Introduction To Rheology

Introduction to Rheology
Basics

RheoTec Messtechnik GmbH Phone: ++49 (035205) 5967-0
Schutterwaelder Strasse 23 Fax: ++49 (035205) 5967-30
D-01458 Ottendorf-Okrilla E-mail: info@rheotec.de
Germany Internet: www.rheotec.de

1
RheoTec Messtechnik GmbH, Ottendorf-Okrilla Introduction to rheology V2.1 E.doc

Content

1 Fundamental rheological terms .................................................................................................. 2
1.1 Introduction ..........................................................................................................................................2
1.2 Definitions ............................................................................................................................................4
1.2.1 Shear stress..................................................................................................................................4
1.2.2 Shear rate .....................................................................................................................................4
1.2.3 Dynamic viscosity .........................................................................................................................6
1.2.4 Kinematic viscosity .......................................................................................................................7
1.3 Factors which affect the viscosity ........................................................................................................8
2 Load-dependent flow behaviour ................................................................................................. 9
2.1 Newtonian flow behaviour..................................................................................................................10
2.2 Pseudoplasticity .................................................................................................................................12
2.3 Dilatancy ............................................................................................................................................13
2.4 Plasticity and yield point.....................................................................................................................14
3 Time-dependent flow behaviour ............................................................................................... 16
3.1 Thixotropy ..........................................................................................................................................16
3.2 Rheopexy...........................................................................................................................................18
4 Temperature-dependent flow behaviour................................................................................... 19
5 Flow behaviour of viscoelastic materials .................................................................................. 20
5.1 Viscoelastic liquids.............................................................................................................................20
5.2 Viscoelastic solids..............................................................................................................................21
6 Flow behaviour of elastic materials........................................................................................... 22
6.1 Strain..................................................................................................................................................22
6.2 Shear modulus...................................................................................................................................22
7 Rheometry ................................................................................................................................ 23
7.1 Tests at controlled shear rate (CSR mode) .......................................................................................24
7.1.1 Viscosity-time test .......................................................................................................................25
7.1.2 Viscosity-temperature test ..........................................................................................................26
7.1.3 Flow and viscosity curves...........................................................................................................27
7.2 Tests at controlled shear stress (CSS mode) ....................................................................................30
7.2.1 Viscosity-time test .......................................................................................................................31
7.2.2 Viscosity-temperature test ..........................................................................................................32
7.2.3 Flow and viscosity curves...........................................................................................................33
7.2.4 Creep and recovery test .............................................................................................................36
8 Measuring geometries in a rotation viscometer ........................................................................ 41
8.1 Coaxial cylinder measuring systems..................................................................................................42
8.2 Dual-slit measuring systems according to DIN 54453.......................................................................44
8.3 Cone-plate measuring systems according to ISO 3219 ....................................................................45
8.4 Plate-plate measuring systems..........................................................................................................47

2

1 Fundamental rheological terms

1.1 Introduction

Material scientists have investigated the flow and strain properties of materials since the 17
th

century. The term rheology was first used in physics and chemistry by E.C. BINGHAM and M.
REINER on 29 April 1929 when the American Society of Rheology was founded in Columbus, Ohio.
Rheological parameters are mechanical properties. They include physical properties of liquids and
solids which describe strain and flow behaviour (temporal variation of strain). Strain is observed in
all materials and substances when exerting external forces.

Rheometry describes measuring methods and devices used to determine rheological properties.

If an external force is exerted on a body, its particles will be displaced relative to each other. This
displacement of particles is known as strain. Type and extent of strain are characteristic properties
of a body.

Ideally elastic bodies undergo elastic strain if external anisotropic forces are exerted on them.
The energy needed for this strain is stored and effects spontaneous full recovery of the original
form if the external force ceases to act.

Ideally viscous bodies undergo an irreversible strain if external anisotropic forces (e.g.
gravitational force) are exerted on them. The input energy is transformed. This increasing viscous
strain is known as flowing. There are only few fluids with practical importance which show (almost)
ideally viscous behaviour. Most materials are neither ideally viscous nor ideally plastic. They rather
exhibit different behaviour and are thus called viscoelastic materials.
3

The most simple model to illustrate rheological properties is the parallel plate model. The top
plate, which has a surface area A [m], is moved by a force F [N = kgm/s] at a speed v [m/s]. The
bottom plate remains at rest. The distance between the plates, to which the material adheres, is
described by h [m]. Now, thinnest elements of the liquid will be displaced between the plates. This
laminar flow is of fundamental importance for rheological investigations. Turbulent flows increase
the flow resistance, thus showing false rheological properties.

Fig. 1-1: Parallel plate model

Shear rate & = v / h in s
-1

Shear stress = F / A in Pa

Viscosity = / & in Pas

Strain = dx / h dimensionless

In addition to the expression & , the symbol D is also used for the shear rate.

Shear tests are usually conducted using rotation viscometers. In contrast to the parallel plate
model, the moved surface performs a rotary movement.
h
v
A
F
moved plate
fix plate
4

( )
Pa
m
Newton N
A Area
F Force
stress Shear
2
= = =
dh
dv
rate Shear =
&
1
s
m
s / m
h ce tan Dis
v Velocity
rate Shear
-
= = =
&
1.2 Definitions

1.2.1 Shear stress

Force F acting on area A to effect a movement in the liquid element between the two plates. The
velocity of the movement at a given force is controlled by the internal forces of the material.

100 Pa = 1 mbar = 1 hPa
old unit: dyn / cm
2
= 0.1 Pa

1.2.2 Shear rate

By applying shear stress a laminar shear flow is generated between the two plates. The uppermost
layer moves at the maximum velocity v
max
, while the lowermost layer remains at rest. The shear
rate is defined as:

where dv Velocity differential between adjacent velocity layers
dh Thickness differential of the flow layers

In a laminar flow the velocity differential between adjacent layers of like thickness is constant
(dv = const., dh = const.) The differential can thus be approximated as follows:

In addition to & , the symbol D is also used for the shear rate in the literature.

