Rheology. Definition of viscosity.

Non-newtonian behaviour.
 Rheology
● Rheology is the science of the flow and deforma-
tion of matter (liquid or “soft” solid) under the ef-
fect of an applied force
● Deformation → change of the shape and the size
of a body due to applied forces (external forces and
internal forces)
– Flow → irreversible deformation (matter is not reverted
to the original state when the force is removed)
– Elasticity → reversible deformation (matter is reverted
to the original form after stress is removed)
 Applications of rheology
● Understanding the fundamental nature of a system (basic
science)
● Quality control (raw materials and products, processes)
● Study of the effect of different parameters on the quality of
a product
● Tuning rheological properties of a system has many
applications in every day's life
• Pharmaceutics
• Cosmetics
• Chemical industry
• Oil-drilling
etc
 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
Deformation forces
 Definitions
● Strain: deformation in term of relative displace-
ment of the particles composing the body
● Stress: measure of internal forces acting within a
(deformable) body
● Shear: deformation of a body in one direction only
(resulting from the action of a force per unit area
τ=shear stress) and having a given perpendicular
gradient (γ=shear strain)
 Ideal and real bodies
● Ideal bodies
1. Ideally elastic: Hookean body (only reversible deforma-
tion, linear relation between stress and strain)
2. Ideally viscous: Newtonian fluids (continuous irre-
versible deformation, flow)
3. Ideally plastic: (no permanent deformation below the
yield stress, and continuous shear rate at and above the
yield stress.)
● Real bodies (combination of the properties above)
– 1+2: viscoelastic materials
– 2+3: plastic materials
 Elastic deformation, ideally elastic
bodies
For ideally elastic bodies, there is a linear relationship between the
relative deformation and the applied force (observation of R.
Hooke on springs)

Shear stress:
F
τ= (in N/m2 = Pa)
A yz
h = h0
Δl
Relative deformation (=strain): ε= (without unit)
l0
E is Young's modulus (in Pa), the measure of the
Hooke's law: stiffness of an isotropic elastic material.
τ=εE For e.g. rubber: E = 0.01 GPa = 1·104 Pa
steel: E = 200 GPa = 2·108 Pa
 Shearing deformation of solids
If a tangential force is acting on the upper plane of a body fixed at its
base a shearing deformation will result

Shear stress:
F
τ= (in N/m2 = Pa)
h < h0 A xz

The deformation will vary perpendicularly with the distance from the base
to the maximal shear plane: dx = f(y) and dxmax= f(h)

The gradient of the shear in this perpendicular direction is called shear

strain: dx
dx max
γ= = (without unit)
dy h
 Shearing deformation of liquids
● In liquids, a constant shear will cause the liquid to flow (viscous de-
formation).
● If the flow is laminar (there are no turbulences) the liquid flows as
layers parallel to the wall of the vessel.
● The velocity of these layers is decreasing from a maximal value to
zero in the direction perpendicular to the wall (the layer adsorbed at
the wall does not move).
● The gradient of the shear in this perpendicular direction is also
called shear strain: dx
γ= (without unit)
dy
● But as the layers of liquid are constantly moving (dx is not constant)
we can define a velocity gradient from the bulk to the wall called
shear rate: dx /dt dv x 1 −1
D = = (unit: =s )
dy dy s
 Newtonian liquids
● In Newtonian liquids shear rate (D) is linearly proportional to shear
stress (τ):
τ = ηD
● The proportionality coefficient η (called viscosity) is constant in
the case of Newtonian liquids: η = const.
● Viscosity is the measure of resistance against flow.

η τ
(Pa·s) (Pa)

η = tg α = τ/D
α

τ (Pa) D (s-1)
Viscosity curve Flow curve
 Ideally plastic bodies
● Ideally plastic bodies would behave as rigid bodies until a yield
value of shear and flow as Newtonian liquids above the yield value:
τ = τ 0+ η D
● These bodies are termed ideal Bingham bodies. They are practically
non-existent.

A mechanical analogue to plastic deforma-

tion is the frictional resistance to sliding of
τ a block on a plane. No displacement oc-
(Pa)
curs until the applied stress reaches the
frictional resistance.
α

τ0 No flow until
the yield stress

D (s-1)
Viscosity curve
 Real materials
● In practice only a few materials have an ideal flow behavior
● Usually rheological properties are a combination of viscous, elas-
tic, and plastic properties
● Moreover these properties change most often non-linearly
● Sometimes the sample is subject to breakdown if sheared, in this
case small dynamic strain or stress is applied during rheological
measurements
– Oscillation: small oscillating τ is applied
– Creep: small constant τ is applied and watch strain increase
– Relaxation: small strain is applied and watch the decay of τ
 Non-newtonian viscosity
● If the relation between shear stress and shear rate is not linear:
non-newtonian viscosity
● Viscosity varies with the shear: η = f(τ) or η = f(D)
● Most viscous materials are non-newtonian
● Non-newtonian behavior depends on the micro- or nanostructure
of the material (breakdown, arrangement, or entanglement)
SHEAR-THINNING SHEAR-THICKENING

