
"
R
R
R
R
t
t G
t
t G
G
+
+
+
=
Four Element
Generalized Maxwell
G
1
1
G
2
G
3
2
G
n
n
=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
2 2
1
'
=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
1
"
i
i
Ri
G
t
=
" 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
'
=
+
=
n
i
Ri
Ri i
t
t G
G
1
2 2
1
"
" G
i
i
Ri
G
t
=
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, (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
"
/
(
P
a
.
s
)
Drilling Fluids
Cox-Merz Rule
1
'
"
n
G
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 or Frequency
Shifting Data
1
' n
n
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
=
) t (
o
) t (
) t ( G or ) t (
=
o
) t (
) t ( J or ) t (
=
) t (
3. Step Strain or Relaxation Test
(not the same than start-up flow)
o
) t (
t
o
) t (
) t ( G
=
Relaxation Modulus
t
) t (
t
o o
G =
o
t
o
t
Relaxation stresses
for materials with
different relaxation
times
Residual stress
Different t
R
1. Start-up Flow
o
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 (
t
o
t
o
o
exp
1
t
) t (
t
1
t
t
) t (
1
t
1
t
o
t
4. Creep Test
) t (
t
) t (
t
G
o
o
=
5. Recoil Test
) t (
t
1
t
o
t
t
t
G
o
o
=
1
t
o
Partial Recoil
permanent
deformation
No Recoil
Full Recoil
G
= +
dt
d
t
R
VISCOELASTIC FLUIDS - MODELING
+ =
d
t
+ =
R
t
dt
v
v v
| |
+ = + +
|
\
p g
t
+ =
R
d
t
dt
t
t G t t t dt ( ) ( ') ( ') '
Generalized Linear
Viscoelastic Model
Strain-rate tensor
G
t t '
Strain-rate tensor
depending on flow
Material Dependent
R
t t
t
R
G t t e
t
'
( ')
=
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
+ + = dt t u s t Ru t u m t F ) ( ) ( ) ( ) (
Acceleration
Velocity
) (
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
Oscillating
Plate
Rigid
Surface
R
S
h
o
Sample
m
eff
Z
h
= == =
4 44 4
3 33 3
3 33 3
2 22 2
( (( ( ) )) )
2 3
2 4
3 2
20 3
eff o
sample
o
m a h
Im Z
a
G
h
= + = + = + = +
( ( ( (
( ( ( (
( (( ( ) )) )
3
o
sample
4
2h
Real Z G
3 a
= == =
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 ) ( ) ( ) ( ) (
Acceleration Acceleration
Velocity Velocity
Displacement Displacement
) (
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
(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
(rad/s)
|
M
o
b
i
l
i
t
y
|
(
m
/
s
120 min
dried
60 min
dried
dried
) (
s
m i R
u
F
Z + = =
2 2
1 1
) (
s
m R
Z
Mobility
+
= =
m
s
peak
=
At Resonance Peak
peak
Zein Structure
Crystallization
GLUTEN FREE PRODUCTS
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. Glutens prolamin constituent, Gliadin, responsible for
viscous behavior, due non-covalent forces (hydrogen
bonding, van der Waals 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 glutens 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
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
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 = + +
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 m 10 m 100 m 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide
1
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 ( )
s
I ( )
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 (0.390.02)
gfedcb
Fraction 20-40%.vaf (0.440.01)
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 m 10 m 100 m 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide
1
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
c
r
e
a
s
e
o
f
p
o
r
e
s
i
z
e
I
n
c
r
e
a
s
e
o
f
S
o
l
u
b
i
l
i
t
y
I
n
c
r
e
a
s
e
o
f
m
e
c
h
a
n
i
c
a
l
p
r
o
p
e
r
t
i
e
s
e
l
a
s
t
i
c
i
t
y
C
o
n
c
e
n
t
r
a
t
i
o
n
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
e
I
n
c
r
e
a
s
e
o
f
S
o
l
u
b
i
l
i
t
y
I
n
c
r
e
a
s
e
o
f
m
e
c
h
a
n
i
c
a
l
p
r
o
p
e
r
t
i
e
s
e
l
a
s
t
i
c
i
t
y
C
o
n
c
e
n
t
r
a
t
i
o
n
o
f
G
e
l
l
i
n
g
A
g
e
n
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 m 10 m 100 m 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide
1
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
(-napthol) in ternary complex
FOOD NANOTECHNOLOGY - Encapsulation
HPSEC profile (UV and RI ) of ternary complex containing -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 m 10 m 100 m 1mm
1cm
Molecular Structures
Water
Sugar
Protein
Polysaccharide
Casein Micelles
Starch Granules
Gels
Polysaccharide
1
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 Newtons 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
+
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
Stress
o
Oscillator
Phase Angle
System:
64 chains of 400 beads;
Small volume fraction = 2.6 %
Non-Bonding: R-shifted L-J (R=1, =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