5

Table 1-1: Typical shear rate ranges
Process

& ranges in s
-1

Example of use

Sedimentation of fine particles in
suspensions
10
-6
... 10
-4
Paints, lacquers,
pharmaceutical solutions
Flowing due to surface characteristics

10
-4
... 10
-1
Paints, printing inks

Dripping under the effect of the
gravitational force
10
-2
... 10
1
Paints, coatings

Extruding

10
0
... 10
2
Polymers

Chewing/ swallowing

10
1
... 10
2
Food

Spreading butter on a slice of bread

10 ... 50 Food

Mixing, agitating

10
1
... 10
3
Substances in process
engineering
Brushing

10
2
... 10
4
Paints, lacquers, pastes

Spraying, spreading

10
3
... 10
6
Paints, lacquers, coatings

Rubbing in

10
4
... 10
5
Creams, lotions

High-speed coating

10
5
... 10
6
Paper coatings

Lubrication of machine parts

10
3
... 10
7
Mineral oils, greases

6

Pas
s
Pa
rate Shear
stress Shear
ity cos vis Dynamic
1
= =
=
-
&
1.2.3 Dynamic viscosity

Viscosity describes the toughness of a material.

The unit Pas (or mPas) is used for the viscosity.

1 Pas = 1000 mPas

old unit: 1 P (Poise) = 100 cP (Centipoise) = 100 mPas (Millipascalsecond)

Substance Dyn. viscosity in mPas
Acetone 0.32
Water 1.0
Ethanol 1.2
Mercury 1.5
Grape juice 2...5
Cream approx. 10
60 % sugar solution 57
Olive oil: approx. 100
Honey approx. 10,000
Plastic melts 10
4
... 10
8

Tar approx. 10
6

Bitumen approx. 10
8

Earth mantle approx. 10
24

Table 1-2: Typical viscosities at 20 C in mPas
7

s
mm
Density
ity cos vis Dynamic
ity cos vis Kinematic
2
=
=
1.2.4 Kinematic viscosity

If ideally viscous materials are tested using a capillary viscometer, such as an UBBELOHDE
viscometer, the kinematic viscosity is determined, not the dynamic viscosity . The kinematic
viscosity is related to the dynamic viscosity through the density of the material.

Old unit: cSt (Centistokes) = mm / s

There used to be several device-specific measuring methods to determine the kinematic viscosity,
e.g. FORD cups, and, accordingly, a large number of units, such as FORD cup seconds, ENGLER
degrees, REDWOOD or SAYBOLD units. These viscosity-dependent values cannot be converted into
absolute viscosities or for non-NEWTONian fluids.

8

1.3 Factors which affect the viscosity

The flow and strain behaviour of a material may be affected by a number of external factors. The
five most important parameters are:

Substance
The viscosity of a material depends on its physical and chemical properties.

Temperature
Temperature has a major effect on the viscosity. For example, several mineral oils lose about 10 %
of their viscosity if the temperature is only increased by 1 K.

Shear rate
The viscosity of most materials depends on the shear rate, i.e. the load.

Time
The viscosity depends on the strain history of a material, in particular on previous loads.

Pressure
If great pressure is exerted on a material, its viscosity may increase as particles are organised in a
more tight structure (resulting in more interaction possibilities).

Other influencing factors are the pH value, magnetic and electric field strength.
9

2 Load-dependent flow behaviour

Flow and viscosity curves
The flow behaviour of a material is characterised by the relation between shear stress and shear
rate & . A & - diagram is often used for graphic representation. Usually, the shear stress is shown
on the ordinate and the abscissa the shear rate, irrespective of whether & or were given for the
measurement. These diagrams are referred to as flow functions or flow curves.

&
[s
-1
]
[Pa]

Fig. 2-1: Flow curve

Plotting the viscosity over the shear rate & or shear stress produces the viscosity function or
viscosity curve.

[mPas]
&
[s
-1
]

Fig. 2-2: Viscosity curve

The measuring result obtained with a viscometer or rheometer is always a flow curve. However,
the viscosity function can be calculated based on the measured values.
10

2.1 Newtonian flow behaviour

If a NEWTONian material is subjected to a shear stress , a shear gradient & of viscous flow is
generated which is proportional to the applied shear stress. The flow function of a NEWTONian
material is a straight line which runs through the origin of the coordinate system at an angle . This
relation between shear stress and shear gradient is described by NEWTONs law of viscosity.

is the material constant of the dynamic shear viscosity. If the viscosity is plotted over the shear
rate (or shear stress) in a viscosity diagram, a straight line which starts at & = 0 s
-1
(or = 0 Pa)
and runs parallel to the abscissa is obtained for an ideally viscous material.

&

&

Fig. 2-3: Flow curves of NEWTONian materials Fig. 2-4: Viscosity curves of NEWTONian materials

The viscosity of a NEWTONian material or ideally viscous material is independent of the shear
rate.

Examples of NEWTONian materials: water, mineral oil, sugar solution, bitumen

. const =
=
&
11

According to NEWTON, a viscous body may be represented by the mechanical model of a damper.

Fig. 2-5: Mechanical model of a NEWTONian body

It can be shown with the help of this model that the material is continuously deformed in the
damper as long as a force acts on the piston. If the force ceases to act, the original shape is not
restored. A viscous strain is characterised in that the energy input to create a flow is fully
transformed into heat in an irreversible process. Materials which show only little interaction
between (usually short) molecules exhibit NEWTONian flow behaviour.

Force F
12

n
K =
&
1 n
K

=
=
&
&
2.2 Pseudoplasticity

Many materials exhibit a strong decrease in viscosity if the shear rate grows. This effect is of great
technical importance. Compared with an ideally viscous material, a pseudoplastic or structurally
viscous material can be pumped through pipelines with a lower energy input at the same flow
velocity.

The proportionality factor / & in the NEWTONian constitutive equation is thus referred to as
a
.
a
is
the apparent viscosity and denotes the viscosity at a certain shear rate &.

