Introduction to Rheology

 Rheology describes the deformation of a body under

the influence of stresses.
 “Bodies” in this context can be either solids, liquids,
or gases.
 Ideal solids deform elastically.
 The energy required for the deformation is fully
recovered when the stresses are removed.
 Introduction to Rheology

 Ideal fluids such as liquids and gases deform

irreversibly -- they flow.
 The energy required for the deformation is dissipated
within the fluid in the form of heat
and cannot be recovered simply by removing the
stresses.
 Introduction to Rheology

• The real bodies we encounter are neither ideal solids

nor ideal fluids.
• Real solids can also deform irreversibly under the
influence of forces of sufficient magnitude
• They creep, they flow.
• Example: Steel -- a typical solid -- can be forced to
flow as in the case of sheet steel when it is pressed
into a form, for example for automobile body parts.
 Introduction to Rheology

• Only a few liquids of practical importance come close to

ideal liquids in their behavior.
• The vast majority of liquids show a rheological behavior
that classifies them to a region somewhere between the
liquids and the solids.
• They are in varying extents both elastic and viscous and
may therefore be named “visco-elastic”.
• Solids can be subjected to both tensile and shear stresses
while liquids such as water can only be sheared.
Ideal solids subjected to shear
stresses react with strain:

5
 Introduction to Rheology

 τ = G ⋅ dL/dy = G ⋅ tan γ ≈ G ⋅ γ
 τ = shear stress = force/area, N/m 2 = Pa
 G = Young’s modulus which relates to the stiffness
of the solid, N/m 2 =Pa
 γ = dL/y = strain (dimensionless)
 y = height of the solid body [m]
 ΔL = deformation of the body as a result of shear
stress [m].
 Introduction to Rheology

 The Young’s modulus G in this equation is a

correlating factor indicating stiffness linked
mainly to the chemical-physical nature of the
solid involved.
 It defines the resistance of the solid against
deformation.
 Introduction to Rheology

 The resistance of a fluid against any

irreversible positional change of its’ volume
elements is called viscosity.
 To maintain flow in a fluid, energy must be
added continuously.
 Introduction to Rheology

 While solids and fluids react very differently when

deformed by stresses, there is no basic difference
rheologically between liquids and gases.
 Gases are fluids with a much lower viscosity than
liquids.
 For example hydrogen gas at 20°C has a viscosity a
hundredth of the viscosity of water.
 Introduction to Rheology

 Instruments which measure the visco-elastic

properties of solids, semi-solids and fluids are
named “rheometers”.
 Instruments which are limited in their use for
the measurement of the viscous flow behavior
of fluids are described as “viscometers”.
 Shear induced flow in liquids can
occur in 4 laminar flow model cases:

11
 Flow between two parallel flat
plates

 When one plate moves and the other is

stationary.
 This creates a laminar flow of layers which
resembles the displacement of individual cards
in a deck of cards.
 Flow in the annular gap between
two concentric cylinders.

 One of the two cylinders is assumed to be stationary

while the other can rotate.
 This flow can be understood as the displacement of
concentric layers situated inside of each other.
 A flow of this type is realized for example in
rotational rheometers with coaxial cylinder sensor
systems.
 Flow through pipes, tubes, or
capillaries.

 A pressure difference between the inlet and the

outlet of a capillary forces a Newtonian liquid to
flow with a parabolic speed distribution across
the diameter.
 This resembles a telescopic displacement of
nesting, tube-like liquid layers sliding over each
other.
 Flow through pipes, tubes, or
capillaries.

 A variation of capillary flow is the flow in channels

with a rectangular cross-section such as slit
capillaries.
 If those are used for capillary rheometry the channel
width should be wide in comparison to the channel
depth to minimize the side wall effects.
Flow between two parallel-plates or
between a cone-and-plate sensor

• Where one of the two is stationary and the

other rotates.
• This model resembles twisting a roll of coins
causing coins to be displaced by a small angle
with respect to adjacent coins.
• This type of flow is caused in rotational
rheometers with the samples placed within
the gap of parallel-plate or cone-and-plate
sensor systems.
Aspects of Rheology
 The basic law

 The measurement of the viscosity of liquids first requires the

definition of the parameters which are involved in flow.
 Then one has to find suitable test conditions which allow the
measurement of flow properties objectively and reproducibly.
 The basic law

 Isaac Newton was the first to express the basic law of

viscometry describing the flow behavior of an ideal liquid:
   * 
 shear stress = viscosity ⋅ shear rate
The parallel-plate model helps to define
both shear stress and shear rate

20
 Shear stress

 A force F applied tangentially to an area A being the interface

between the upper plate and the liquid underneath, leads to a
flow in the liquid layer.
 The velocity of flow that can be maintained for a given force is
controlled by the internal resistance of the liquid, i.e. by it’s
viscosity.
 Shear stress

τ =F (force)/A (area)
N (Newton)/m 2 = Pa [Pascal]
 Shear rate

 The shear stress τ causes the liquid to flow in a special pattern.