τ η τ η
(Pa) (Pa·s) (Pa) (Pa·s)

D (s-1) D (s-1) D (s-1) D (s-1)

 The Weissenberg effect
● A spinning rod is placed in a polymer solution composed of long chains
● Polymer chains are drawn towards the rod
● Long polymers get wrapped around the rod
● Entanglement of the polymer chains make the wrapped chains to
stretch
● The stretched chains pull the free polymers towards the rod

Low viscosity High viscosity

Newtonian liquid Viscoelastic liquid
 Influences on the viscosity

η (c , T , p , t ) = τ
D

Viscosity depends on:

● concentration (c) If the shear rate
changes during an ap-
● temperature (T)
plication, the internal
● pressure (p) structure of the sample
● time (t)
will change and the
change in stress or vis-
● shear rate (D)
cosity can then be seen.
 Apparent viscosity

The ratio of stress to rate of strain, calculated from measure-

ments of forces and velocities as though the liquid were Newto-
nian. IUPAC definition

n Nonlinearity factor
( τ − τ0)
η=
D
This is a general equation valid also for systems
having a yield stress value (τ0).
 Shear-thinning behavior

Structural changes due to the forces – changes in viscosity:

ordering of molecules or particles

( τ)
n

η= n<1
D
 Shear-thickening behavior

Structural changes due to the forces – changes in viscosity,

disordering of the particles or molecules

E.g. wet sand or

mixture of water
and cornstarch
( τ)
n

η= n>1
D
http://video.google.com/videoplay?docid=-4684348427588167444&ei=4JfVStqgI86z-AbYhtGrCg&hl=hu#
 Example of shear-thickening system
Hydrogel: 5% PVA + 5% sodium borate

Force~0 : viscous fluid

weak force : plastic

medium force, : elastic

Very strong force, rigid solid

http://www.youtube.com/watch?v=f2XQ97XHjVw&feature=related
 Yield stress
τ η
(Pa) (Pa·s)

n
( τ − τ0)
η=
τ0 D

D (s-1) τ0 τ (Pa)
Viscosity curve Flow curve

Below the yield value the sample keeps

Everyday's example: a cardhouse
its shape and behaves as a solid body.
Above the yield value the structure
breaks down and sample start to flow.
The yield value shows how strong the
structure is.
 Explanation of yield value

The height of the energy bar-

rier indicates how stable the
system is.
Vmax>>kT kinetically sta-
ble sol
gel

~ yield value

In a “secondary minimum” a much weaker and potentially

reversible adhesion between particles exists in a gel
structure. These weak flocs are sufficiently stable not to be
broken up by Brownian motion, but may dissociate under
an externally applied force such as vigorous agitation
 Time-dependent effects
● When viscosity at a given shear depends on time, the system is
– Thixotropic: constant shear causes a decrease in viscosity
• very common property (e.g. ketchup, yoghurt, paints, etc.)
– Rheopectic: constant shear causes an increase in viscosity
• very few materials are rheopectic (gypsum paste, printer ink)
● If time-dependent effects are significant, flow and viscosity curves
present a hysteresis loop (curves measured by increasing shear
do not coincide with curves measured by decreasing shear)
● These effects are caused by the breakdown or buildup of ordered
structures within the flowing matter
 Hysteresis loop
Flow curve of thixotropic systems
with and without yield stress

τ
(Pa) Viscoplastic

Hysteresis loops

Red: with increasing shear rate, sys-

τ0 tem is breaking down
Blue: with decreasing shear rate,
system is building up
Viscous

D (s-1)
Flow curves
 Polymer solutions
● Dilute polymer solutions have generally shear-
thinning properties
● Viscosity of these solutions increases with increas-
ing molar weight
– hydrodynamic radius of the polymer coil increases with
molar weight
– larger radius means more pronounced interaction with
solvent molecules (=”friction”) → increase in viscosity
● Empirical relation between (intrinsic) viscosity and
molecular weight: the Mark-Houwink equation
 Molar weight determination by
viscosity
Relative viscosity Specific viscosity
ηsolution ηsolution
ηr = η ηsp = ηr −1 = η −1
solvent solvent

Graphical determination of [η]

250

200
ηspec/c Mark-Houwink equation
150
a
100
[ η] = K M
ln ηrel/c
50
[η]: intrinsic viscosity
0
K: empirical constant
0 0.02 0.04 0.06 M: molar mass
c, g/mL
a: solvent-polymer interaction parameter
 Dynamic measurements
Stress relaxation (recoil, loosen up, be tired out)

Small oscillation stress and strain

shift

D
Elastic term in phase (δ=0),
viscous term out of phase (δ=90°),
viscoelastic (δ~45°)