Mathematical expression for pseudoplastic materials according to OSTWALD DE WAELE:

where n < 1 for pseudoplastic materials

Transformed into a viscosity function:

&

&

Fig. 2-6: Flow curve of a pseudo- Fig. 2-7: Viscosity curve of a
plastic material pseudoplastic material

Examples: suspensions, dispersions, paints, lacquers, creams, lotions, gels

Materials are referred to as pseudoplastic if a force acting on the body causes the particle size to
change, the particles to be oriented in the direction of flow, or an agglomerate to be dissolved.
/ & = const.
13

n
K =
&
1 n
K
+
=
=
&
&
2.3 Dilatancy

The viscosity of dilatant materials also depends on the shear rate. It increases as the shear rate
grows. Dilatant behaviour can cause trouble in technological processes.

Mathematical expression according to OSTWALD DE WAELE:

where n > 1 for dilatant materials

Transformed into a viscosity function:

&

&

Fig. 2-8 Flow curve of a dilatant material Fig. 2-8 Viscosity curve of a dilatant material

Dilatant behaviour is found rather seldom.

Examples: concentrated corn starch dispersions, wet sand, several ceramic suspensions,
several surfactant solutions

Note: If in case of high shear rates the flow in the measuring gap is no longer laminar, but
becomes turbulent, this may falsely suggest dilatant behaviour.
14

+ =
&
B B
f
+ =
&
C C
f
+ =
p
H
m f
&
2.4 Plasticity and yield point

Plasticity describes structurally viscous liquids which have an additional yield point
o
. A practical
example of such a material is toothpaste. At rest, toothpaste establishes an network of inter-
molecular bonding forces. These forces prevent individual volume elements to be displaced when
the material is at rest. If an external force which is smaller than the internal forces (bonding forces)
acts on the material, the resulting strain is reversible, as with solids. However, if the external forces
exceed the internal bonding forces of the network, the material will start flowing, the solid turns into
a liquid.

Definition of the yield point
o

Maximum shear stress at the shear rate & = 0 s
-1

Thus, if F
external
< F
internal
, the material does not flow
if F
external
> F
internal
, the material starts to flow

Examples: Toothpaste, PVC paste, emulsion paint, lipstick, fats, printing ink, butter

Flow curves and mathematical expression of materials with a yield point
Flow curves of plastic liquids do not start in the origin of the coordinate system, but run on the
ordinate axis until the yield point
o
is reached, then they converge from the ordinate. The flow
curves can be expressed mathematically using a number of equations, depending on the actual
material. For example, the flow curve of chocolate is typically based on the CASSON model.

Mathematical expression according to BINGHAM:

(where f
B
= yield point according to
BINGHAM)

Mathematical expression according to CASSON:

(where f
C
CASSON)

Mathematical expression according to HERSCHEL and BULKLEY:

(where f
H
HERSCHEL and BULKLEY)
where p < 1 for pseudoplastic and p > 1 for dilatant materials
15

o

&

o

&

Fig. 2-10: Flow curve according to BINGHAM Fig. 2-11: Flow curve according to HERSCHEL
and BULKLEY

Physical causes for the occurrence of yield points in dispersions are intermolecular particle-particle
and particle-dispersing agent interactions.

- VAN DER WAALS forces
- Dipole-dipole interactions
- Hydrogen bonds
- Electrostatic interactions

The ST. VENANT model (with static friction) is a mechanical model used to describe plastic
behaviour.

Fig. 2-12: ST. VENANT model for plastic materials
16

3 Time-dependent flow behaviour

3.1 Thixotropy

Thixotropy is a property exhibited by non-NEWTONian liquids, they return to their original viscosity
only with a delay after the shear force ceased to act. In addition, these materials often also have a
yield point.

Tomato ketchup is an example of such a material. When stirred or shaken, ketchup becomes
thinner and only returns to its original viscosity after allowing to rest for a while. Per definition, a
thixotropic material does not only thin depending on the shear rate, but it additionally returns to its
original viscosity after a material-specific period of rest. Theses gel-sol and sol-gel changes in
thixotropic materials are reproducible.

Yoghurt serves as a counter-example: it becomes thinner when stirred, but does not return to its
original thickness. Yoghurt thus does not exhibit thixotropic flow behaviour.

t
Shear at
Sample at rest

&
= const.
( & = 0.1 s
-1
)

Fig. 3-1: Viscosity-time curve of a thixotropic material

Two transitional areas can be easily identified in the viscosity-time curve shown above. A gel is
quickly transformed into a sol at a constant shear force. During the period of rest the material-
specific network structures are re-established, i.e. the sol turns back into a gel.
17

&

&

Fig. 3-2: Flow and viscosity curve of a pseudoplastic and a thixotropic material

The flow curve shows that the measured rising and declining curves are not congruent. The area
between the two curves (hysteresis area) defines the extent of the time-dependent flow behaviour.
The larger the area the more thixotropic is the material.

Examples: paints, foodstuff, cosmetics, pastes
UP
DOWN
DOWN
UP
18

3.2 Rheopexy

Rheopectic materials exhibit greater viscosity while they are subject to shear stress. Structures are
established in the material during the application of mechanical shear forces. The original viscosity
is only restored with a delay after the shear forces ceased to act on the material, by disintegrating
this structure.

t
Shear at
Sample at rest ( & = 0.1 s
-1
)

&
= const.

Fig. 3-3: Viscosity-time curve of a rheopectic material

This process of viscosity increase and decrease can be repeated as often as you wish.
In contrast to thixotropy, true rheopexy is very rare.

&

&

Fig. 3-4: Flow and viscosity curve of a pseudoplastic and a rheopectic material

Examples: several latex dispersions, several casting slips, several surfactant solutions
UP UP
DOWN
DOWN
19

T
B
e A =
4 Temperature-dependent flow behaviour

As mentioned above, the viscosity of a material is a function of temperature. Exact temperature
control and accurate indication of the measuring temperature is thus of major importance in
viscosity measurements.