 A maximum flow speed Vmax is found at the upper boundary.
 The speed drops across the gap size y down to Vmin = 0 at the
lower boundary contacting the stationary plate.
 Shear rate

• Laminar flow means that infinitesimally thin liquid layers slide

on top of each other, similar to the cards in a deck of cards.
• One laminar layer is then displaced with respect to the
adjacent ones by a fraction of the total displacement
encountered in the liquid between both plates.
• The speed drop across the gap size is named “shear rate” and
in it’s general form it is mathematically defined by a
differential.
 Shear rate

In case of the two parallel plates with a linear speed

drop across the gap the differential in the equation
reduces to:
 Shear rate

 In the scientific literature shear rate is denoted as 

 The dot above the γ indicates that shear rate is the
time-derivative of the strain caused by the shear
stress acting on the liquid lamina.
Shear rate
 Solids vs Liquids

• Comparing equations [1] and [7] indicates another

basic difference between solids and liquids:
• Shear stress causes strain in solids but in liquids it
causes the rate of strain.
• This simply means that solids are elastically
deformed while liquids flow.
• The parameters G and η serve the same purpose
of introducing a resistance factor linked mainly to
the nature of the body stressed.
 Dynamic viscosity

 Solving equation [2] for the dynamic viscosity η gives:

 Dynamic viscosity

• The unit of dynamic viscosity η is the “Pascal ⋅

second” [Pa⋅s].
• The unit “milli-Pascal ⋅ second” [mPa⋅s] is also often
used.
– 1 Pa ⋅ s = 1000 mPa ⋅ s
• It is worthwhile noting that the previously used
units of “centiPoise” [cP] for the dynamic viscosity η
are interchangeable with [mPa⋅s].
– 1 mPa⋅s = 1 cP
Typical viscosity values at 20°C
[mPa⋅s]

31
 Kinematic viscosity

 When Newtonian liquids are tested by means of

some capillary viscometers, viscosity is determined
in units of kinematic viscosity υ.
 The force of gravity acts as the force driving the
liquid sample through the capillary.
 The density of the sample is one other additional
parameter.
 Kinematic viscosity

 Kinematic viscosity υ and dynamic viscosity η are

linked.
 Flow and viscosity curves

• The correlation between shear stress and shear rate

defining the flow behavior of a liquid is graphically
displayed in a diagram of τ on the ordinate and on
the abscissa.
• This diagram is called the “Flow Curve”.
• The most simple type of a flow curve is shown In
Figure 4.
• The viscosity in equation(2) is assumed to be
constant and independent of .
Flow Curve

35
 Viscosity Curve


• Another diagram is very common: η is plotted versus 
• This diagram is called the “Viscosity Curve”.
• The viscosity curve shown in Fig. 5 corresponds to the flow
curve of Fig. 4.
• Viscosity measurements always first result in the flow curve.
• It’s results can then be rearranged mathematically to allow
the plotting of the corresponding viscosity curve.
• The different types of flow curves have their counterparts in
types of viscosity curves.
Viscosity Curve

37
Shear Rate Dependence
Shear Rate Dependence
Effect of Temperature
Effect of Branching
Overall
Molecular Wt. Distribution
 Viscosity parameters

 Viscosity, which describes the physical property of a

liquid to resist shear-induced flow, may depend on 6
independent parameters:
 Viscosity Parameters

• “S” - This parameter denotes the physical-chemical

nature of a substance being the primary influence on
viscosity, i.e. whether the liquid is water, oil, honey,
or a polymer melt etc.
• “T” - This parameter is linked to the temperature of
the substance. Experience shows that viscosity is
heavily influenced by changes of temperature. As an
example: The viscosity of some mineral oils drops by
10% for a temperature increase of only 1°C.
 Viscosity Parameters

• “p” - This parameter “pressure” is not experienced as often

as the previous ones.
• Pressure compresses fluids and thus increases intermolecular
resistance.
• Liquids are compressible under the influence of very high
pressure-- similar to gases but to a lesser extent.
• Increase of pressure tends to increase the viscosity.
• As an example: Raising the pressure for drilling mud from
ambient to 1000 bar increases it’s viscosity by some 30%.
 Viscosity Parameters

