Rheology

M.Badu
 What is Rheology

• Rheology is the study of the flow of materials that behave in an

interesting or unusual manner. Oil and water flow in familiar, normal
ways, whereas mayonnaise, peanut butter, chocolate, bread dough,
flow in complex and unusual ways. In rheology, we study the flows
of unusual materials.”

• Normal (Newtonian) fluids (air, water, oil, honey) follow the same
scientific laws. On the other hand, there are also fluids that do not
follow the Newtonian flow laws.

• These non-Newtonian fluids, for example mayo, paint, molten

plastics, foams, clays, and many other fluids, behave in a wide
variety of ways. The science of studying these types of unusual
materials is called rheology”
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 Rheology

• Study of deformation and flow of matter

• A fluid is a substance that deforms continuously under

the action of a shearing force.

• Inquiry into the flow behavior of complex fluids

• Complex fluids do not follow Newton’s Law or Hooke’s

Law (of elasticity)

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 Newton’s Law of Viscosity

• Newton’s Law of Viscosity states that the shear stress (𝜏τ) in a

fluid is directly proportional to the rate of strain (or velocity
gradient) within the fluid
Newtonian vs. Non-Newtonian Fluids

•Newtonian fluids (like water and air) obey this law, meaning
their viscosity remains constant regardless of the applied shear
stress.

•Non-Newtonian (Complex) fluids (like blood, ketchup, and

some polymer solutions) do not obey Newton’s Law of
Viscosity. Their viscosity can change depending on the stress or
strain applied.
 Examples of Complex Fluids
• Foods
– Emulsions (mayonaisse, ice cream)
– Foams (ice cream, whipped cream)
– Suspensions (mustard, chocolate)
– Gels (cheese)
• Biofluids
– Suspension (blood)
– Gel
– Solutions
• Personal Care Products
– Suspensions (nail polish, face scrubs)
– Solutions/Gels (shampoos, conditioners)
– Foams (shaving cream)
• Electronic and Optical Materials
– Liquid Crystals (Monitor displays)
– Melts (soldering paste)
• Pharmaceuticals
– Gels (creams, particle precursors)
– Emulsions (creams)
– Aerosols (nasal sprays)
• Polymers
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 Rheology’s Goals

1. Establishing the relationship between applied

forces and geometrical effects induced by
these forces at a point (in a fluid).

– The mathematical form of this relationship is called

the rheological equation of state, or the
constitutive equation.
– The constitutive equations are used to solve
macroscopic problems related to continuum
mechanics of these materials.

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 Rheology’s Goals

2. Establishing the relationship between

rheological properties of material and its
molecular structure (composition).

– Related to:
• Estimating quality of materials
• Understanding laws of molecular movements
• Intermolecular interactions
– Interested in what happens inside a point during
deformation of the medium.

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Rheological analysis is based on the use
of continuum theories
– There is no discontinuity in transition from one geometrical point
to another, and the mathematical analysis of infinitesimal
quantities can be used; discontinuities appear only at boundaries

– Properties of materials may change in space (due to gradients)

but such changes occur gradually
• changes are reflected in space dependencies of material
properties entering equations of continuum theories

– Continuity theories may include an idea of anisotropy of

properties of material along different directions.

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Rheology as an Interdisciplinary Science

Physics Chemistry
Explanation and prediction
of rheological properties Direct correlation between
chemical parameters and
• molecular physics rheological properties
• statistical physics Rheology
• thermodynamics, etc… (of Liquids) • molecular mass
• MWD
• chemical structures
• intermolecular interactions

Material Design

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Rheology as an Interdisciplinary Science
Rheological studies give background for formulation of boundary
problems in dynamics of liquids (governing equations and their solutions)
to find numerical values of macro properties.

Rheology
(of Liquids)

Mechanics Technology/
of Engineering
Continuum
Analysis of flow problems.
New applications

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Rheology as an Interdisciplinary Science

Physics Chemistry

Rheology
(of Liquids)

Mechanics Technology/
of Engineering
Continuum

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 Rheological Properties
• Stress
– Shear stress
– Normal stress
– Normal Stress differences
• Viscosity most commonly sought
– Steady-state (i.e. shear) rheological quantity
– Extensional
– Complex
• Viscoelastic Modulus
– G’ – storage modulus
– G” – loss modulus
• Creep, Compliance, Decay
• Relaxation times

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 Newtonian Fluids

• Newtonian fluids are those whose

viscosity is independent of shear
rate. The viscosity of these materials
will remain a constant no matter how
fast they are forced to flow through a
pipe or channel. Examples of
Newtonian fluids would include
water, organic solvents, and honey.
 non-Newtonian Fluids

• In contrast to Newtonian fluids, the

viscosity of non-Newtonian fluids
varies depending on the shear rate.
Shear-rate-dependent fluids can
show either shear thickening or shear
thinning behavior.
 Common Non-Newtonian Behavior

• shear thinning
• shear thickening
• yield stress
• viscoelastic effects
– Weissenberg effect
– Fluid memory
– Die Swell

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 Shear thinning and Shear
thickenning
• The sample is called shear thickening if the viscosity of the
fluid increases as the shear rate increases.