The viscosity-temperature curve of a material is found at a constant shear rate. In most materials,
the viscosity decreases as the temperature is raised. In ideally viscous materials, this phenomenon
can be described with the help of the ARRHENIUS equation:

where T .......... temperature in Kelvin
A, B .. material constants

T

Fig. 4-1: Viscosity-temperature curve

Viscosity-temperature curves are also often established in order to trace certain reactions. For
example, the curing temperature can be determined for powder lacquers (see Fig. 4-2, curve a), or
the chocolate melting process can be followed (see Fig. 4-2, curve b).

a
b

T

Fig. 4-2: Viscosity-temperature curves of certain reactions
20

5 Flow behaviour of viscoelastic materials

Viscoelastic materials exhibit both viscous and elastic properties. Because of physical differences,
a distinction is made between viscoelastic liquids and viscoelastic solids. The elastic portion of
viscoelastic liquids is described by HOOKES law, which is also known as the spring model, the
viscous portion by NEWTONS damper model.

5.1 Viscoelastic liquids

Viscoelastic materials and purely viscous materials can only be distinguished if they are stirred, for
example. Rheological phenomena cannot be observed while they are at rest. In a viscous liquid, a
rotating agitator causes centrifugal forces, which drive volume elements of the liquid towards the
wall of the cup. This means that a dip is formed around the agitator shaft. In contrast, in elastic
liquids the rotating agitator causes normal forces which are so great that they do not only
compensate the centrifugal forces but exceed them. Consequently, volume elements of the liquid
are thus dawn up the agitator shaft. This phenomenon of masses creeping up a rotating shaft due
to the acting normal forces is called the WEISSENBERG effect.

Fig. 5-1: Flow behaviour of a viscous and a viscoelastic liquid

A force acting on a viscoelastic material (see Fig. 5-2) causes the spring to be deformed
immediately, but the damper reacts with a delay. If the force ceases to act, the spring will return
immediately while the damper remains displaced, so that the material partly remains strained. That
means that there is no full restoration of shape. The amount of the spring return corresponds with
the elastic portion, the amount of the remaining strain (damper) corresponds with the viscous
portion. A viscoelastic liquid can thus be described using a model where damper and spring are
arranged in series. Honouring JAMES C. MAXWELL (18311879), this series connection is also
called the MAXWELL model.
21

Fig. 5-2: Maxwell model

Examples of viscoelastic liquids are gels and silicone rubber compounds

5.2 Viscoelastic solids

If a force is exerted on a viscoelastic solid a delayed strain will take place, because the
displacement of the spring is impeded by the damper. If the force ceases to be exerted, the body
will fully return to its original shape (but again delayed by the damper). That means that there is a
full restoration of shape. It can thus be said that a viscoelastic solid is characterised in that it has
the ability of reversible strain. The model to describe such materials is again a combination of
spring and damper models. In contrast to viscoelastic liquids, however, the two elements are
connected in parallel, as in the KELVIN-VOIGT model.

Fig. 5-3: KELVIN-VOIGT model

An example of a viscoelastic solid is hard rubber.
22

Pa
1
Pa
Strain
stress Shear
G ulus mod Shear = =
=
=
h
s
= tan
6 Flow behaviour of elastic materials

6.1 Strain

A cube with an edge length h shall be investigated here as the volume element in order to illustrate
the strain . The bottom face of the volume element is fixed. A force F acts on its top face, which is
thereby displaced by the amount s.

Fig. 6-1: Unloaded volume element Loaded volume element

Mathematical expression:

Strain is a dimensionless parameter. A deformation angle of 45 corresponds with a strain of 1
or 100%.

The symbol for the shear rate ( & ) can be derived from that for the strain (). The shear rate
describes the strain change d during a period of time dt. Consequently, & is the derivative of strain
with respect to time t. In other words, the shear rate can be considered to be the strain rate.

6.2 Shear modulus

In purely elastic bodies, the ratio of shear stress and resulting strain is constant. This material-
specific parameter described the stiffness of the material and is known as the shear modulus G.

The shear modulus can be in the MPa (10
6
Pa) range in very stiff bodies.
h
h
s
F

23

7 Rheometry

Viscometers or rheometers used to determine the rheological properties are called absolute
viscometers if the measured values are based on the basic physical units of force [N], length [m]
and time [s].

dynamic viscosity = [N/m
2
] [s] = force / length
2
time = [Pa] [s]

Viscometers are measuring devices which are used to determine the viscosity depending on the
rotational speed (= shear rate), time and temperature.

Rheometers are devices which are additionally able to determine the viscous and viscoelastic
product properties depending on the force (shear stress) exerted in both rotation/ creep test and
oscillation test.

Absolute viscometers have the advantage that the results of the measurements are independent of
the device manufacturer or measuring equipment used. The material under investigation is filled
into the two-part measuring system, where a shear force is applied.

The measurements must be conducted under certain boundary conditions in order to obtain correct
results.

The applied shear force must only produce a stratified laminar flow. Vortices and turbulences in
the measuring system consume much energy so that viscosity values up to 40 % above the true
viscosity are obtained.

The material under investigation should be homogeneous. It is not recommended to mix
substances during the measurement. Due to the different specific weights of the components a
phase separation of the mix may occur during the measurement. The changed composition of
the mix in the measuring gap may lead to erroneous viscosity values.

The material must adhere to the walls. The force exerted on the top plate must be fully
transmitted on to the sample. This condition is not fulfilled if the boundary layers of the material
under investigation do not properly adhere to the parts of the measuring system. Problems in
this respect may be encountered with materials such as fats.

The elasticity of the sample must not be too high. The shear forces acting on the sample may
otherwise result in extreme normal forces such that the material creeps out of the measuring
gap. When handling elastic materials, the shear rate must be chosen such that normal stress
does not affect the measuring result.