• -Parameter “shear rate” is a decisive factor influencing the

viscosity of very many liquids.
• Increasing shear rates may decrease or increase the viscosity.
• “t” Parameter “time” denotes the phenomenon that the
viscosity of some substances, usually dispersions, depends on
the previous shear history, i.e. on the length of time the
substance was subjected to continuous shear or was allowed
to rest before being tested.
 Viscosity Parameters

• “E” - Parameter “electrical field” is related to a

family of suspensions characterized by the
phenomenon that their flow behavior is strongly
influenced by the magnitude of electrical fields
acting upon them.
• These suspensions are called either “electro-viscous
fluids” (EVF) or “electro-rheological fluids” (ERF).
 Viscosity Parameters

• They contain finely dispersed dielectric particles such

as aluminum silicates in electro-conductive liquids
such as water which may be polarized in an electrical
field.
• They may have their viscosity changed instantaneously
and reversibly from a low to a high viscosity level, to
a dough-like material or even to a solid state as a
function of electrical field changes, caused by voltage
changes.
Substances
Fluid Behaviour
Fluid Types
Non Newtonian
Power Law Fluid
Types of Fluids

55
 Newtonian Liquids

• Newton assumed that the graphical equivalent of his

equation [2] for an ideal liquid would be a straight
line starting at the origin of the flow curve and
would climb with a slope of an angle α.
• Any point on this line defines pairs of values for τ
and .
• Dividing one by the other gives a value of η ([8]).
• This value can also be defined as the tangent of the
slope angle α of the flow curve: η = tan α .
 Newtonian Liquids

• Because the flow curve for an ideal liquid is straight,

the ratio of all pairs of τ and -values belonging to
this line are constant.
• This means that η is not affected by changes in shear
rate.
• All liquids for which this statement is true are called
“Newtonian liquids” (both curves 1 in Fig. 6).
• Examples: water, mineral oils, bitumen, molasses.
 Non-Newtonian Liquids

 All other liquids not exhibiting this “ideal” flow

behavior are called “Non-Newtonian Liquids”.
 They outnumber the ideal liquids by far.
 Pseudo-plastic Liquids

 Liquids which show pseudo-plastic flow behavior

under certain conditions of stress and shear rates are
often just called “pseudo-plastic liquids” (both curves
2 in Fig. 6)
 These liquids show drastic viscosity decreases when
the shear rate is increased from low to high levels.
 Pseudo-plastic Liquids

• Technically this can mean that for a given force or

pressure more mass can be made to flow or the
energy can be reduced to sustain a given flow rate.
• Fluids which become thinner as the shear rate
increases are called “pseudo-plastic”.
• Very many substances such as emulsions,
suspensions, or dispersions of technical and
commercial importance belong to this group.
Pseudo-plastic Liquids

61
 Pseudo-plastic Liquids

• Many liquid products that seem homogeneous are in fact

composed of several ingredients: particles of irregular shape
or droplets of one liquid are dispersed in another liquid.
• On the other hand there are polymer solutions with long
entangled and looping molecular chains.
• At rest, all of these materials will maintain an irregular
internal order and correspondingly they are characterized by a
sizable internal resistance against flow, i.e. a high viscosity.
 Pseudo-plastic Liquids

• With increasing shear rates, matchstick-like particles

suspended in the liquid will be turned lengthwise in the
direction of the flow.
• Chain-type molecules in a melt or in a solution can disentangle,
stretch and orient themselves parallel to the driving force.
• Particle or molecular alignments allow particles and molecules
to slip past each other more easily.
 Pseudo-plastic Liquids

• Shear can also induce irregular lumps of aggregated

primary filler particles to break up and this can help a
material with broken-up filler aggregates to flow
faster at a given shear stress.
• For most liquid materials the shear-thinning effect is
reversible -- often with some time lag -- i.e. the liquids
regain their original high viscosity when the shearing
is slowed down or terminated: the chain-type
molecules return to their natural state of non-
orientation.
 Pseudo-plastic Liquids

• At very low shear rates pseudo-plastic liquids behave

similarly to Newtonian liquids having a defined
viscosity η0 independent of shear rate -- often called
the “zero shear viscosity”.
• A new phenomenon takes place when the shear rate
increases to such an extent that the shear induced
molecular or particle orientation by far exceeds the
randomizing effect of the Brownian motion: the
viscosity drops drastically.
 Pseudo-plastic Liquids

