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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)
Applications of rheology
Pharmaceutics
Cosmetics
Chemical industry
Oil-drilling
etc
Deformation
Deformation forces
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 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.)
Shear stress:
F
=
(in N/m2 = Pa)
A yz
h = h0
l
Relative deformation (=strain): =
(without unit)
l0
Hooke's law:
=E
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)
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
= D
(Pa)
(Pas)
= tg = /D
D (s-1)
(Pa)
Viscosity curve
Flow curve
= 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
Non-newtonian viscosity
If the relation between shear stress and shear rate is not linear:
non-newtonian viscosity
(Pa)
SHEAR-THICKENING
(Pa)
(Pas)
D (s-1)
D (s-1)
(Pas)
D (s-1)
D (s-1)
Low viscosity
High viscosity
Newtonian liquid
Viscoelastic liquid
(c , T , p , t ) =
D
Viscosity depends on:
concentration (c)
temperature (T)
pressure (p)
time (t)
shear rate (D)
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
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
)
(
=
n>1
http://video.google.com/videoplay?docid=-4684348427588167444&ei=4JfVStqgI86z-AbYhtGrCg&hl=hu#
Yield stress
(Pa)
(Pas)
( 0)
=
D
D (s-1)
Viscosity curve
(Pa)
Flow curve
Time-dependent effects
Hysteresis loop
Flow curve of thixotropic systems
with and without yield stress
(Pa)
Viscoplastic
Hysteresis loops
Viscous
D (s-1)
Flow curves
Polymer solutions
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
Dynamic measurements
Stress relaxation (recoil, loosen up, be tired out)
Small oscillation stress and strain
shift