The shear stress applied according to the laws of viscosity is proportional to the shear rate and
shall only be as great as is necessary to maintain stationary flow conditions, i.e. a flow at
constant velocity. The force that is necessary to accelerate or decelerate the flow is not
considered in this equation.

The NEWTONian relation = / & shows that the viscosity can be determined using either of two
different measuring methods.
24

7.1 Tests at controlled shear rate (CSR mode)

(CSR controlled shear rate)

With this measuring method, the rotational speed n is preset at the rheometer, and the shear rate
is calculated based on the gap h and the rotational speed n (or circumferential speed v of the
shearing area). The flow resistance moment M (or the shear force F) of the braking, tough material
under investigation is measured. This torque M is converted into the rheological parameter of
shear stress using the shear area A of the measuring system.

physical setting rheological setting
rot. speed n [min
-1
]
shear rate [s
-1
]
physical result
torque M [mNm]
rheological result
shear stress [Pa]

=
measurement

&

&

The dynamic viscosity is calculated from the shear stress and shear rate & (or D).
25

7.1.1 Viscosity-time test

A constant shear rate is applied for a certain period of time. The shear stress is measured as a
function of time. The viscosity determined according to the viscosity equation is obtained in relation
to time. This test is used in practice in stability investigations, to study hardening reactions and with
thixotropic materials.

&
[s
-1
]
t [s]

Fig. 7-1: Conditions: shear rate = const., temperature = const.

3
1
2

t [s]
[Pa]

3
1
2

t [s]
[Pas]

1 Material with a viscosity which does not change over time (e.g. calibration oil)
2 Material with a viscosity which decreases over time (e.g. ketchup)
3 Material with a viscosity which increases over time (e.g. hardening lacquer)

Fig. 7-2: Results of the viscosity-time tests

26

7.1.2 Viscosity-temperature test

At a constant shear rate, a temperature ramp is preset and the viscosity is measured in relation to
temperature. In practice, this test is conducted when it comes to investigating temperature-
dependent hardening or melting reactions.

T
[C]
t [s]

Fig. 7-3: Conditions: shear rate = const., variable temperature

2
1

T [C]
[Pa]

2
1

T [C]
[Pas]

1 Material with a viscosity which decreases as the temperature rises (e.g. chocolate)
2 Material with a viscosity which increases as the temperature rises (e.g. hardening lacquer)

Fig. 7-4: Results of the viscosity-temperature tests
27

7.1.3 Flow and viscosity curves

At a constant temperature, a shear rate - time profile is preset. The shear stress is measured for
each shear rate value and the corresponding viscosity is calculated from those measuring results.

t [s]
[s
-1
]
&

Fig. 7-5: Conditions: variable shear rate, temperature = const.

A constant viscosity value is found in materials with ideally viscous behaviour (NEWTONian
materials), such as water. In materials with pseudoplastic behaviour the viscosity decreases as the
shear rate rises (shear thinning). In contrast, in materials with dilatant behaviour the viscosity
increases as the shear rate rises (shear thickening).

2
4
3
1

[Pa]
&
[s
-1
]

4
3
1
2

[Pas]
&
[s
-1
]

1 NEWTONian material
2 Pseudoplastic material
3 Plastic material
4 Dilatant material

Fig. 7-6: Flow and viscosity curves of materials with different rheological behaviour
T=const.
28

Flow and viscosity curves are often plotted such that the viscosity values are shown at both rising
and falling shear rate. Between the two sections of the curve (up ramp, down ramp) there is often a
section where the shear rate is kept constant.

t [s]
&
[s
-1
]

Fig. 7-7: Conditions

In addition to load-dependent flow behaviour (pseudoplasticity, dilatancy), the results of the
measurements then also allow information about time-dependent flow behaviour to be derived. In
practice, the area between the up and down curves is often used as a measure for time-dependent
flow properties, i.e. for the thixotropy of the material. Materials which require a long time after
maximum shear to re-establish their structure show in the diagram a large area between the two
curves (hysteresis area).

&

&


UP
UP
DOWN
DOWN
29

In order to be able to compare measured curves with respect to the hysteresis areas, an identical
measuring profile must be selected for the individual measurements, i.e. the duration of the
individual test phases, the total test duration, the shear rate profile and the temperature must be
identical.

In addition to pseudoplastic behaviour, thixotropic behaviour can also facilitate certain materials to
be processed. Thanks to the reduced viscosity over time, there is less power required for pumping,
mixing, spraying or brushing. An advantage of thixotropic coatings is that they spread more
smoothly after application and bubbles which are possibly created during the application process
can escape more easily.

Pseudoplasticity and thixotropy are two rheological properties which exist fully independent of
each other. They should not be mistaken.
30

7.2 Tests at controlled shear stress (CSS mode)

(CSS controlled shear stress)

In controlled shear stress tests, the torque M is preset at the rheometer, and the shear stress is
calculated from the torque M and the shear area A of the measuring system. The rotational
speed n achieved by the plunger due to the applied torque is measured. This rotational speed n is
converted into the rheological parameter of shear rate using the appropriate measuring system
factor.

physical setting
rheological setting
torque M [mNm]
shear rate [s
-1
]
physical result
rot. speed n [min
-1
]
rheological result
shear stress
[Pa]

=
measurement
&

&

The dynamic viscosity is calculated from the shear stress and shear rate & .
31

7.2.1 Viscosity-time test

A constant shear stress is applied to the material under investigation for a certain period of time.
The achieved shear rate & is measured as a function of time. The viscosity determined according
to the viscosity equation is obtained in relation to time. This test is applied in practice when
studying hardening reactions. It boasts an advantage over the controlled shear rate test: during
hardening the viscosity of the material increases and at a constant shear stress the shear rate falls.
This gradually reduces the foreign movement which interferes with the hardening process.

[Pa]
t [s]

Fig. 7-9: Conditions: shear stress = const., temperature = const.