 Reaching extremely high shear rates the viscosity

will approach asymptotically a finite constant level:
η1.
 Going to even higher shear rates cannot cause
further shear-thinning: The optimum of perfect
orientation has been reached.
Pseudo-plastic Liquids

67
 Dilatant Liquids

• There is one other type of material characterized by a

shear rate dependent viscosity: “dilatant” substances
-- or liquids which under certain conditions of stress
or shear rate show increasing viscosity whenever
shear rates increase. (Curves 3 in Fig. 6)
• Dilatancy in liquids is rare.
• This flow behavior most likely complicates
production conditions, it is often wise to reformulate
the recipe in order to reduce dilatancy.
 Plasticity

• It describes pseudo-plastic liquids which additionally

feature a yield point. (both curves 4 in Fig. 6)
• They are mostly dispersions which at rest can build up
an intermolecular/interparticle network of binding
forces (polar forces, van der Waals forces, etc.).
• These forces restrict positional change of volume
elements and give the substance a solid character
with an infinitely high viscosity.
 Plasticity

• Forces acting from outside, if smaller than those

forming the network, will deform the shape of this
solid substance elastically.
• Only when the outside forces are strong enough to
overcome the network forces -- surpass the threshold
shear stress called the “yield point” -- does the
network collapse.
• Volume elements can now change position
irreversibly: the solid turns into a flowing liquid.
 Plasticity

 Typical substances showing yield points include oil

well drilling muds, greases, lipstick masses,
toothpastes and natural rubber polymers.
 Plastic liquids have flow curves which intercept the
ordinate not at the origin, but at the yield point level
of τ0.
 Thixotropy

 For pseudo-plastic liquids, thinning under the

influence of increasing shear depends mainly on the
particle/molecular orientation or alignment in the
direction of flow surpassing the randomizing effect
of the Brownian movement of molecules.
 This orientation is again lost just as fast as orientation
came about in the first place.
 Thixotropy

 Plotting a flow curve of a non-Newtonian liquid not

possessing a yield value with a uniformly increasing
shear rate -- the “up-curve” --, one will find that the
“down-curve” plotted with uniformly decreasing
shear rates will just be superimposed on the “up-
curve”: they are just on top of each other or one sees
one curve only.
Thixotropy

74
 Thixotropy

• It is typical for many dispersions that they not only show

this potential for orientation but additionally for a time-
related particle/molecule-interaction.
• This will lead to bonds creating a three-dimensional
network structure which is often called a “gel”.
• In comparison to the forces within particles or molecules,
these bonds -- they are often hydrogen or ionic bonds --
are relatively weak: they rupture easily, when the
dispersion is subjected to shear over an extended period
of time (Fig. 9).
 Thixotropy

• When the network is disrupted the viscosity drops with shear

time until it asymptotically reaches the lowest possible level
for a given constant shear rate.
• This minimum viscosity level describes the “sol”-status of the
dispersion.
• A thixotropic liquid is defined by it’s potential to have it’s gel
structure reformed, whenever the substance is allowed to rest
for an extended period of time.
• The change of a gel to a sol and of a sol to a gel is reproducible
any number of times.
Thixotropy

77
 Thixotropy

• Fig. 10 describes thixotropy in graphical form.

• In the flow curve the “up-curve” is no longer directly
underneath the “down-curve”.
• The hysteresis now encountered between these two
curves surrounds an area “A” that defines the
magnitude of this property called thixotropy.
• This area has the dimension of “energy” related to
the volume of the sample sheared which indicates
that energy is required to break down the thixotropic
structure
 Thixotropy

 For the same shear rate there are now two

different points I and II.
 These two viscosity values are caused by a
shear history at I being much shorter than at II.
 If it took 3minutes to get to point I and 6
minutes to the maximum shear rate, it will be 9
minutes until point II is reached.
 Rheopectic Flow Behavior

• Rheopective liquids are characterized by a viscosity

increase related to the duration of shear.
• When these liquids are allowed to rest they will recover
the original -- i.e. the low -- viscosity level.
• Rheopective liquids can cycle infinitely between the
shear-time related viscosity increase and the rest-time
related decrease of viscosity.
• Rheopexy and thixotropy are opposite flow properties.
• Rheopexy is very rare.
Types of Rheometers
Controlled Stress

82
83
When to Use

84
Plate and Cone

85
Plate and Cone

86
Plate and Cone

87
Plate and Cone

88
Parallel Plate

89
Parallel Plate

90
Parallel Plate

91
 


92
Capillary Rheometer

93
Shear rate calculation for capillary
rheometer

94
Viscosity calculation for capillary
rheometer

95