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NON-IDEAL RHEOLOGICAL BEHAVIOR

FLUID (VISCOUS BEHAVIOR) SOLID (ELASTIC BEHAVIOR)
Newtonian Non-Newtonian Non-Hookean Hookean
FLUID-SOLID
Time-Dependent
Rheopectic Thixotropic
Structural Models
Time-Independent
Power Law Bingham Herschel-Bulkley Other Models
Non-Linear Elastic
Viscoelastic
Maxwell Burgers Kelvin
Dilatant Pseudoplastic

q =
t


=
shear stress
shear rate
According to
Newton
NON-NEWTONIAN FLUIDS
Fluid systems may be non-ideal in two ways:
1. The viscosity may depend on shear rate

2. The viscosity may depend on time

Some (many) may have both


http://youtube.com/watch?v=f2XQ97XHjVw

Newtonian fluids, viscosity does not depend on
the shear rate. Fluid begins to flow when ever
a shear stress is applied

FLUID q (mPa.s)
Water 1
Coffee cream 10
Vegetable oil 100
Honey 10,000
Asphalt 100,000

Shear Rate (s
-1
)
.
Shear Stress
t (Pa)
Honey
Oil
Water
q = slope of
this line
SHEAR-DEPENDENT FLUIDS
Plastic (Bingham Plastic): some finite
shear stress must be applied before the
material will flow. This minimum stress
required is known as the yield stress.
Examples include margarine, whipped
toppings, mayonnaise, or catsup.

Shear Rate (s
-1
)
.
Shear Stress
t (Pa)
True Bingham
Yield stress
Apparent viscosity
q
A
=t/ given by
slope of this line
Shear Rate (s
-1
)
.
Apparent
Viscosity
q
A


Pseudoplastic (shear thinning): An increasing
shear force gives a more than proportional
increase in shear rate.
The material seems less viscous at higher
shear rates.
Examples include some salad dressings,
concentrated fruit juices, and French mustard.

Shear Rate (s
-1
)
.
Shear Stress
t (Pa)
q
A
Shear Rate (s
-1
)
.
Apparent
Viscosity
q
A


Dilatant (shear thickening): Increasing shear
force gives a less than proportional increase
in shear rate; the material seems to be more
viscous at higher shear rates.
Dilatant food systems are not common.
Examples are some cooked starch
suspensions.

Wet sand
Wet starch at
40-70% solids
Shear Rate (s
-1
)
.
Shear Stress
t (Pa)
q
A
Shear Rate (s
-1
)
.
Apparent
Viscosity
q
A


Herschel-Bulkley: these fluids exhibit
both a yield stress and pseudoplastic
behavior

Shear Rate (s
-1
)
.
Shear Stress
t (Pa)

MODELS FOR SHEAR
DEPENDENT FLUIDS

Power Law model: shear stress varies
as the shear rate to some power



where K is the consistency index, and n is
the flow behavior index.


t = K


n

Bingham model: model of Newtonian
fluid, but includes a yield stress term,
and the plastic viscosity q

t = t
o
+q'



Herschel-Bulkley model: power law but
includes a yield stress term to.

t = t
o
+ K


n

Casson model: used to estimate yield
stress. Official method for interpreting
chocolate flow data. The Casson plastic
viscosity is given by q
c
=K
c
2
, and the
Casson yield stress by t
c
=K
oc
2
.

t = t
o
+q
a



Powell-Eyring model:

t =q


+
q
o
q

|
sinh
1
(|

)
where o and | are constants, q
o
is the limiting viscosity
at zero shear rate, and q

is the limiting viscosity at


infinite shear rate. The Powell-Eyring models
allow characterizing materials that show Newtonian
viscosities at very low or very high shear rates, but
deviate at intermediate shear rates.
HERSCHEL-BULKLEY MODEL
One of the most used models
Viscous behavior of Newtonian fluids,
Bingham plastics, pseudoplastic, and
dilatant materials can all be described
as special cases

FLUID K n t
o
EXAMPLES
Herschel-Bulkley >0 0<n< >0 Fish paste, raisin paste
Newtonian >0 1 0 Water, fruit juice, milk
Pseudoplastic >0 0<n<1 0 Applesauce, banana puree
Dilatent >0 1<n< 0 40% raw corn starch, some honey
Bingham Plastic >0 1 >0 Tomato paste, some yogurts


TIME DEPENDENT VISCOUS
BEHAVIOR
For some fluids, the shear stress may
change at a given shear rate as time
passes. This is another form of non-
Newtonian behavior.

Thixotropic: shear stress decreases with
time at constant shear rate; alternately,
the apparent viscosity decreases with
time. The change is reversible; the fluid
rebuilds itself once shearing is
removed. Includes some starch paste
gels.

Shear Thinning: apparent viscosity
decreases with time; however, the
change is irreversible-the material is
less viscous once the shearing is
removed. Foods more often behave as
shear thinning materials than as true
thixotropic materials.

Rheopectic: shear stress increases with
time at constant shear rate; the
apparent viscosity increases with time.
The change is reversible. Rare in food
systems.

Shear Thickening: shear stress
increases with time at constant shear
rate; the apparent viscosity increases
with time. The change is irreversible-
the material stays thick once shear is
removed.
At constant shear rate . . .
q
a

Time
Thixotropic
Shear thinning
Rheopectic
Shear thickening
Shear on Shear off
Time dependency also seen in experiments
designed to test shear dependency
Shear Rate (s
-1
)
.
Shear Stress
t (Pa)
up
down
up
down
MOLECULAR INTERPRETATIONS
OF VISCOSITY
Viscosity and Energy Dissipation:
viscosity represents the resistance to flow
introduced by frictional forces in the fluid.
Some of the energy is dissipated as heat.
Increased heat does in fact represent
increased motion at the molecular level,
but this motion is random, not directed.


Stress (F/A) along
upper layer
Some molecules move along
upper layer. Some move to lower
levels transf erring momentum to
molecules there.. Some of that
energy becomes directed in the
flow direction. Some becomes
randomized into thermal motion
NON-IDEAL BEHAVIOR
Shear Dependency. Shear dependency
usually arises in high molecular weight
polymers (xanthan gum, starches). One
explanation is that at low shear rates,
interchain entanglements greatly increase the
viscosity. As shear rate increases , the
individual chains become more oriented
along the lines of flow.



Low shear-
polymer entanglement
High shear-
polymer entanglement

Bingham plastic may be due to a high
degree of polymer entanglement
forming a pseudo-gel. The solvent
cannot flow through this structure until a
sufficient shear force is exerted to
break up the structure. In systems with
aggregated particles, pseudoplastic
behavior may occur when increased
shear causes the particles to separate.



Dilatancy: at low shear conditions, particles
are closely packed. The void spaces
between particles is minimal and are filled
with solvent (water). As shear stress
increases, the total volume increases,
increasing the volume of void space.
However, the solvent doesnt fill all of the void
space, creating a dryness which increases
the resistance to shearing stress.


No/Low Shear
High Shear
Time-Dependence
Similar arguments can be made for fluids that
become more or less viscous over time at
constant shear rate. For example, for a
thixotropic fluid, molecules become more and
more disentangled over time, thus leading to
a decrease in viscosity. If the shear force is
removed, the molecules may reaggregate or
become entangled again over time.