[s
-1
]
2
3
1

&

t [s]

3
2
1

t [s]
[Pas]

1 Material with a viscosity which does not change over time (e.g. calibration oil)
2 Material with a viscosity which decreases over time (e.g. ketchup)
3 Material with a viscosity which increases over time (e.g. hardening lacquer)

Fig. 7-10: Results of the viscosity-time tests
32

= const.
7.2.2 Viscosity-temperature test

At a constant shear stress, a temperature ramp is preset and the viscosity is measured in relation
to temperature. In practice, this test is conducted when it comes to investigating temperature-
dependent hardening or melting reactions.

T
[C]
t [s]

Fig. 7-11: Conditions: shear stress = const., variable temperature

[s
-1
]
1
2

&

T [C]

2
1

T [C]
[Pas]

1 Material with a viscosity which decreases as the temperature rises (e.g. chocolate)
2 Material with a viscosity which increases as the temperature rises (e.g. jellying starch)

Fig. 7-12: Results of the viscosity-temperature tests

33

T=const.
7.2.3 Flow and viscosity curves

At a constant temperature, a shear stress - time profile is preset. The shear rate is measured for
each shear stress value and the corresponding viscosity is calculated from those measuring
results.

[Pa]
t [s]

Fig. 7-13: Conditions: variable shear stress, temperature = const.

A constant viscosity value is found in materials with ideally viscous behaviour (NEWTONian
materials), such as water. In materials with pseudoplastic behaviour the viscosity decreases as the
shear stress rises. In contrast, in materials with dilatant behaviour the viscosity increases as the
shear stress rises.

2
4
3
1

[Pa]

&
[s
-1
]

4
3
1
2

[Pas]
&
[s
-1
]

1 NEWTONian material
2 Pseudoplastic material
3 Plastic material
4 Dilatant material

Fig. 7-14: Flow and viscosity curves of materials with different rheological behaviour:
34

T=const.
In mathematics, the given parameter is usually plotted on the abscissa, and the resulting
parameter on the ordinate. In contrast, in rheology & is plotted on the abscissa and on the
ordinate, irrespective of whether shear rate or shear stress are given for the measurement.

The shear stress test is the only measuring method where the yield point can be determined
metrologically. Only if the applied shear stress exceeds the network bonding forces in the material
under investigation the material will start to flow, i.e. a measurable shear rate is obtained. In the
flow curve shown in Fig. 7-6, material 3 exhibits a yield point. The flow curve does not pass the
origin of the coordinate system, but shows a certain translation on the Y axis. In plastic materials
an additional shear stress is required in order to obtain a shear rate in the material.

Also in controlled shear stress tests, flow and viscosity curves are often plotted such that the
viscosity values are shown at both rising and falling shear stress. Between the two sections of the
curve (up ramp, down ramp) there is often a section where the shear stress is kept constant.

[Pa]
t [s]

Fig. 7-15: Conditions

In addition to the yield point value (if any), the results of the measurements then also allow
information about load-dependent flow behaviour (pseudoplasticity, dilatancy), and time-dependent
flow behaviour (thixotropy, rheopexy) to be derived.

35

&

&


In order to be able to compare measured curves with respect to the hysteresis areas, which
provides information about the thixotropic or rheopectic behaviour of a material, an identical shear
rate range should be selected for the individual measurements, and the duration of the individual
test phases, the total test duration and the temperature must be identical. As various shear rates
can result from a shear stress setting, a shear stress controlled measurement is less suitable for
comparing hysteresis areas than a shear rate controlled test. The amount of thixotropy and
rheopexy is determined from the flow curves by finding the difference between the areas under the
up and down sections of the curve. Thixotropic materials have positive, rheopectic materials
negative values.
UP
UP
DOWN
DOWN
36

7.2.4 Creep and recovery test

The creep test forms a simple and quick method used to find the viscoelastic properties of the
material under investigation (with exact distinction between the viscous and elastic portions).

The mobile part of the measuring arrangement is loaded with a constant shear stress (
x
) for a
certain period of time (t
0
bis t
2
). The sample reacts on this force with a deformation, i.e. the material
starts to creep. In the second part of the test (t
2
bis t
4
), the material is relieved from the shear
stress so that it can recover.

x

t
0
t
2
t
4

[Pa]
t [s]

Fig. 7-17: Creep and recovery test

7.2.4.1 Ideally elastic materials

A piece of vulcanised rubber will be now be looked at as an example for an ideally elastic material.
The constant shear stress applied leads to a certain twist in the sample, i.e. it shows the strain .
The angle of such strain is characterised by the spring modulus of elasticity of the purely elastic
solid. Shear stress and resulting strain show a linear relation. If the force is doubled, the strain
will also double. HOOKEs spring model serves as a model for ideally elastic materials. The strain is
maintained as long as the deforming force keeps acting. 100 % of the strain energy is stored in the
spring. The sample will be 100 % relieved if the force ceases to be exerted.

37

t
0
t
2
t
4

t [s]

Fig. 7-18: Creep and recovery curve of an ideally elastic material (according to HOOKE)

7.2.4.2 Ideally viscous material

Serving as an example for a material with ideally viscous behaviour, water shows a completely
different behaviour. The constant shear stress applied leads to a strain which increases linearly
over time, i.e. it shows flowing. The input energy is used up for the flowing process. If the sample is
relieved, the strain obtained by this moment of time will be maintained. NEWTONs damper model
is used to describe an ideally viscous material.

t
0
t
2
t
4

t [s]

Fig. 7-19: Creep and recovery curve of an ideally viscous material (according to NEWTON)

38

7.2.4.3 Viscoelastic liquids and solids

The reaction of viscoelastic liquids on applied shear stress shows characteristics of both elastic
and viscous strain. A partial recovery by the elastic portion
E
can be observed, but the portion of
viscous strain
V
remains.

t
0
t
2
t
4
V

t [s]

E
Elastic portion (recovery)
V
Viscous portion

Fig. 7-20: Creep and recovery curve of a viscoelastic liquid

In a viscoelastic solid, a delayed but complete recovery can be observed, i.e.
V
is almost zero.

