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Introduction To Rheology PDF
Introduction To Rheology PDF
Basics
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1
Thixotropy ..........................................................................................................................................16
Rheopexy ...........................................................................................................................................18
Strain..................................................................................................................................................22
Shear modulus ...................................................................................................................................22
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
1.1
Introduction
Material scientists have investigated the flow and strain properties of materials since the 17th
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.
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.
A
moved plate
h
fix plate
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.
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.
Shear stress =
Force F N (Newton)
=
= Pa
Area A
m2
Shear rate
By applying shear stress a laminar shear flow is generated between the two plates. The uppermost
layer moves at the maximum velocity vmax, while the lowermost layer remains at rest. The shear
rate is defined as:
Shear rate & =
where
dv
dh
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:
Velocity v m / s
=
= s -1
Dis tan ce h
m
In addition to & , the symbol D is also used for the shear rate in the literature.
Process
Example of use
Paints, lacquers,
pharmaceutical solutions
Paints, coatings
Extruding
Polymers
Chewing/ swallowing
Food
10 ... 50
Food
Mixing, agitating
Substances in process
engineering
Brushing
Spraying, spreading
Rubbing in
Creams, lotions
High-speed coating
Paper coatings
1.2.3
Dynamic viscosity
Shear stress Pa
=
= Pas
Shear rate &
s -1
Substance
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
Tar
approx. 106
Bitumen
approx. 108
Earth mantle
approx. 1024
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.
1.3
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.
[Pa]
& [s-1]
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.
RheoTec Messtechnik GmbH, Ottendorf-Okrilla
10
2.1
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.
= const.
&
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
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
11
According to NEWTON, a viscous body may be represented by the mechanical model of a damper.
Force F
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.
12
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.
/ & = const.
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:
= K & n
where n < 1 for pseudoplastic materials
Transformed into a viscosity function:
=
= K & n1
&
&
&
Fig. 2-6: Flow curve of a pseudoplastic material
13
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:
= K & n
where n > 1 for dilatant materials
Transformed into a viscosity function:
= K & n+1
&
&
Fig. 2-8 Flow curve of a dilatant material
&
Fig. 2-8 Viscosity curve of a dilatant material
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
2.4
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 intermolecular 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
Examples: Toothpaste, PVC paste, emulsion paint, lipstick, fats, printing ink, butter
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:
= fB + B &
= fC + C &
= fH + m & p
15
o
&
&
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.
16
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.
Shear at
& = const.
t
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 materialspecific network structures are re-established, i.e. the sol turns back into a gel.
17
UP
UP
DOWN
DOWN
&
&
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
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.
Shear at
Sample at rest ( & = 0.1 s-1)
& = const.
t
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.
UP
UP
DOWN
DOWN
&
&
Fig. 3-4: Flow and viscosity curve of a pseudoplastic and a rheopectic material
Examples: several latex dispersions, several casting slips, several surfactant solutions
19
= A e
B
T
where
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).
T
Fig. 4-2: Viscosity-temperature curves of certain reactions
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20
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.
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
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.
22
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.
F
s
Mathematical expression:
tan =
s
=
h
6.2
Shear modulus
In purely elastic bodies, the ratio of shear stress and resulting strain is constant. This materialspecific parameter described the stiffness of the material and is known as the shear modulus G.
Shear stress Pa
=
= Pa
Strain
1
The shear modulus can be in the MPa (106 Pa) range in very stiff bodies.
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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/m2] [s] = force / length2 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.
RheoTec Messtechnik GmbH, Ottendorf-Okrilla
24
7.1
physical setting
rot. speed n [min-1]
rheological setting
shear rate
& [s-1]
measurement
physical result
torque M [mNm]
rheological result
shear stress [Pa]
&
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.
[Pa]
[Pas]
t [s]
t [s]
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 temperaturedependent hardening or melting reactions.
T
[C]
t [s]
Fig. 7-3: Conditions: shear rate = const., variable temperature
[Pa]
[Pas]
T [C]
T [C]
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
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.
& [s
-1
T=const.
t [s]
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).