• A common example of shear thickening fluids is a mixture of

cornstarch and water.

• Samples are shear thinning if the viscosity decreases as the

shear rate increases.

• Shear thinning fluid are ubiquitous in industrial and biological

processes.

• Common examples include ketchup, paints, blood. These

fluids are also known as pseudoplastics
The relationship between the viscosity and the shear rate was
used to determine the flow properties of the emulsions.

Effect of the fat/water ratio on the flow Effect of sodium alginate on the flow of
of emulsions emulsions
The weak associative interactions of the fat particles as a result of weak particle
network structure and the weak gel network formed breaks as the shear rate increases
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 Dependence of the viscoelastic response on the fat/water
ratio

10/90 15/85

Change in the storage (G′) and loss (G′′) moduli, complex viscosity (Eta*) and tan δ of
the emulsion with increasing fat content. 18
The extent of network formation with increasing the amount
of sodium alginate in the emulsion

Sosa-Herrera M.G, et al, Food Hydrocol., 2012 19

 Summary of findings

• The emulsion stability was influenced by amount of the fat

dispersed. High amounts of dispersed fats were stable against
creaming whiles lower fats were not stable against creaming

• The presence of both sodium alginate and Tween 20

emulsifiers were shown to exhibit a synergistic effect to
influence the stability of the emulsion against particle
aggregation.

• For the long-term physical stability, the presence of the fat and
sodium alginate introduces rigidity to the emulsions, which
dictates the viscoelastic responds of the emulsion system.
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 Shear Thinning and Shear Thickening

• shear thinning – tendency of some materials to decrease in

viscosity when driven to flow at high shear rates, such as by
higher pressure drops

Increasing shear rate

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 Shear Thickening

• shear thickening – tendency of some materials to

increase in viscosity when driven to flow at high
shear rates

Dr. Aldo Acevedo - ERC

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SOPS
Phenomenological Modeling of Shear Thinning and Thickening

• Generalized Newtonian Equation:

  ( )

n 1
• Power Law Model:
 m
– m=m n=1 Newtonian
– m n>1 Shear Thickening, Dilatant
– m n<1 Shear Thinning

• Slope of log h vs log g is constant

• Advantages: simple, success at predicting Q vs DP
• Disadvantages: does not describe Newtonian Plateau at small
shear rates
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Modeling of Shear Thinning and Thickening
• Carreau-Yasuda Model
n 1
 ( )   
[1  ( ) ]a a

0  
a – affects the shape of the transition region
l – time constant determines where it changes from constant to
power law
n – describes the slope of the power law
h0, h∞ - describe plateau viscosities

• Advantages: fits most data

• Disadvantages: contains 5 parameters, do not give molecular
insight into polymer behavior

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 Yield Stress
• Tendency of a material to flow only when stresses are
above a treshold stress

• Bingham Model:
    y
 y

 () 

0    y

ty = yield stress, always positive
m0 = viscosity at higher shear rates

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 Elastic and Viscoelastic Effects
• Weissenberg Effect (Rod Climbing Effect)
– does not flow outward when stirred at high speeds

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 Elastic and Viscoelastic Effects
• Fluid Memory
– Conserve their shape over time periods or seconds or
minutes
– Elastic like rubber
– Can bounce or partially retract
– Example: clay (plasticina)

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 Elastic and Viscoelastic Effects

• Viscoelastic fluids subjected to a stress deform

– when the stress is removed, it does not instantly vanish
– internal structure of material can sustain stress for some
time
– this time is known as the relaxation time, varies with
materials
– due to the internal stress, the fluid will deform on its own,
even when external stresses are removed
– important for processing of polymer melts, casting, etc..

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 Recoverable versus permanent:

The deformation is recoverable if Deformation is permanent if

the material returns to its initial the material remains
shape when the stress is deformed when the stress
removed. is removed.

While elastic deformation is recoverable, viscous and plastic

deformations are not.
The behavior of real materials is better described by
combining simple models in series or parallel. For
example:

A visco-elastic (or
Maxwell) solid:

An elasto-plastic
(Prandtl) material:
 A visco-plastic (or
Bingham) material:

A firmo-viscous
(Kelvin or Voight)
material:

It turns out that rocks subjected to small strains (seismic

waves, slip on faults, etc.) behave as linear elastic
materials.
 Deformation
 Solids or liquids in rest keep their shape (=form) unchanged

 When forces act on these bodies, deformation can occur if the force
exerted is larger than the internal forces holding the body in its original
form

 Deformation is the transient or permanent shape change of a given body

 transient or reversible deformation (elasticity): when the force acting upon

the body ends, the shape reverts to its original state and the deformation
work (=energy) is recovered

 permanent or irreversible deformation (flow): shape does not re- vert to its
original state, the deformation energy can not be re- covered

 Deformation forces
 The deformation forces (also often called loading) which act on a
solid body or a liquid can be

 Static: the force is acting constantly and its direction and

magnitude are constant (constant loading)

 Dynamic: the magnitude and/or direction of the force(s) are

variable as a function of time (variable loading)

 cyclic

 acyclic