A material shall now be scrutinised which consists of macromolecules (parallel connection of
spring 2 and damper 2) linked by springs (spring 1) in a highly viscous oil (damper 3). This model
is also known as the BURGER model.

Fig. 7-21: BURGER model
39

The applied shear stress initially leads to a spontaneous jump in strain (dilatation of spring
elements 1 which are situated in the orientation of the strain), the strain rate then drops. During
that time the macromolecules are oriented, the twisted springs tensioned and the macromolecules
stretched up to their mechanically maximal possible size (delayed viscoelastic strain of spring 2
and damper 2). If more force is applied, the strain will again increase linearly if the macromolecules
are irreversible disentangled and caused to flow with the viscous matrix mass (viscous strain of
damper 3).

If the test duration is long enough, all dampers and springs finally show maximum dilatation. During
the relieve phase, two types of recovery take place. Spring 1 returns to its original tension
immediately (elastic recovery), and the parallel connection of spring 2 and damper 2 recovers with
a delay (viscoelastic recovery). Damper 3 remains fully displaced, so that a partial strain is
maintained. If this remaining strain is very small (
V
near 0 %), the material is called a viscoelastic
solid, otherwise it is a viscoelastic liquid.

Creep curve (t
0
to t
2
) Recovery curve (t
2
to t
4
)

1
..... Purely elastic strain (spring 1)
2
..... Viscoelastic strain (parallel connection of spring 2 and damper 2)
3
..... Purely viscous strain (damper 3)
max
Maximum strain:
1
+
2
+
3

.. Gradient angle of the strain curve on achievement of the stationary flow condition (depending on the
viscosity of the strained material)
E
Elastic recovery portion
V
Viscous recovery portion

Fig. 7-22: Creep and recovery curve with analysed parameters
40

( )
t , f =
x

( )
x
f =
x
) t ( J ) t ( =
x
t / ) t ( = ) t ( J
tan
= =
x
3
x
0
In the load phase, unstationary flowing occurs in the linearly viscoelastic range between the
points of time, t
0
and t
1
. The viscosity here depends on the applied shear stress and time.

Stationary viscous flowing is observed between the points of time, t
1
and t
2
. The viscosity does no
longer depend on the elapsed loading time.

The zero viscosity
0
corresponds with the behaviour of damper 3 in the BURGER model (see
Fig. 7-13). It can be determined as

where the shear rate
3
= d / dt = tan

If determined at smallest shear rates, the zero viscosity
0
is a material constant, which contains
information e.g. about the molecular weight of non-networked macromolecules.

In creep tests a constant shear stress is applied and the time-dependent strain is measured.
Mathematically, the relation between stress and strain can be expressed as follows:

This equation introduces the time-dependent compliance factor J(t). Like the zero viscosity, it is a
material-specific quantity. It is a measure of the softness or flexibility of a material. The greater the
compliance the more can the material be strained under the application of a certain shear stress.

in [Pa]

41

8 Measuring geometries in a rotation viscometer

The measuring systems used in a rotation viscometer usually consist of a rotating and a rigid part.
The rotating plunger is turned at either a preset speed or a preset torque.

Two measuring principles are distinguished in coaxial measuring systems:
(1) The SEARLE principle Rotating plunger and resting cup (or bottom plate)
(2) The COUETTE principle Rotating cylinder (or bottom plate) and resting plunger

Measuring systems which employ the COUETTE principle have drawbacks when it comes to
temperature control, because it is more difficult technically to seal a rotating face than a fixed one.
This is why the use of COUETTE systems is often restricted to low speeds.

Fig. 8-1: Cylinder measuring arrangement- Cylinder measuring arrangement
according to the SEARLE principle according to the COUETTE principle
42

R
a

8.1 Coaxial cylinder measuring systems

DIN 53018 describes the coaxial measuring system. Coaxial means that rotating member and
resting member of the measuring system are disposed on one rotation axis. Such cylinder
measuring systems are also known as concentric measuring systems. The terms of the parallel
plate model can be applied to the round cylinder, if its surface area is idealised as many small
plane faces.

R
i
..... Radius of the plunger (inner cylinder)
R
a
.... Radius of the cup (outer cylinder)
r ...... Distance of a layer of the liquid from the rotation axis
v(r) .... Distribution of the circumferential speed in the measuring gap

Fig. 8-2: Cross-section through a Searle cylinder measuring system

The shear stress distribution (r) and the shear rate distribution & (r) are dependent on the radii of
the measuring system. In order to obtain near-linear distributions & (r) and (r) , the measuring gap
must not be too large. DIN 53019 thus specifies a maximum ratio of radii = R
a
/R
i
In other words,
the DIN standard defines the ratio of radii, but not the absolute radii or gap size.

The ratio of radii = R
a
/R
i
is specified in the DIN standard to be 1.1, preferably 1.0847.
R
i
v(r)
43

3
i
R
M 0446 . 0
=
n 291 . 1 =
&
Coaxial cylinder measuring system according to DIN 53019

L .. Length of the plunger (inner cylinder)
L .. Immersed skirt length
L .. Distance between bottom edge of plunger
and cup base
R
i
..... Radius of the plunger (inner cylinder)
R
a
.. Radius of the cup (outer cylinder)
R
s
..... Radius of the plunger skirt
...... Opening angle of the plunger cone

Fig. 8-3: Cylinder measuring system according to DIN 53019 / ISO 3219

DIN 53019 prescribes the following geometrical arrangement for cylinder measuring systems:

Ratio of radii = R
a
/R
i
1.1 (preferably 1.0847)
90 150 (preferably 120 1)
L / R
i
3 (preferably 3.00)
L
1
/ R
i
1 (preferably 1.00)
L
2
/ R
i
1 (preferably 1.00)
R
s
/ R
i
0.3

Calculation of the shear stress from the torque M (measuring systems according to DIN 53019)

M in [mNm], R
i
in [m], in [Pa]

Calculation of the shear rate & from the rotational speed n (measuring systems according to
DIN 53019)

n in [min
-1
], & in [s
-1
]

44

8.2 Dual-slit measuring systems according to DIN 54453

This special coaxial cylinder measuring system with a particularly large shear area was
standardised to be able to investigate materials which have a very small viscosity (such as water-
based lacquers, for example). The plunger has the shape of a tube and the cup has a cylindrical
core section. This dual-slit measuring system thus takes advantage of two shear faces, an inner
and an outer plunger surface.