3
2
[Pa]
[Pas]
1
2
3
& [s-1]
& [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
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.
& [s-1]
t [s]
Fig. 7-7: Conditions
UP
UP
DOWN
DOWN
&
&
Fig. 7-8: Flow and viscosity curve of a pseudoplastic and a thixotropic material
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
physical setting
torque M [mNm]
rheological setting
shear stress [Pa]
measurement
physical result
rot. speed n [min-1]
rheological result
shear rate
& [s-1]
&
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]
[Pas]
3
1
1
3
t [s]
2
t [s]
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
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 temperaturedependent hardening or melting reactions.
T
[C]
= const.
t [s]
Fig. 7-11: Conditions: shear stress = const., variable temperature
&
-1
[Pas]
[s ]
T [C]
T [C]
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
7.2.3
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=const.
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.
[Pa]
3
2
1
[Pas]
1
2
3
& [s-1]
& [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
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=const.
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
UP
UP
DOWN
DOWN
&
&
Fig. 7-16: Flow and viscosity curve of a pseudoplastic and a thixotropic material
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.
36
7.2.4
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 (t0 bis t2). The sample reacts on this force with a deformation, i.e. the material
starts to creep. In the second part of the test (t2 bis t4), the material is relieved from the shear
stress so that it can recover.
[Pa]
x
t0
t2
t4
t [s]
37
t0
t2
t4
t [s]
Fig. 7-18: Creep and recovery curve of an ideally elastic material (according to HOOKE)
t0
t2
t4
t [s]
Fig. 7-19: Creep and recovery curve of an ideally viscous material (according to NEWTON)
38
V
t0
t2
t4
t [s]
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.
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.
40
In the load phase, unstationary flowing occurs in the linearly viscoelastic range between the
points of time, t0 and t1. The viscosity here depends on the applied shear stress and time.
= f ( x , t )
Stationary viscous flowing is observed between the points of time, t1 and t2. The viscosity does no
longer depend on the elapsed loading time.
= f ( x )
The zero viscosity 0 corresponds with the behaviour of damper 3 in the BURGER model (see
Fig. 7-13). It can be determined as
0 =
x
x
=
3 tan
( t ) = J( t ) x
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.
J( t ) = ( t ) / t x
in [Pa]
41
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:
42
8.1
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.
v(r)
Ri
Ra
Ri .....
Ra ....
r ......
v(r) ....
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 = Ra/Ri In other words,
the DIN standard defines the ratio of radii, but not the absolute radii or gap size.
The ratio of radii = Ra/Ri is specified in the DIN standard to be 1.1, preferably 1.0847.
43
L ..
L ..
L ..
......
Fig. 8-3:
DIN 53019 prescribes the following geometrical arrangement for cylinder measuring systems:
Ratio of radii = Ra/Ri 1.1 (preferably 1.0847)
90 150 (preferably 120 1)
L / Ri 3 (preferably 3.00)
L1 / Ri 1 (preferably 1.00)
L2 / Ri 1 (preferably 1.00)
Rs / Ri 0.3
Calculation of the shear stress from the torque M (measuring systems according to DIN 53019)
0.0446 M
Ri3
Calculation of the shear rate & from the rotational speed n (measuring systems according to
DIN 53019)
& = 1.291 n
44
8.2
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 waterbased 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.
R4
R3
L
R2
R1
= R4 / R3 = R2 / R1 1.15
immersed length:
L 3 R3
45
8.3
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 widespread. 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.
flattened
cone tip
correct filling
approx. 1 mm
Fig. 8-5: Filling the cone-plate measuring system and detail of a cut-off cone tip
46
R .....
......
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
3 M
2 R 3
= GK M
& =
= k n
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.
RheoTec Messtechnik GmbH, Ottendorf-Okrilla
47
8.4
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 .....
H .....
The area A in the parallel plate model corresponds with the rotating area A of the upper measuring
plate, where A = R2. The moving force is expressed as F = M / R.
Calculation of the shear stress from the torque M
(R) =
3 M
2 R3
= GP M
48
& (R) =
v R
=
h
h
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.