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Rheology. Definition of viscosity.

Non-newtonian behaviour.

Rheology

Rheology is the science of the flow and deformation of matter (liquid or soft solid) under the effect 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 revert to its original state, the deformation energy can not be recovered

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 displacement 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
=shear stress) and having a given perpendicular
gradient (=shear strain)

Ideal and real bodies

Ideal bodies
1. Ideally elastic: Hookean body (only reversible deformation, linear relation between stress and strain)
2. Ideally viscous: Newtonian fluids (continuous irreversible 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
=
(in N/m2 = Pa)
A yz

h = h0

l
Relative deformation (=strain): =
(without unit)
l0
Hooke's law:
=E

E is Young's modulus (in Pa), the measure of the


stiffness of an isotropic elastic material.
For e.g. rubber: E = 0.01 GPa = 1104 Pa
steel:
E = 200 GPa = 2108 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
=
(in N/m2 = Pa)
A xz

h < h0

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
=
=
dy

max

(without unit)

Shearing deformation of liquids

In liquids, a constant shear will cause the liquid to flow (viscous deformation).
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
dx
called shear strain:

dy

(without unit)

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:
dv x
dx /dt
1
1

D =

dy

dy

(unit:

=s )

Newtonian liquids

In Newtonian liquids shear rate (D) is linearly proportional to shear


stress ():

= D

The proportionality coefficient (called viscosity) is constant in


the case of Newtonian liquids: = const.
Viscosity is the measure of resistance against flow.

(Pa)

(Pas)

= tg = /D

D (s-1)

(Pa)

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:

= 0+ D

These bodies are termed ideal Bingham bodies. They are practically
non-existent.
A mechanical analogue to plastic deformation is the frictional resistance to sliding of
a block on a plane. No displacement occurs until the applied stress reaches the
frictional resistance.

(Pa)

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, elastic, 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 is applied

Creep: small constant is applied and watch strain increase

Relaxation: small strain is applied and watch the decay of

Non-newtonian viscosity

If the relation between shear stress and shear rate is not linear:
non-newtonian viscosity

Viscosity varies with the shear: = f() or = 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

(Pa)

SHEAR-THICKENING

(Pa)

(Pas)

D (s-1)

D (s-1)

(Pas)

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

(c , T , p , t ) =
D
Viscosity depends on:
concentration (c)
temperature (T)
pressure (p)
time (t)
shear rate (D)

If the shear rate


changes during an application, the internal
structure of the sample
will change and the
change in stress or viscosity can then be seen.

Apparent viscosity
The ratio of stress to rate of strain, calculated from measurements of forces and velocities as though the liquid were Newtonian.
IUPAC definition

( 0)
=
D

Nonlinearity factor

This is a general equation valid also for systems


having a yield stress value (0).

Shear-thinning behavior
Structural changes due to the forces changes in viscosity:
ordering of molecules or particles

)
(
=

n<1

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

)
(
=

n>1

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

(Pa)

(Pas)

( 0)
=
D

D (s-1)

Viscosity curve

Everyday's example: a cardhouse

(Pa)

Flow curve

Below the yield value the sample keeps


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 barrier indicates how stable the
system is.
Vmax>>kT kinetically stable 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

Rheopectic: constant shear causes an increase in viscosity

very common property (e.g. ketchup, yoghurt, paints, etc.)


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

(Pa)

Viscoplastic

Hysteresis loops

Red: with increasing shear rate, system 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 shearthinning properties


Viscosity of these solutions increases with increasing 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

solution
r =
solvent

solution
sp = r 1 =
1
solvent

Graphical determination of []

250
200

Mark-Houwink equation

spec/c
150

[ ] = K M

100

ln rel/c
50
0
0

0.02

c, g/mL

0.04

0.06

[]: intrinsic viscosity


K: empirical constant
M: molar mass
a: solvent-polymer interaction parameter

Dynamic measurements
Stress relaxation (recoil, loosen up, be tired out)
Small oscillation stress and strain
shift

Elastic term in phase (=0),


viscous term out of phase (=90),
viscoelastic (~45)