L
R
R
1
2
R
3
R
4

Fig. 8-4: Dual-slit measuring system according to DIN 54453

According to DIN 54453,
ratio of radii: = R
4
/ R
3
= R
2
/ R
1
1.15
immersed length: L 3 R
3

45

8.3 Cone-plate measuring systems according to ISO 3219

In the cone-plate measuring system, the material to be investigated is disposed between the
bottom plate and the measuring cone. According to DIN 53018, the cone angle must be rather
small in order to allow the simplified expression tan = ( in rad) to be applied. The cone angle
of that measuring system is chosen such that for each point on the cone surface the ratio of
angular speed and distance to the plate is constant. This means that there is a constant shear rate
across the entire radius of the measuring cone. The tip of the cone must just touch the bottom
plate in this geometry. In order to prevent the cone tip from wear and at the same time to provide
the possibility to measure materials which contain fillers, most rheometer manufacturers lift the
cone tip by a certain amount (30180 m). Measuring cones with an angle of 1 are most wide-
spread. However, in order to be more flexible when it comes to measuring materials which contain
fillers, dispersions are often measured using cones with an angle of 4 . This guarantees a laminar
flow to be generated in the measuring gap despite the dispersed particles. As a rule of thumb, a
laminar flow can be assumed as long as the particle diameter is five times smaller than the gap.

In addition to a constant shear rate across the entire measuring gap, the cone-plate measuring
system has further advantages, such as high shear rates, small sample quantities and easy
cleaning.

In order to obtain accurate results of the measurements, it is of major importance to conduct them
very carefully. The measuring cone must be adjusted such that its imaginary tip just touches the
bottom measuring plate. Another point is that of filling the measuring system. It is filled correctly if
the material under investigation is visible approx. 1 mm around the entire circumference of the
cone. The material must not escape from the measuring gap or rest on top of the measuring cone
during the measurement.

Fig. 8-5: Filling the cone-plate measuring system and detail of a cut-off cone tip
correct filling
approx. 1 mm
flattened
cone tip
46

M G
R 2
M 3
K
3
=

=
n k =
=
&

R ..... Outer radius of the cone
...... Opening angle of the cone

Fig. 8-6: Cone-plate measuring system according to ISO 3219 / DIN 53018

The area A in the parallel plate model corresponds with the cone area A = R. The moving force
is expressed as F = M / R

Calculation of the shear stress from the torque M

Torque M in [mNm], R
i
in [m], in [Pa]

G
K
is a constant of the measuring system which depends on the cone radius. The larger the cone
radius the greater is the sensitivity of the measuring system.

Calculation of the shear rate &
The velocity v in the parallel plate model corresponds with the circumferential speed v = R in
the rotating system.

= 2 n / 60 where is the angular speed in [rad/s] und n the rotational speed in [min
-1
]

Using the simplified expression tan = for small cone angles, the shear rate & can be calcul-
ated from the rotational speed n according to the following equation:

where k is a conversion factor which is independent of the cone angle. At a cone angle of 1 k = 6,
at an angle of 2 k = 3 and at an angle of 4 k = 0.75. This means that at a constant rotational
speed the shear rate is the higher the smaller the cone angle. Angles are given in [rad] or [degree],
where 2 rad = 360 i.e. 1 rad = 57.3 and 1 = 0.0175 rad.

R
47

( ) M G
R 2
M 3
R
P
3
=

=
8.4 Plate-plate measuring systems

The plate-plate measuring system consists of two parallel plates. It is characterised by the plate
radius R and the variable distance h between the plates. The material under investigation is
disposed between the two plates. DIN 53018 specifies that the plate distance h shall be much
smaller than the radius of the measuring plate. A gap of between 0.3 mm and 3 mm is
recommended. Plate-plate measuring devices are used if the material under investigation contains
large filler particles. The gap should be determined such that it is at least five times as large as the
largest particles contained in the material. The shear rate is not constant across the entire plate
radius, like in the cone-plate system, but there is a relatively large shear rate range. The shear rate
in the centre of the upper measuring plate is zero. The specified shear rate is always that related to
the outer radius R of the measuring plate, that is the maximum shear gradient.

R ..... Radius of the measuring plate
H ..... Distance (gap) between the upper and lower measuring plate

Fig. 8-7: Plate-plate measuring system

The area A in the parallel plate model corresponds with the rotating area A of the upper measuring
plate, where A = R
2
. The moving force is expressed as F = M / R.

Calculation of the shear stress from the torque M

Torque M in [mNm], R in [m], in [Pa]

G
P
is a constant of the measuring system which depends on the plate radius and the distance h.
The larger the plate radius the greater is the sensitivity of the measuring system.
h
R
48

( )
h
R
h
v
R

= =
&
Calculation of the shear rate &
The plate distance h in the parallel plate model corresponds with the distance h between the upper
and lower measuring plate; the velocity v in the parallel plate model corresponds with the
circumferential speed v = R in the rotating system.

= 2 n / 60 where is the angular speed in [rad/s] und n the rotational speed in [min
-1
]

In contrast to the cone-plate measuring system, the shear rate depends on the radius. It is zero in
the centre of the plate (r = 0), has a maximum at the edge of the plate (r = R) and shows a linear
gradient.

At a constant angular speed or rotational speed n, if the plate distance h is increased the shear
rate in the measuring gap will fall.

Introduction To Rheology

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Introduction To Rheology

Uploaded by

Copyright:

Available Formats

Introduction to Rheology

You might also like